TWI771575B - Underlayer film forming composition for imprinting, set, curable composition for imprinting, laminate, method for producing laminate, method for forming pattern, and method for producing semiconductor device - Google Patents

Abstract

The present invention provides an underlayer film-forming composition for imprint comprising a polymer and a solvent, wherein the polymer includes a structural unit and a polymerizable group derived from a monomer having a pKa of 4.0 or less. Furthermore, the present invention relates to a kit, a curable composition for imprint, a laminate, a method for manufacturing the laminate, a method for forming a pattern, and a method for manufacturing a semiconductor device related to the underlayer film forming composition for imprint.

Description

Underlayer film forming composition for imprinting, set, curable composition for imprinting, laminate, method for producing laminate, method for forming pattern, and method for producing semiconductor device

The present invention relates to a composition for forming an underlayer film for imprint, a set, a curable composition for imprint, a laminate, a method for manufacturing the laminate, a method for forming a pattern, and a method for manufacturing a semiconductor device.

The imprint method is a method of forming a desired structure on a resin layer by transferring a pattern of a mold. Among them, after photo-curing the curable composition by irradiating light through a translucent mold or a translucent substrate by a photoimprint method, a fine pattern can be transferred to the photo-cured material by peeling off the mold. In this method, since imprinting can be performed at room temperature, it can be applied to the field of precision processing of ultrafine patterns such as fabrication of semiconductor integrated circuits. Recently, new developments such as a nano-casting method combining these advantages and a reverse imprinting method for producing a three-dimensional multilayer structure have been reported. As a coating method of the curable composition for imprint, ink jet coating is being studied (for example, Patent Document 1). The curable composition for imprinting is usually dropped on the base material as droplets of about 1 to 100 pL. By using inkjet coating, the coating amount can be adjusted according to the thickness of the imprint pattern, and a uniform imprint pattern can be secured. There are the following examples: In order to further enhance the adhesion between the imprint layer formed of the imprint curable composition and the substrate, an underlayer film formed from the imprint underlayer film-forming composition is applied between the two (patent). Documents 2 and 3) or an adhesive layer (Patent Documents 4 and 5). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2005-533393 [Patent Document 2] Japanese Patent Laid-Open No. 2013-093552 [Patent Document 3] Japanese Patent Laid-Open No. 2014-093385 [Patent Document 4] Japanese Patent Laid-Open No. 2016-146468 [Patent Document 5] Japanese Patent Laid-Open No. 2017-206695

In the photoimprint method, as described above, a curable composition for imprint is coated on the surface of a substrate, and the surface is irradiated with light in a state in contact with a mold to harden the curable composition for imprint. The finished embossing layer. Then, the process of peeling off the mold is included. In the process of peeling off the mold, the imprint layer (hardened material) may peel off from the substrate and adhere to the mold. One of the reasons for this is considered to be that the adhesive force between the substrate and the imprint layer is not as high as the adhesive force between the mold and the imprint layer. In order to solve such a problem, for example, the techniques described in the above-mentioned Patent Documents 2 to 5 have been proposed, whereby a certain degree of solution has been achieved. However, with the expansion of the use of the imprint method and the active development of products using the imprint method, it is important to secure the adhesiveness for various substrates in addition to securing the adhesiveness between the substrate and the imprint layer. Accordingly, an object of the present invention is to provide an underlayer film-forming composition for imprint that can ensure sufficient adhesion to various substrates, a set using the underlayer film-forming composition for imprint, and a curable composition for imprinting A product, a laminate, a method for manufacturing the laminate, a method for forming a pattern, and a method for manufacturing a semiconductor device.

In view of the above-mentioned problems, the present inventors have studied a technique for forming a composition using an underlayer film for imprint in an imprint method. Furthermore, it was found that the above-mentioned problems can be solved by using a polymer contained in the underlayer film-forming composition for imprinting using a polymerizable group and a partial structure having an acidity with a low pKa. Specifically, the above-mentioned problems are solved by the mechanism of the following <1> and the mechanisms of <2> to <23> which are preferred embodiments thereof.

<1> An underlayer film-forming composition for imprint comprising a polymer and a solvent, wherein the polymer includes a structural unit and a polymerizable group derived from a monomer having a pKa of 4.0 or less. <2> The underlayer film-forming composition for imprinting according to <1>, wherein the polymer is an acrylic resin. <3> The underlayer film-forming composition for imprinting according to <1> or <2>, wherein the polymer has a weight average molecular weight of 2,000 or more. <4> The underlayer film-forming composition for imprinting according to any one of <1> to <3>, wherein the polymerizable group which the polymer has is a (meth)acryloyl group. <5> The underlayer film-forming composition for imprinting according to any one of <1> to <4>, wherein the structural unit derived from a monomer having a pKa of 4.0 or less in the polymer is derived from a pKa It is a constituent unit of a monomer of 3.0 or less. <6> The underlayer film-forming composition for imprinting according to any one of <1> to <5>, wherein the constituent unit derived from a monomer having a pKa of 4.0 or less has a composition selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfur group, and a At least one of the group of substituted carboxylic acid group, dithiocarboxylic acid group, sulfonic acid group, phosphoric acid monoester group, phosphoric acid diester group and phosphoric acid group. <7> The underlayer film-forming composition for imprinting according to any one of <1> to <6>, wherein 99.0 mass % or more of the underlayer film-forming composition for imprinting is a solvent. <8> The underlayer film-forming composition for imprinting according to any one of <1> to <7>, wherein the polymer has a polymerizable group-containing structural unit. <9> A kit comprising the underlayer film-forming composition for imprinting and the curable composition for imprinting according to any one of <1> to <8>. <10> A curable composition for imprint, which is used in the set described in <9>. <11> A laminate comprising a substrate, an underlayer film formed from the underlayer film-forming composition for imprinting described in any one of <1> to <8> on a surface of the substrate, and an underlayer film formed of the underlayer film-forming composition for imprinting on the surface of the substrate. An embossing layer formed of a curable composition for embossing on the surface of the film. <12> The laminate according to <11>, wherein As the above-mentioned substrate, a substrate having an organic layer as the outermost layer was used. <13> The laminate according to <11> or <12>, wherein As the above-mentioned substrate, a layer having an alkalinity was used as the outermost substrate. <14> A method for producing a laminate, comprising: applying the underlayer film-forming composition for imprinting according to any one of <1> to <8> to the surface of a substrate to form an underlayer film for imprinting ; and a process for applying a curable composition for imprinting on the surface of the above-mentioned lower layer film. <15> The method for producing a laminate according to <14>, wherein As the above-mentioned substrate, a substrate having an organic layer as the outermost layer was used. <16> The method for producing a laminate according to <14> or <15>, wherein As the above-mentioned substrate, a layer having an alkalinity was used as the outermost substrate. <17> A pattern forming method, comprising: a process of forming an underlayer film on a surface of a substrate using the underlayer film forming composition for imprinting described in any one of <1> to <8>; applying on the above-mentioned underlayer film Process for forming a composition for imprinting an underlayer film to form a curable composition layer for imprinting; a process for bringing a casting mold into contact with the above-mentioned curable composition layer for imprinting; A process of exposing the hardening composition layer; and a process of peeling the above-mentioned casting mold from the above-mentioned exposed curable composition layer for imprinting. <18> The pattern forming method according to <17>, wherein As the above-mentioned substrate, a substrate having an organic layer as the outermost layer was used. <19> The pattern forming method according to <17> or <18>, wherein As the above-mentioned substrate, a layer having an alkalinity was used as the outermost substrate. <20> The pattern forming method according to any one of <17> to <19>, wherein the underlayer film-forming composition for imprinting is applied to the substrate surface by a spin coating method. <21> The pattern forming method according to any one of <17> to <20>, wherein the curable composition for imprinting is applied to the underlayer film by an ink jet method. <22> A manufacturing method of a semiconductor device including the pattern forming method according to any one of <17> to <21>. [Inventive effect]

The composition for forming an underlayer film for imprint of the present invention can ensure sufficient adhesiveness with respect to various substrates. Furthermore, a set using the underlayer film forming composition for imprint, a curable composition for imprint, a laminate, a method for manufacturing the laminate, a method for forming a pattern, and a method for manufacturing a semiconductor device can be provided.

Hereinafter, the content of the present invention will be described in detail. In addition, in this specification, "-" is used in the meaning including the numerical value described before and after it as a lower limit and an upper limit. In this specification, "(meth)acrylate" means acrylate and methacrylate. In the present specification, "imprinting" refers to pattern transfer preferably having a size of 1 nm to 10 mm, and more preferably refers to pattern transfer (nanoimprinting) of a size of about 10 nm to 100 μm. In the notation of groups (atomic groups) in this specification, those not substituted and unsubstituted include those without a substituent and those with a substituent. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups), but also substituted alkyl groups (substituted alkyl groups). In this specification, "light" includes not only light or electromagnetic waves of wavelengths in the regions of ultraviolet, near-ultraviolet, far-ultraviolet, visible, and infrared, but also radiation. Radiation includes, for example, microwaves, electron beams, extreme ultraviolet (EUV), and X-rays. In addition, laser light such as a 248 nm excimer laser, a 193 nm excimer laser, and a 172 nm excimer laser can also be used. The light may be monochromatic light (single wavelength light) passed through the filter, or light having a plurality of different wavelengths (composite light). The weight average molecular weight (Mw) in the present invention refers to what is measured by gel permeation chromatography (GPC) when there is no particular description. In the present invention, when there is no particular description, the temperature is set to 23°C. The boiling point in the present invention refers to the boiling point in 1 atmospheric pressure (1 atm=1013.25 hPa).

The composition for forming an underlayer film for imprint of the present invention is characterized in that it contains a polymer and a solvent, and the polymer contains a structural unit and a polymerizable group of a monomer having an atomic pKa of 4.0 or less (in this specification, the polymer is called specific polymers). Thereby, favorable adhesiveness of an imprint layer and a board|substrate can be implement|achieved. In particular, by its preferred embodiment, it is possible to realize a low-defect imprinting process regardless of the substrate type.

<Specific polymer> The specific polymer used in this invention contains the structural unit of the monomer whose atomic pKa is 4.0 or less. The pKa of the monomer is preferably 3.0 or less, more preferably 2.5 or less, and even more preferably 2.0 or less. As a lower limit, it is -3.0 or more actually, and it is 1.0 or more.

In the present specification, pKa represents pKa in an aqueous solution, and is a value calculated by the method described in the examples described later.

The constituent unit of the monomer having an atomic pKa of 4.0 or less is selected from the group consisting of a hydroxyl group (alcoholic hydroxyl group, phenolic hydroxyl group), a carboxyl group, an amide group, an imide group, a urea group, a urethane group, a cyano group, ether group (preferably polyalkyleneoxy group), cyclic ether group, lactone group, sulfonyl group, sulfonic acid group, sulfonamido group, sulfonimide group, phosphoric acid group, phosphate ester group and butyronitrile group At least one of the group (hereinafter, sometimes abbreviated as "acid group") is preferable. Wherein, it is preferred to have at least one selected from the group consisting of hydroxyl group, carboxyl group, thiocarboxylic acid group, dithiocarboxylic acid group, sulfonic acid group, phosphoric acid monoester group, phosphoric acid diester group and phosphoric acid group, At least one selected from the group consisting of a sulfonic acid group, a phosphoric acid monoester group, a phosphoric acid diester group, and a phosphoric acid group is further preferred.

Among the monomers with a pKa of 4.0 or less, the molecular weight is preferably 50 or more, more preferably 100 or more, still more preferably 150 or more, and even more preferably 200 or more. In addition, the molecular weight is preferably 1,000 or less, more preferably 800 or less, further more preferably less than 600, and still more preferably 600 or less. By setting it as such a range, the effect of improvement of film-forming property and improvement of adhesiveness can be exhibited more effectively.

Examples of the polymerizable group of a monomer having a pKa of 4.0 or less include a (meth)acryloyl group, an epoxy group, an oxetanyl group, a methylol group, a methylol ether group, and a vinyl ether. Base et al. The (meth)acryloyl group is particularly preferred from the viewpoint of ease of polymerization. In this specification, the polymerizable group specified and exemplified here is referred to as the polymerizable group Ps.

The monomer having a pKa of 4.0 or less preferably has a structure represented by an acid group-linking group-polymerizable group. The linking group here is exemplified by the linking group L described later.

In the specific polymer, among all the structural units, the ratio of the structural units derived from monomers with pKa 4.0 or less is based on the molar ratio when each structural unit is used as a monomer, preferably 0.5 mass % or more, and 1 mass % The above is more preferable, and 3 mass % or more is further preferable. Moreover, as an upper limit, 50 mass % or less is preferable, 30 mass % or less is more preferable, and 15 mass % or less is further more preferable. A specific polymer may contain only 1 type of structural unit derived from the monomer with pKa 4.0 or less, and may contain 2 or more types. When two or more types are contained, it is preferable that the total amount is in the above-mentioned range.

A specific polymer has a polymerizable group. The polymerizable group may be bonded to the side chain of the specific polymer or may be bonded to the terminal. In the present invention, the specific polymer preferably has a structural unit containing a polymerizable group. In addition, regarding the specific polymer, the structural unit derived from the monomer with pKa 4.0 or less may have a polymerizable group, and may include a polymerizable group other than the structural unit derived from the monomer with pKa 4.0 or less. It is preferable that the structural unit includes a structural unit having a polymerizable group, other than a structural unit derived from a monomer having a pKa of 4.0 or less. Specific examples of the polymerizable group include the polymerizable group Ps, and a (meth)acryloyl group is particularly preferred. The polymerizable group is preferably introduced into the polymer in a form incorporated into a structural unit. The above-mentioned specific polymer has a polymerizable group, so that the underlayer film for imprint forms a cross-linked structure, and can prevent cohesion failure of the underlayer film at the time of peeling, and can ensure more effective adhesiveness. In the specific polymer, among all the structural units, the ratio of the structural unit having a polymerizable group is based on the molar ratio when each structural unit is used as a monomer, preferably 50% by mass or more, more preferably 70% by mass or more, 85 mass % or more is more preferable. Moreover, as an upper limit, 99.5 mass % or less is preferable, 99 mass % or less is more preferable, and 97 mass % or less is still more preferable. A specific polymer may contain only 1 type of structural unit which has a polymerizable group, and may contain 2 or more types. When two or more types are contained, it is preferable that the total amount is in the above-mentioned range.

In a specific polymer, among all the structural units, the total ratio of the structural unit having an acid group and the structural unit having a polymerizable group is 90% by mass or more based on the molar ratio when each structural unit is used as a monomer. Preferably, 95 mass % or more is more preferable, and 97 mass % or more is further preferable. The upper limit may be 100% by mass.

The specific polymer is preferably at least one selected from the group consisting of acrylic resin, novolac resin, epoxy resin, polyurethane resin, phenolic resin, polyester resin and melamine resin, acrylic resin, polyester resin and novolac resin At least one of the group of resins is more preferred, and acrylic resins are further preferred.

Acrylic resin generally refers to polymers of acrylic acid, acrylate, and methacrylate, or to monomers that have these as the main component and can be copolymerized with these, such as styrene, vinyl methyl, vinyl acetate, and acrylonitrile. Copolymerized resin. The acrylic resin can be synthesized by addition-polymerizing an acrylic monomer. Addition polymerization is caused by free radicals, cations, and anions, and is called radical polymerization, cationic polymerization, and anionic polymerization, respectively. The most widely used in industry is free radical polymerization. Examples of acrylic monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, and n-butyl (meth)acrylate. , Isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylate ) lauryl acrylate.

The phenolic resin is produced by the reaction of phenol as a trifunctional monomer (substituted phenol may be bifunctional or monofunctional) and formaldehyde as a bifunctional monomer under an acid or alkaline catalyst. What is obtained by an acid catalyst is called a novolac, and what is obtained by an alkaline catalyst is called a resol. Resol resins are self-hardening by heating. Novolacs harden if heated with a hardener such as hexamethylenetetramine (HMTA). Examples of the raw material include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, and 2,6-xylenol. Phenol, 3,4-xylenol, 3,5-xylenol, resorcinol, p-tert-butylphenol, p-nonylphenol, bisphenol, etc. Melamine resin is a thermosetting synthetic resin obtained by the addition condensation of melamine (2,4,6-triamino-1,3,5-triamine) and formaldehyde. Since an amino group (-NH2) is used as a reactive group together with a urea resin etc., it can be counted as one of the amino resin. It has excellent transparency, hardness, colorability, heat resistance, arc resistance, etc., so it has a wide range of applications such as molding materials, decorative boards, and coatings. Melamine uses amine group as a reactive group and reacts with formaldehyde to become methylol melamine. Methylol melamine from monomethylol melamine to hexamethylol melamine, all the substituents can be easily obtained as a mixture.

Epoxy resin is a general term for compounds having two or more epoxy groups in one molecule, and generally, it is not hardened even if it can be heated by itself, and a hardener or a catalyst is required to obtain a hardened product. It becomes an insoluble and infusible thermosetting resin by adding a hardener to perform an addition reaction, so that no volatile matter is generated and the processability is good. As the curing agent, various first amines, second amines, acid anhydrides, and phenolic resins can be used. Manufacture of an epoxy resin is performed by two methods based on the reaction of the compound which has active hydrogen and epichlorohydrin, and the oxidation of the compound which has a double bond. Examples of compounds having active hydrogen include 2,2-bis(4-hydroxyphenyl)propane (alias bisphenol A), 4,4'-dihydroxydiphenylmethane (alias bisphenol F), 2,2, 2-bis(3,5-dibromo-4-hydroxyphenyl)propane (alias tetrabromobisphenol A), o-cresol, hexahydrophthalic acid, m-aminophenol, p-aminophenol. As other epoxy resin raw materials, novolak-type phenolic resin, dimer acid, polybutadiene, soybean oil, alicyclic compound, tetrahydrophthalic acid, p-hydroxybenzoic acid, m-xylylenediamine, Hydantoin compounds, cyanuric acid, etc.

The polyester resin is obtained by the polycondensation reaction of dibasic acid and dihydric alcohol, and the main chain has an ester bond (-COO-). As a dibasic acid, terephthalic acid, naphthalene dicarboxylic acid, cyclohexane dicarboxylic acid, adipic acid, maleic anhydride, fumaric acid, itonic acid, etc. are mentioned. As the polybasic acid polyol, propylene glycol, ethylene glycol, and diethylene glycol are often used. Among them, other dihydric alcohols are appropriately distinguished and used according to the properties of the resin. As polyesters generally used as plastic materials, in addition to PET (polyethylene terephthalate), there is polybutylene terephthalate which replaces the ethylene glycol component of PET with tetramethylene glycol. Esters (PBT) or polycyclohexanedimethyl terephthalate (PCT) substituted with cyclohexanedimethanol, and also known as polycyclohexanedicarboxylic acid substituted with 2,6-naphthalenedicarboxylic acid 2,6-ethylene naphthalate (PEN), etc.

Polyurethane (PU) is a group of polymers having a urethane bond (urethane bond) obtained by the reaction of polyisocyanate and polyol. When any compound to be reacted is also bifunctional, the current thermoplastic PU can be obtained, and at least one of the compounds is trifunctional or more or a PU that forms a network structure when a side chain reaction occurs.

Regarding the above resins, "Plastic Dictionary" (Asakura Publishing Co., Ltd.) edited by Miyasaka Keisho et al. can also be referred to.

R¹ 為氫原子或甲基，甲基為較佳。 X^R 為氧原子或NH，氧原子為較佳。 n為1～3的整數，1或2為較佳，1為更佳。 m為1～5的整數，1或2為較佳，1為更佳。 R為成為pKa4.0以下之部分結構（酸基）為較佳。式（1）～式（6）中的R為2個以上時，複數個R可相互鍵結而形成環。酸基的較佳者與上述pKa4.0以下的單體所具有之酸基相同。 在式（1）～（6）中，主鏈或苯環在發揮本發明的效果之範圍內可具有後述之取代基T。又，R或取代基T亦可與主鏈鍵結而形成環。The specific polymer preferably has a main chain represented by a structural unit represented by any one of the following formulae (1) to (6). [Chemical formula 1]

R ¹ is a hydrogen atom or a methyl group, preferably a methyl group. X ^R is an oxygen atom or NH, preferably an oxygen atom. n is an integer of 1 to 3, preferably 1 or 2, more preferably 1. m is an integer of 1 to 5, preferably 1 or 2, more preferably 1. R is preferably a partial structure (acid group) having a pKa of 4.0 or less. When there are two or more Rs in the formulae (1) to (6), a plurality of Rs may be bonded to each other to form a ring. The preferred acid group is the same as the acid group possessed by the above-mentioned monomer having a pKa of 4.0 or less. In the formulae (1) to (6), the main chain or the benzene ring may have a substituent T, which will be described later, within a range in which the effects of the present invention are exhibited. In addition, R or the substituent T may be bonded to the main chain to form a ring.

R¹ 為氫原子或甲基，甲基為較佳。 X^R 為氧原子或NH，氧原子為較佳。 n為1～3的整數，1或2為較佳，1為更佳。 m為1～5的整數，1或2為較佳，1為更佳。 R² 為分別獨立地包含聚合性基之取代基。R² 中所含之聚合性基為上述Ps為較佳。式（1-1）～式（1-6）中的R² 為2個以上時，複數個R² 可相互鍵結而形成環。又，在發揮本發明的效果之範圍內，在式（1-1）～式（1-6）的主鏈及苯環可由取代基T取代。 作為R² ，下述式（T2）為較佳。R² 的式量為80以上1000以下為較佳，100以上800以下為更佳，150以上600以下為進一步較佳。 -（L⁴ ）_n6 -（P）_n7 ……（T2） L⁴ 為下述連接基L，其中，伸烷基、伸芳基、（低聚）伸烷氧基、羰基、氧原子、該些組合之連接基為較佳。n6為0或1，1為較佳。P為包含聚合性基之基團，Ps或Ps與由連結基團L構成之基團為較佳。n7為1～6的整數，1或2為較佳。再者，n7為2以上時，L⁴ 成為3價以上的連接基即可，例如，可舉出包含3價以上的烷烴結構的基（碳數1～12為較佳，1～6為更佳，1～3為進一步較佳）、烯烴結構的基（碳數2～12為較佳，2～6為更佳，2～3為進一步較佳）或芳基結構的基（碳數6～22為較佳，6～18為更佳，6～10為進一步較佳）之連接基。再者，（低聚）伸烷氧基可為單伸烷氧基亦可為低聚伸烷氧基。L⁴ 的連接原子數為1～24為較佳，1～12為更佳，1～6為進一步較佳。 特定聚合物包含由式（1）表示之構成單元，為共聚物時，包含由式（1-1）表示之構成單元為較佳。關於式（2）～式（6），亦同樣地分別包含由式（1-2）～式（1-6）表示之構成單元為較佳。The above-mentioned specific polymer-based copolymer is also preferable. It is preferable that the copolymerization component contains at least one of the structural units represented by any one of the following formulae (1-1) to (1-6) together with the structural units of the above formulae (1) to (6). [Chemical formula 2]

R ¹ is a hydrogen atom or a methyl group, preferably a methyl group. X ^R is an oxygen atom or NH, preferably an oxygen atom. n is an integer of 1 to 3, preferably 1 or 2, more preferably 1. m is an integer of 1 to 5, preferably 1 or 2, more preferably 1. R ² is a substituent each independently containing a polymerizable group. The polymerizable group contained in R ² is preferably the above-mentioned Ps. When R ^{2 in formula (1-1) to formula (1-6) is two or more, a plurality of R 2 may} be bonded to each other to form a ring. Moreover, the main chain and benzene ring of Formula (1-1) - Formula (1-6) may be substituted by the substituent T within the range which exhibits the effect of this invention. As R ² , the following formula (T2) is preferable. The formula amount of R ² is preferably 80 or more and 1000 or less, more preferably 100 or more and 800 or less, and even more preferably 150 or more and 600 or less. -(L ⁴ ) _n6 -(P) _n7 ......(T2) L ⁴ is the following linking group L, wherein an alkylene group, an arylidene group, an (oligo)alkaneoxy group, a carbonyl group, an oxygen atom, the These combinations of linkers are preferred. n6 is 0 or 1, with 1 being preferred. P is a group containing a polymerizable group, and Ps or Ps and a group composed of a linking group L are preferable. n7 is an integer of 1 to 6, preferably 1 or 2. Furthermore, when n7 is 2 or more, L ⁴ may be a linking group of trivalent or more, for example, a group containing a trivalent or more alkane structure (preferably carbon number 1-12, more preferably 1-6). preferably, 1-3 are further preferred), alkene structure group (carbon number 2-12 is preferred, 2-6 is more preferred, 2-3 is further preferred) or aryl structure group (carbon number 6 ~22 is better, 6~18 is better, 6~10 is further better) the linking group. In addition, the (oligo)alkaneoxy group may be a monoalkeneoxy group or an oligomeric alkaneoxy group. The number of linking atoms of L ⁴ is preferably 1-24, more preferably 1-12, and still more preferably 1-6. The specific polymer contains the structural unit represented by the formula (1), and when it is a copolymer, it is preferable to contain the structural unit represented by the formula (1-1). It is also preferable that the structural unit represented by the formula (1-2) to the formula (1-6) is included in the formula (2) to the formula (6), respectively.

It is also preferable that the specific polymer further contains a structural unit (sometimes referred to as "other structural unit") without an acid group and a polymerizable group. It is preferable that another structural unit has the skeleton of the said formula (1-1)-(1-6). Among them, the substituent R ² is the substituent R ³ that does not have an acid group and a polymerizable group. Other main chains or benzene rings may be substituted with the substituent T within the scope of exerting the effects of the present invention. In addition, R ³ or the substituent T may be bonded to the main chain to form a ring. R ³ is preferably the following formula (T3). The formula amount of R ³ is preferably 80 or more and 1000 or less, more preferably 100 or more and 800 or less, and even more preferably 150 or more and 600 or less. -(L ⁵ ) _n8 -(T1) _n9 ......(T3) L ⁵ is a linking group L described later, wherein an alkylene group, an aryl group, an (oligo)alkaneoxy group, a carbonyl group, an oxygen atom, these Combinations of linkers are preferred. The number of linking atoms of L ⁵ is preferably 1-24, more preferably 1-12, and still more preferably 1-6. n8 is 0 or 1. T ¹ is a substituent T described later, and among them, an alkyl group which may be substituted by a halogen atom, an aryl group which may be substituted by a halogen atom, and an arylalkyl group which may be substituted by a halogen atom are preferable. n9 is an integer of 1 to 6, preferably 1 or 2. When n9 is 2 or more, L ⁵ may be a linking group of trivalent or more, for example, a group containing a trivalent or more alkane structure (preferably carbon number 1-12, more preferably 1-6, 1 ~3 is further preferred), alkene structure group (carbon number 2-12 is preferred, 2-6 is more preferred, 2-3 is further preferred) or aryl structure group (carbon number 6-22 is Preferably, 6 to 18 are more preferably, 6 to 10 are further preferred) linking groups.

Examples of the substituent T include alkyl (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 6) and arylalkyl (preferably having 7 to 21 carbon atoms, 7-15 is more preferable, 7-11 is further preferable), alkenyl (carbon number 2-24 is preferable, 2-12 is more preferable, 2-6 is further preferable), alkynyl (carbon number 2 ~12 is better, 2-6 is better, 2-3 is further better), hydroxyl, amine group (carbon number 0-24 is better, 0-12 is better, 0-6 is further better ), thiol group, carboxyl group, aryl group (preferably with carbon number 6-22, more preferably 6-18, and further preferably 6-10), heteroaryl (preferably with carbon number 1-22, 1 ~16 is more preferred, 1-12 is further preferred), alkoxy (carbon number 1-12 is preferred, 1-6 is more preferred, 1-3 is further preferred), aryloxy (carbon number is more preferred) 6-22 is better, 6-18 is better, 6-10 is further better), acyl group (carbon number 2-12 is better, 2-6 is better, 2-3 is further better) , aryloxy (the number of carbons 2-12 is preferred, 2-6 is more preferred, 2-3 is further preferred), aryloxy (the number of carbons 7-23 is preferred, 7-19 is more preferred, 7-11 are further preferred), aryloxy (the number of carbons 7-23 is preferred, 7-19 is more preferred, 7-11 is further preferred), carbamoyl (the number of carbons 1-12 is further preferred) Preferably, 1-6 is more preferred, 1-3 is further preferred), sulfamoyl (carbon number 0-12 is preferred, 0-6 is more preferred, 0-3 is further preferred), sulfonic acid Acid group, alkylsulfonyl group (preferably carbon number 1-12, more preferably 1-6, further preferred 1-3), arylsulfonyl group (preferably carbon number 6-22, 6 ~18 is more preferred, 6-10 is further preferred), heterocyclic group (carbon number 1-12 is preferred, 1-8 is more preferred, 2-5 is further preferred, including 5-membered ring or 6-membered ring ring is preferred), (meth)acryloyl, (meth)acryloyloxy, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), oxo group (=O), Amine group (=NR ^N ), alkylene group (=C(R ^N ) ₂ ) and the like. R ^N is a hydrogen atom, an alkyl group (preferably carbon number 1-12, more preferably 1-6, further preferably 1-3), alkenyl (preferably carbon number 2-12, 2-6 is More preferably, 2-3 is further preferred), alkynyl (carbon number 2-12 is preferred, 2-6 is more preferred, 2-3 is further preferred), aryl (carbon number 6-22 is preferred) preferably, 6-18 is more preferred, 6-10 is further preferred), heteroaryl (carbon number 1-22 is preferred, 1-16 is more preferred, 1-12 is further preferred), wherein hydrogen Atom, methyl, ethyl or propyl are preferred. R ^N may have each group defined by the substituent T within the range in which the effects of the present invention are exhibited. The alkyl moiety, alkenyl moiety and alkynyl moiety contained in each substituent may be chain, cyclic, straight chain or branched. When the said substituent T is a group which can obtain a substituent, it may have a substituent T. For example, the alkyl group may be a halogenated alkyl group, or may be a (meth)acryloyloxyalkyl group, an aminoalkyl group, or a carboxyalkyl group.

Examples of the linking group L include alkylene (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 6), and alkenylene (preferably having 2 to 12 carbon atoms). , 2-6 is better, 2-3 is further better), alkynylene (carbon number 2-12 is better, 2-6 is better, 2-3 is further better), (oligomerization) Alkyleneoxy (the carbon number of the alkylene group in one structural unit is preferably 1-12, more preferably 1-6, further preferably 1-3; the number of repetitions is preferably 1-50, 1-40 is more preferred, 1-30 is further preferred), aryl group (carbon number 6-22 is preferred, 6-18 is more preferred, 6-10 is further preferred), oxygen atom, sulfur atom , sulfonyl, carbonyl, thiocarbonyl, -NR ^N - and the linking group of combinations of these. The alkylene group may have the following substituents T. For example, an alkylene group may have a hydroxyl group. The number of atoms contained in the linking group L excluding hydrogen atoms is preferably 1-50, more preferably 1-40, and further preferably 1-30. The number of linking atoms refers to the number of atoms located in the shortest distance in the atomic group participating 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 there are also 4 atoms in addition to hydrogen atoms. On the other hand, the shortest atom participating in the connection is -CCO-, which becomes three. As the number of linking atoms, 1 to 24 are preferable, 1 to 12 are more preferable, and 1 to 6 are further preferable. Furthermore, the above-mentioned alkylene group, alkenylene group, alkynylene group, and (oligo)alkaneoxy group may be chain or cyclic, or may be linear or branched.

The weight average molecular weight of the specific polymer is preferably 2,000 or more, more preferably 3,000 or more, still more preferably 4,000 or more, still more preferably 6,000 or more, still more preferably 10,000 or more, and particularly preferably 15,000 or more. The upper limit of the weight average molecular weight is not particularly limited. For example, it is preferably 200,000 or less, more preferably 100,000 or less, more preferably 70,000 or less, even more preferably 50,000 or less, and may be 35,000 or less. By making the weight average molecular weight more than the said lower limit, the film stability at the time of a baking process improves, and the surface shape at the time of formation of an imprint underlayer film can be improved more. Moreover, by making a weight average molecular weight below the said upper limit value, the solubility to a solvent becomes high, and application by spin coating etc. becomes easier. The wettability of the curable composition for imprint is improved by maintaining the fluidity by setting the molecular weight in an appropriate range. The degree of dispersion (Mw/Mn) of the specific polymer is preferably 3.0 or less, more preferably 2.5 or less. The lower limit of the degree of dispersion may be 1.0, but it is a sufficient practical level even if it is 1.5 or more.

The content of the specific polymer in the underlayer film-forming composition for imprinting is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more. As the upper limit, 10 mass % or less is preferable, 7 mass % or less is more preferable, 5 mass % or less is more preferable, 4 mass % or less is more preferable, 3 mass % or less is further preferable, and 1 mass % may be used Below, it may be 0.7 mass % or less. The content rate of the nonvolatile components of the specific polymer (referring to components other than the solvent in the composition, the same applies hereinafter) is preferably 5 mass % or more, more preferably 20 mass % or more, and 30 mass % or more More preferably, 50 mass % or more is more preferable, 80 mass % or more is more preferable, 90 mass % or more is further more preferable, and it may be 95 mass % or more, or 99 mass % or more. As an upper limit, it may be 100 mass %. By making this amount more than the said lower limit, the effect by a blended polymer can be exhibited suitably, and it becomes easy to produce a uniform thin film. On the other hand, by setting it as the said upper limit or less, the effect of using a solvent is exhibited suitably, and it becomes easy to form a uniform film in 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, it is preferable that the total amount is in the above-mentioned range.

[表2]

[表3]

[表4]

Examples of the specific polymer include the following polymers, but the present invention is not to be construed as being limited thereto. In addition, the crosslinkable unit in the table corresponds to the structural unit having the above-mentioned polymerizable group Ps (for example, corresponding to formulae (1-1) to (1-6)), and the acidic unit is derived from the above-mentioned pKa 4.0 or less. The structural units of the monomer (for example, formulae (1) to (6)) correspond. [Table 1]

[Table 2]

[table 3]

[Table 4]

＜Solvent＞ The underlayer film-forming composition for imprint contains a solvent (hereinafter, sometimes referred to as a "solvent for an underlayer film"). The solvent is preferably a compound having a liquid at 23°C and a boiling point of 250°C or lower, for example. Typically, the non-volatile components end up forming the underlying film. The underlayer film-forming composition for imprint preferably contains 99.0% by mass or more of the solvent for an underlayer film, more preferably 99.5% by mass or more, and may be 99.6% by mass or more. In the present invention, a liquid system means that the viscosity at 23°C is 100,000 mPa･s or less. By making the ratio of a solvent into the said range, the film thickness at the time of film formation is kept thin, and the pattern formability at the time of an etching process improves. The solvent may contain only one type or two or more types in the underlayer film-forming composition for imprinting. When two or more types are contained, it is preferable that the total amount is in the above-mentioned 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, more preferably 160°C or lower, and still more preferably 130°C or lower. The lower limit is actually 23°C, but 60°C or higher is more practical. Since the solvent can be easily removed from an underlayer film by making a boiling point into the said range, it is preferable.

The solvent for the underlayer film is preferably an organic solvent. The solvent is preferably a solvent having any one or more of an ester group, a carbonyl group, a hydroxyl group, and an ether group. Among them, it is preferable to use an aprotic polar solvent.

Specific examples include alkoxy alcohol, propylene glycol monoalkyl ether carboxylate, propylene glycol monoalkyl ether, lactate, acetate, alkoxypropionate, chain ketone, cyclic ketone, lactone and alkylene carbonates.

Examples of the alkoxy alcohol include methoxyethanol, ethoxyethanol, methoxypropanol (for example, 1-methoxy-2-propanol), and ethoxypropanol (for example, 1-ethoxypropanol). propyl-2-propanol), propoxypropanol (e.g., 1-propoxy-2-propanol), methoxybutanol (e.g., 1-methoxy-2-butanol, 1-methyl oxy-3-butanol), ethoxybutanol (eg, 1-ethoxy-2-butanol, 1-ethoxy-3-butanol), methyl pentanol (eg, 4-methyl base-2-pentanol), etc.

The propylene glycol monoalkyl ether carboxylate is preferably 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. Methyl ether acetate (PGMEA) is particularly preferred.

Moreover, as propylene glycol monoalkyl ether, propylene glycol monomethyl ether (PGME) or propylene glycol monoethyl ether is preferable. As the lactate, ethyl lactate, butyl lactate or propyl lactate are preferred. As acetate, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, Isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate Or 3-methoxybutyl acetate is preferred. As the alkoxypropionate, methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) are preferred. As chain ketones, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutanone, phenylacetone , methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, acetone acetone, ionone (ionone), diacetone alcohol, acetone methanol, acetophenone, methyl naphthyl ketone, methyl pentane Ketones are preferred. As the cyclic ketone, methylcyclohexanone, isophorone or cyclohexanone is preferable. As the lactone, γ-butyrolactone (γBL) is preferable. As the alkylene carbonate, propylene carbonate is preferred.

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

Preferred examples of the ester-based solvent having 7 or more carbon atoms and 2 or less heteroatoms include amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, and propyl acetate. Amyl acid, hexyl propionate, butyl propionate, isobutyl isobutyrate, heptyl propionate, butyl butyrate, etc., and isoamyl acetate (Isoamyl acetate) is particularly preferred.

In addition, it is also preferable to use a solvent having a flash point (hereinafter, also referred to as p component) of 30°C or higher. As such components, propylene glycol monomethyl ether (component p: 47°C), ethyl lactate (component p: 53°C), ethyl 3-ethoxypropionate (component p: 49°C), methyl amyl ketone (component p: 42°C), cyclohexanone (component p: 30°C), amyl acetate (component p: 45°C), methyl 2-hydroxyisobutyrate (component p: 45°C), γ-butyrate Esters (component p: 101°C) or propylene carbonate (component p: 132°C) are preferred. Among them, propylene glycol monoethyl ether, ethyl lactate, amyl acetate or cyclohexanone are further preferred, and propylene glycol monoethyl ether or ethyl lactate is particularly preferred.

As the solvent for the underlayer film, preferred solvents include alkoxy alcohols, propylene glycol monoalkyl ether carboxylate, propylene glycol monoalkyl ether, lactate, acetate, alkoxypropionate, chain Form ketones, cyclic ketones, lactones and alkylene carbonates.

＜Other ingredients＞ The composition for forming an underlayer film for imprint may contain, in addition to the above, one or two of the above alkylene glycol compounds, polymerization initiators, polymerization inhibitors, antioxidants, leveling agents, tackifiers, Surfactant, etc. As the thermal polymerization initiator and the like, each component described in JP 2013-036027 A, JP 2014-090133 A, and JP 2013-189537 A can be used. Regarding the content and the like, the descriptions of the above-mentioned gazettes can also be referred to.

＜＜Alkylene glycol compound＞＞ The underlayer film-forming composition for imprint may contain an alkylene glycol compound. The alkylene glycol compound preferably has 3-1000 alkylene glycol structural units, more preferably has 4-500, more preferably has 5-100, more preferably has 5-50 . The weight average molecular weight (Mw) of the alkylene glycol compound is preferably 150-10,000, more preferably 200-5,000, still more preferably 300-3,000, and even more preferably 300-1,000. Alkylene glycol compounds are exemplified by polyethylene glycol, polypropylene glycol, these mono- or dimethyl ethers, mono- or dioctyl ethers, mono- or dinonyl ethers, mono- or didecyl ethers, monostearate, Monoester, monoadipate, monosuccinate, polyethylene glycol and polypropylene glycol are preferred. The surface tension of the alkylene glycol compound at 23°C is preferably 38.0 mN/m or more, more preferably 40.0 mN/m or more. The upper limit of the surface tension is not particularly limited, but is, for example, 48.0 mN/m or less. By blending the above-mentioned compound, the wettability of the curable composition for imprint provided just above the underlayer film can be improved. The surface tension was measured using a surface tensiometer SURFACE TENS-IOMETER CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd. at 23°C using a glass plate. The unit is represented by mN/m. Two samples were prepared for each level, and each was measured three times. The arithmetic mean value of a total of 6 times was adopted as the evaluation value.

When an alkylene glycol compound is contained, it is 40 mass % or less of nonvolatile components, preferably 30 mass % or less, more preferably 20 mass % or less, and even more preferably 1 to 15 mass %. The alkylene glycol compound may be used only 1 type, and may use 2 or more types. When two or more types are used, it is preferable that the total amount is in the above-mentioned range.

＜＜Polymerization initiator＞＞ The underlayer film-forming composition for imprinting may contain a polymerization initiator, preferably at least one of a thermal polymerization initiator and a photopolymerization initiator. By including a polymerization initiator, the reaction of the polymerizable group contained in the underlayer film-forming composition for imprint is accelerated, and the adhesiveness tends to be improved. A photopolymerization initiator is preferable from the viewpoint of improving the crosslinking 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. In addition, in the present invention, a plurality of photopolymerization initiators may be used in combination.

As the photoradical polymerization initiator, any known compounds can be used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalogenated methyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaaryl phosphine compounds, etc. Oxime compounds such as bisimidazoles and oxime derivatives, organic peroxides, sulfur compounds (thio compounds), ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo-based Compounds, azide compounds, metallocene compounds, organoboron compounds, iron-arene complexes, etc. For details of these, reference can be made to the descriptions in paragraphs 0165 to 0182 of JP 2016-027357 A, which are incorporated herein. As an acylphosphine compound, 2,4,6- trimethylbenzyl-diphenyl-phosphine oxide etc. are mentioned. In addition, commercially available IRGACURE-819, IRGACURE1173, and IRGACURE-TPO (product names: all manufactured by BASF Corporation) can be used.

The content of the photopolymerization initiator used in the above-mentioned composition for forming an underlayer film for imprint, when blending, is, for example, 0.0001 to 5% by mass, preferably 0.0005 to 3% by mass, and 0.01% of the nonvolatile components. -1 mass % is more preferable. When two or more types of photopolymerization initiators are used, the total amount thereof falls within the above-mentioned range.

<Storage container> A conventionally known storage container can be used as the storage container of the underlayer film-forming composition for imprinting. Moreover, as a container, it is also preferable to use a multilayer bottle having a container inner wall composed of six kinds of 6-layer resins or a bottle having a 7-layer structure of 6 kinds of resins for the purpose of suppressing contamination of impurities into the raw material or the composition. As such a container, the container described in Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

＜Surface Free Energy＞ The surface free energy of the imprint underlayer film formed from the imprint underlayer film-forming composition of the present invention is preferably 30 mN/m or more, more preferably 40 mN/m or more, and even more preferably 50 mN/m or more. The upper limit is preferably 200 mN/m or more, more preferably 150 mN/m or more, and even more preferably 100 mN/m or more. The measurement of surface free energy can be performed using a surface tensiometer SURFACE TENS-IOMETER CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd. at 23°C using a glass plate.

<Curable composition for imprint> The underlayer film-forming composition of the present invention is generally used as a composition for forming an underlayer film of a curable composition for imprinting. The composition and the like of the curable composition for imprinting are not particularly limited, but it is preferable to include a polymerizable compound.

L²⁰ 為1+q2價的連接基團，例如，1+q2價的烷烴結構的基團（碳數1～12為較佳，1～6為更佳，1～3為進一步較佳）、烯烴結構的基團（碳數2～12為較佳，2～6為更佳，2～3為進一步較佳）、芳基結構的基團（碳數6～22為較佳，6～18為更佳，6～10為進一步較佳）、雜芳基結構的基團（碳數1～22為較佳，1～18為更佳，1～10為進一步較佳，作為雜原子，可舉出氮原子、硫原子、氧原子，5員環、6員環、7員環為較佳）或包含組合該些之基團之連接基團。作為組合2個芳基之基團，可舉出具有聯苯或二苯基烷烴、聯伸苯基、茚等的結構之基團。作為組合雜芳基結構之基團與芳基結構的基團者，可舉出具有吲哚、苯并咪唑、喹喔啉、咔唑等的結構之基團。 R²¹ 及R²² 分別獨立地表示氫原子或甲基。 L^{21 及} L²² 分別獨立地表示單鍵或上述連接基團L，其中，具有雜原子之連接基團為較佳。L²⁰ 與L²¹ 或L²² 可以經由或不經由連接基L鍵結而形成環。L²⁰ 、L²¹ 及L²² 可具有上述取代基T。取代基T可鍵結複數個而形成環。取代基T為複數個時，可以彼此相同，亦可彼此不同。 q2為0～5的整數，0～3的整數為較佳，0～2的整數為更佳，0或1為進一步較佳。<<Polymerizable compound>> It is preferable that the curable composition for imprint contains a polymerizable compound, and it is more preferable that the polymerizable compound constitutes the largest component. The polymerizable compound may have one polymerizable group in one molecule, or may have two or more. At least one of the polymerizable compounds contained in the curable composition for imprint preferably contains 2 to 5 polymerizable groups in one molecule, more preferably 2 to 4, and 2 or 3 For further preference, it is further preferred to include three. At least one of the polymerizable compounds contained in the curable composition for imprint contains an aromatic ring (preferably carbon number 6 to 22, more preferably 6 to 18, and further preferably 6 to 10) and an alicyclic ring (The number of carbon atoms is preferably 3 to 24, more preferably 3 to 18, and more preferably 3 to 6). At least one of them is preferred, and it is further preferred to contain an aromatic ring. The aromatic ring is preferably a benzene ring. The molecular weight of the polymerizable compound is preferably 100 to 900. At least one of the above-mentioned polymerizable compounds is preferably represented by the following formula (I-1). [Chemical formula 3]

L ²⁰ is a 1+q2-valent linking group, for example, a 1+q2-valent alkane structure group (the number of carbons is preferably 1-12, more preferably 1-6, and more preferably 1-3), Groups of olefin structure (preferably with carbon number 2-12, more preferably with 2-6, further preferably with 2-3), groups with aryl structure (preferably with carbon number of 6-22, with 6-18 More preferably, 6-10 are further preferred), groups of heteroaryl structure (carbon number 1-22 is preferred, 1-18 is more preferred, 1-10 is further preferred, as a heteroatom, can be A nitrogen atom, a sulfur atom, an oxygen atom, a 5-membered ring, a 6-membered ring, and a 7-membered ring are preferred) or a linking group including a group combining these. As a group which combines two aryl groups, the group which has a structure, such as biphenyl, a diphenylalkane, a biextended phenyl group, an indene, is mentioned. As a group which combines the group of a heteroaryl structure and the group of an aryl structure, the group which has structures, such as indole, a benzimidazole, a quinoxaline, a carbazole, is mentioned. R ²¹ and R ²² each independently represent a hydrogen atom or a methyl group. L ^{21 and} L ²² each independently represent a single bond or the above-mentioned linking group L, and among them, a linking group having a heteroatom is preferable. L ²⁰ and L ²¹ or L ²² may be bonded via or not via a linker L to form a ring. L ²⁰ , L ²¹ and L ²² may have the above-mentioned substituent T. A plurality of substituents T may be bonded to form a ring. When there are plural substituents T, they may be the same or different from each other. q2 is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and even more preferably 0 or 1.

Examples of the polymerizable compound include the compounds used in the following examples, the compounds described in paragraphs 0017 to 0024 of JP-A No. 2014-090133 and the examples described in JP-A No. 2015-009171 The compounds described in paragraphs 0024 to 0089 of Japanese Patent Application Laid-Open No. 2015-070145, the compounds described in paragraphs 0023 to 0037 of Japanese Patent Application Laid-Open No. 2015-070145, and the compounds described in paragraphs 0012 to 0039 of International Publication No. 2016/152597, but the present invention It is not to be construed by this limitation.

The polymerizable compound is preferably contained in the curable composition for imprinting in an amount of 30% by mass or more, more preferably 45% by mass or more, more preferably 50% by mass or more, still more preferably 55% by mass or more, and may be 60% by mass or more. The mass % or more may be 70 mass % or more. Moreover, the upper limit is preferably less than 99 mass %, more preferably 98 mass % or less, and can also be 97 mass % or less.

The boiling point of the polymerizable compound is preferably set according to the relationship with the specific compound contained in the above-mentioned underlayer film-forming composition for imprint, and the ratio is preferably designed. The boiling point of the polymerizable compound is preferably 500°C or lower, more preferably 450°C or lower, and even more preferably 400°C or lower. The lower limit is preferably 200°C or higher, more preferably 220°C or higher, and even more preferably 240°C or higher.

＜＜Other ingredients＞＞ The curable composition for imprint may contain additives other than the polymerizable compound. As other additives, a polymerization initiator, a surfactant, a sensitizer, a mold release agent, an antioxidant, a polymerization inhibitor, and the like may be contained. Specific examples of the curable composition for imprint that can be used in the present invention include those described in JP 2013-036027 A, JP 2014-090133 A, and JP 2013-189537 A composition, and these contents are incorporated into this specification. Moreover, about the preparation of the curable composition for imprinting, and the formation method of a film (pattern formation layer), the description of the said gazette can also be referred, and these content are incorporated in this specification.

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 even more preferably 1% by mass or less of the curable composition for imprint. The curable composition for imprint can also be made to contain substantially no polymer (preferably a weight-average molecular weight greater than 1,000, more preferably a weight-average molecular weight greater than 2,000, and more preferably a polymer with a weight-average molecular weight greater than 10,000) state. Substantially not containing a polymer means, for example, that the content of the polymer is 0.01 mass % or less of the curable composition for imprint, preferably 0.005 mass % or less, and more preferably not containing it at all.

＜＜Properties, etc.＞＞ The viscosity of the curable composition for imprinting is preferably 20.0 mPa･s or less, more preferably 15.0 mPa･s or less, still more preferably 11.0 mPa･s or less, and even more preferably 9.0 mPa･s or less. Although it does not specifically limit as a lower limit of the said viscosity, For example, it can be 5.0 mPa·s or more. Viscosity is measured as follows. The viscosity was measured using an E-type rotational viscometer RE85L manufactured by TOKI SANGYO CO., LTD, and a standard cone/rotor (1°34'×R24). The temperature of the sample cup was adjusted to 23°C. The unit is expressed by mPa･s. Other details about the measurement are based on JISZ8803:2011. Two samples were prepared for each level, and each was measured three times. The arithmetic mean value of a total of 6 times was adopted as the evaluation value.

The surface tension (γResist) of the curable composition for imprinting is preferably 28.0 mN/m or more, more preferably 30.0 mN/m or more, and may be 32.0 mN/m or more. By using the curable composition for imprint with high surface tension, the capillary force is increased, and high-speed filling of the mold pattern with the curable composition for imprint can be performed. The upper limit of the surface tension is not particularly limited, but from the viewpoints of the relationship with the underlayer film and the compatibility with inkjet, 40.0 mN/m or less is preferable, and 38.0 mN/m or less is more preferable. is 36.0 mN/m or less. The surface tension of the curable composition for imprinting was measured by the following method.

The Ohnishi parameter of the curable composition for imprinting is preferably 5.0 or less, more preferably 4.0 or less, and even more preferably 3.7 or less. The lower limit of the Ohnishi parameter of the curable composition for imprinting is not particularly limited, but may be, for example, 1.0 or more, and further 2.0 or more. The Ohnishi parameter can be obtained by substituting the numbers of carbon atoms, hydrogen atoms, and oxygen atoms of the total constituent components into the following equations for the polymerizable compound of the curable composition for imprinting. Ohnishi parameter = the sum of the number of carbon atoms, hydrogen atoms and oxygen atoms / (the number of carbon atoms - the number of oxygen atoms)

＜＜Storage container＞＞ As the storage container of the curable composition for imprint used in the present invention, a conventionally known storage container can be used. Moreover, as a container, it is also preferable to use a multilayer bottle having a container inner wall composed of six kinds of 6-layer resins or a bottle having a 7-layer structure of 6 kinds of resins for the purpose of suppressing contamination of impurities into the raw material or the composition. As such a container, the container described in Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

<Pattern and Pattern Forming Method> A method for forming a pattern according to a preferred embodiment of the present invention includes: a process of forming an underlayer film on the surface of a substrate using the underlayer film forming composition for imprinting of the present invention (underlayer film forming process); The surface is better) The process of applying the lower layer film forming composition for imprint to form the curable composition layer for imprint (the process of forming the curable composition layer for imprint), making the mold and the above curable composition for imprint The process of layer contact; the process of exposing the above-mentioned curable composition layer for imprint in contact with the above-mentioned casting mold; and the process of peeling the above-mentioned casting mold from the above-mentioned exposed curable composition layer for imprinting. Hereinafter, the pattern forming method (the manufacturing method of the cured product pattern) will be described based on ( 1 ) to ( 7 ) of FIG. 1 . Obviously, the structure of the present invention is not limited to the drawings.

<<Underlayer film formation process>> As shown in FIG. 1 ( 1 ) and FIG. 1 ( 2 ), in the underlayer film formation process, the underlayer film 2 is formed on the surface of the substrate 1 . The underlayer film is preferably formed on the substrate by applying the composition for forming an underlayer film for imprinting to a layered form. The substrate 1 may have an undercoat layer or an adhesive film unless it is constituted by a single layer.

The method of applying the underlayer film-forming composition for imprinting to the substrate is not particularly limited, and a generally known application method can be employed. Specifically, examples of applicable methods include dip coating, pneumatic coating, curtain coating, wire bar coating, gravure coating, extrusion coating, and spin coating. The coating method, the slit scanning method or the ink jet method, and the spin coating method are preferred. In addition, after applying the underlayer film forming composition for imprinting to the substrate in a layered form, the solvent is volatilized (dried) by heat to form an underlayer film as a thin 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, and may be 5 nm or more, 7 nm or more, or 10 nm or more. In addition, the thickness of the underlayer film is preferably 40 nm or less, more preferably 30 nm, still more preferably 20 nm, and may be 15 nm or less. By making the film thickness equal to or more than the above lower limit value, the spreadability (wettability) of the curable composition for imprinting on the underlayer film is improved, and a uniform residual film after imprinting can be formed. By setting the film thickness to be equal to or less than the above-mentioned upper limit value, the residual film after imprinting becomes thin, and the unevenness of the film thickness is less likely to occur, and the uniformity of the residual film tends to be improved.

The material of the substrate is not particularly limited, and the description in paragraph 0103 of JP-A No. 2010-109092 can be referred to, and these contents are incorporated into the present specification. In the present invention, silicon substrates, glass substrates, quartz substrates, sapphire substrates, silicon carbide (silicon carbide) substrates, gallium nitride substrates, aluminum substrates, amorphous alumina substrates, polycrystalline alumina substrates, and (spin-on carbon), SOG (spin-on glass), silicon nitride, silicon oxynitride, and substrates composed of GaAsP, GaP, AlGaAs, InGaN, GaN, AlGaN, ZnSe, AlGa, InP, or ZnO. In addition, as a specific material example of a glass substrate, aluminosilicate glass, aluminoborosilicate glass, and barium borosilicate glass are mentioned. In the present invention, a silicon substrate and a substrate coated with SOC (spin-on carbon) are preferred.

In the present invention, it is preferable to use a substrate having an organic layer as the outermost layer. Examples of the organic layer of the substrate include an amorphous carbon film formed by CVD (Chemical Vapor Deposition) or a spin-coating carbon film formed by dissolving a high carbon material in an organic solvent and forming by spin coating. Examples of the spin-coating type carbon film include nortricycloene copolymers, hydronaphthol novolak resins, naphthol dicyclopentadiene copolymers, phenol dicyclopentadiene copolymers, Japanese Patent Laid-Open No. 2005- Fluorene bisphenol novolak described in JP-A No. 128509, acenaphthene copolymer and indene copolymer described in JP-A No. 2005-250434, and fullerene having a phenol group described in JP-A No. 2006-227391 , bisphenol compound and the novolak resin, dibisphenol compound and the novolak resin, novolak resin of adamantane phenol compound, hydroxyvinylnaphthalene copolymer, bisnaphthol described in Japanese Patent Laid-Open No. 2007-199653 Compounds and the novolak resin, ROMP, a resin compound shown as a tricyclopentadiene copolymer. As an example of the SOC, the description in paragraph 0126 of Japanese Patent Laid-Open No. 2011-164345 can be referred to, and the content thereof is incorporated into this specification.

The contact angle of water on the surface of the substrate is preferably 20° or more, more preferably 40° or more, and even more preferably 60° or more. The upper limit is actually 90° or less. The contact angle was measured according to the method described in the examples described later.

In the present invention, it is preferable to use a substrate having an alkaline layer as the outermost layer (hereinafter, referred to as an alkaline substrate). Examples of basic substrates include substrates containing basic organic compounds (for example, amine-based compounds, ammonium-based compounds, etc.) and inorganic substrates containing nitrogen atoms.

<<The process of forming the curable composition layer for imprinting>> In the application process, for example, as shown in FIG. 1 ( 3 ), the curable composition 3 for imprinting is applied to the surface of the underlayer film 2 described above. The method of applying the curable composition for imprinting is not particularly limited, and reference can be made to paragraph 0102 of Japanese Patent Application Laid-Open No. 2010-109092 (the publication number corresponding to the US application is US Patent Application Publication No. 2011/0183127). described, and the contents are incorporated into this specification. It is preferable that the curable composition for imprinting is applied to the surface of the underlayer film by an ink jet method. Moreover, the application of the curable composition for imprint can be performed by multiple application|coating. In the method of arranging droplets on the surface of the lower layer film by an ink jet method or the like, the amount of the droplets is preferably about 1 to 20 pL, and the droplets are preferably arranged at intervals on the surface of the lower layer film. As a droplet interval, the interval of 10-1000 micrometers is preferable. In the case of the ink jet method, the droplet interval is the arrangement interval of the nozzles for ink jetting. Furthermore, the volume ratio of the underlayer film 2 to the film-like imprint curable composition 3 applied to the underlayer film is preferably 1:1 to 500, more preferably 1:10 to 300, and 1:50 to 200 for further better. Further, a 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, the method comprising applying an imprint to the surface of the underlayer film formed from the underlayer film-forming composition for imprinting. Process of hardening composition. Furthermore, the manufacturing method of the laminated body of the preferred embodiment of the present invention includes a process of applying the above-mentioned underlayer film forming composition for imprinting to a layered form on a substrate, and includes applying the underlayer film for imprinting to the above-mentioned layered form. The formation of the composition is preferably at 100-300°C, more preferably at 130-260°C, further preferably at 150-230°C, and the heating (baking) process is more preferable. The heating time is preferably 30 seconds to 5 minutes.

＜＜Mold Contact Process＞＞ For example, as shown in FIG. 1 ( 4 ), in the mold contact process, the above-mentioned curable composition 3 for imprint is brought into contact with a mold 4 having a pattern for transferring a pattern shape. By going through such a process, a desired hardened product pattern (imprint pattern) is obtained. Specifically, in order to transfer a desired pattern to the film-shaped curable composition for imprint, the surface of the film-shaped curable composition for imprint 3 is covered with the casting mold 4 .

The mold may be a light-transmitting mold or a non-light-transmitting mold. When a light-transmitting mold is used, it is preferable to irradiate the curable composition 3 for imprinting with light from the mold side. In the present invention, it is more preferable to use a light-transmitting mold, and to irradiate light from the mold side. A mold that can be used in the present invention is a mold having a pattern for transfer. The pattern which the said mold has, for example, can be formed by photolithography, an electron beam scanning method, etc. with desired processing precision, However, in this invention, the manufacturing method of a mold pattern is not specifically limited. Moreover, the pattern formed by the hardened|cured material pattern manufacturing method of the preferred embodiment of this invention can also be used as a mold. The material constituting the light-transmitting mold used in the present invention is not particularly limited, and examples thereof include light-transmitting resins such as glass, quartz, polymethyl methacrylate (PMMA), and polycarbonate resins, transparent metal vapor-deposited films, and polycarbonate resins. Soft films such as dimethyl siloxane, photohardening films, metal films, etc., quartz is preferred. It does not specifically limit as a non-light-transmitting type casting_mold|template material used when a light-transmitting board|substrate is used in this invention, What is necessary is just to have predetermined intensity|strength. Specifically, ceramic materials, vapor-deposited films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, and substrates such as SiC, silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon are exemplified. There is no particular limitation.

In the manufacturing method of the said hardened|cured material pattern, when performing imprint lithography using the curable composition for imprinting, it is preferable to make a mold pressure 10 atmospheres or less. By setting the mold pressure to 10 atmospheres or less, the mold or the substrate tends to be less deformed and the pattern accuracy tends to be improved. Moreover, it is also preferable from the viewpoint that there is a tendency that the apparatus can be reduced due to the low pressure. The mold pressure is preferably selected from a range where the residual film of the curable composition for imprint touching the convex portion of the mold is reduced, and the uniformity of the transfer of the mold can be ensured. Moreover, it is also preferable to carry out the contact between the curable composition for imprinting and the mold in an atmosphere containing helium gas or condensable gas, or both of helium gas and condensable gas.

<<Light irradiation process>> In the light irradiation process, light is irradiated to the said curable composition for imprinting, and a hardened|cured material is formed. The irradiation dose of light irradiation in the light irradiation process may be sufficiently larger than the minimum irradiation dose required for curing. The irradiation dose required for curing is appropriately determined by examining the consumption of unsaturated bonds of the curable composition for imprinting, and the like. The type of light to be irradiated is not particularly limited, but ultraviolet light is exemplified. In addition, in the imprint lithography applied to the present invention, the substrate temperature at the time of light irradiation is usually set to room temperature, but in order to improve the reactivity, light irradiation may be performed simultaneously with heating. As a preparatory stage for light irradiation, if it is in a vacuum state, it is effective in preventing the incorporation of air bubbles, suppressing the decrease in reactivity due to the incorporation of oxygen, and improving the adhesion between the mold and the curable composition for imprinting. Light irradiation was performed in a vacuum state. Furthermore, in the above-described method for producing a pattern of a cured product, the preferred degree of vacuum at the time of light irradiation is in the range of 10 ^-1 Pa to normal pressure. When performing exposure, it is more preferable to set the exposure illuminance 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-described method for manufacturing a cured product pattern, after curing the film-like curable composition for imprint (pattern forming layer) by light irradiation, a process of heating and curing the cured pattern may be further included as necessary. As a temperature for heat-hardening the curable composition for imprinting after light irradiation, 150-280 degreeC is preferable, and 200-250 degreeC is more preferable. In addition, as time for applying heat, 5 to 60 minutes is preferable, and 15 to 45 minutes is more preferable.

＜＜Demolding process＞＞ In the demolding process, the above-mentioned hardened material and the above-mentioned casting mold are separated ((5) in FIG. 1 ). The obtained hardened|cured material pattern can be utilized for various uses as mentioned later. That is, in this invention, the laminated body which further has the hardened|cured material pattern formed of the curable composition for imprinting on the surface of the said underlayer film is disclosed. In addition, the film thickness of the pattern-forming layer including the curable composition for imprint used in the present invention varies depending on the application, but is about 0.01 μm to 30 μm. In addition, as will be described later, etching and the like can also be performed.

<The cured product pattern and its application> As described above, the cured product pattern formed by the above-mentioned manufacturing method of the cured product pattern can be used as a permanent film used in a liquid crystal display device (LCD) or the like, or as an etching resist for manufacturing a semiconductor element (mask for lithography). In particular, this specification discloses a method for manufacturing a semiconductor device (circuit board), which includes a process for obtaining a cured product pattern by the method for manufacturing a cured product pattern according to a preferred embodiment of the present invention. Furthermore, in the method for manufacturing a semiconductor device according to a preferred embodiment of the present invention, there may be a process and formation of etching or ion implantation on a substrate using the cured product pattern obtained by the above-described manufacturing method of the cured product pattern as a mask. The manufacturing process of electronic components. The above-mentioned semiconductor device is preferably a semiconductor element. That is, in this specification, the manufacturing method of the semiconductor device containing the above-mentioned pattern formation method is disclosed. Furthermore, the present specification discloses a method of manufacturing an electronic device including a process of obtaining a semiconductor device by the above-mentioned method of manufacturing a semiconductor device and a process of connecting the above-mentioned semiconductor device to a control mechanism for controlling the above-mentioned semiconductor device. In addition, by forming a grid pattern on the glass substrate of the liquid crystal display device using the pattern formed by the above-mentioned method for manufacturing the cured product pattern, it is possible to inexpensively manufacture a large screen size (eg, 55 inches, more than 60 inches) with less reflection or absorption. inch) polarizer. For example, the polarizing plate described in Japanese Patent Laid-Open No. 2015-132825 or International Publication No. 2011/132649 can be produced. As shown in FIG. 1 ( 6 ) and FIG. 1 ( 7 ), the cured product pattern formed by 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, by the above-described cured product pattern manufacturing method, a fine cured product pattern of, for example, nanometer or micron order is formed on the substrate. In the present invention, in particular, nanoscale fine patterns can be formed, and furthermore, it is effective in that a pattern with a size of 50 nm or less, especially 30 nm or less can be formed. The lower limit value of the size of the cured product pattern formed by the above-mentioned cured product pattern manufacturing method is not particularly limited, but can be, for example, 1 nm or more. In addition, the present invention also discloses a method for producing a casting mold for imprinting, which includes a process of obtaining a pattern of a hardened product on a substrate by the method for producing a pattern of a hardened product according to a preferred embodiment of the present invention, and using the above-mentioned hardening obtained The process of etching the object pattern on the above-mentioned substrate. A desired cured product pattern can be formed on a substrate by etching using hydrogen fluoride or the like in wet etching and etching using an etching gas such as CF ₄ in dry etching. The cured product pattern is particularly good in etching resistance to dry etching. That is, the pattern formed by the above-described method for manufacturing a cured product pattern is preferably used as a mask for lithography.

Specifically, the pattern formed by the present invention can be preferably used for the production of a guide pattern, etc., which is used for fine pattern formation (directed self-assembly, DSA (directed self-assembly) using the following self-organization) ), that is, recording media such as magnetic disks, light-receiving elements such as solid-state imaging elements, light-emitting elements such as LED (light emitting diode) or organic EL (organic electroluminescence), optical devices such as liquid crystal display devices (LCD), Optical components such as diffraction gratings, relief holography, optical waveguides, filters, microlens arrays, thin film transistors, organic transistors, color filters, anti-reflection films, polarizers, polarizing elements, optical films, columns and other components for flat panel displays , Nano biological devices, immunoassay wafers, deoxyribonucleic acid (DNA) separation wafers, microreactors, photonic liquid crystals, block copolymers. [Example]

The following examples are given to further illustrate the present invention in detail. Materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Synthesis of A-1/B-1 (90/10) Copolymer> Into the flask, 100 g of water was added as a solvent, and the temperature was raised to 90°C under a nitrogen atmosphere. To this water, glycidyl methacrylate; 16.0 g (0.16 mol) (FUJIFILM Wako Pure Chemical Corporation), the following disodium phosphate 2-propenyloxyethyl; 1.8 g (7 mmol) ( FUJIFILM Wako Pure Chemical Corporation), 2,2'-azobis(2-(2-imidazolin-2-yl)propane dihydrochloride) (VA-044); 1.0 g (3 mmol) (FUJIFILM Wako Pure Chemical Corporation), water; 50 g of the mixture was added dropwise for 2 hours. After the dropwise addition was completed, a copolymer was further obtained by stirring at 90° C. for 4 hours. To the solution of the above copolymer was added acrylic acid; 11.6 g (0.16 moles) (FUJIFILM Wako Pure Chemical Corporation), tetraethylammonium bromide (TEAB); 2.1 g (FUJIFILM Wako Pure Chemical Corporation), 4-hydroxy-tetramethyl Piperidine-1-oxyl (4-HO-TEMPO); 50 mg (FUJIFILM Wako Pure Chemical Corporation), reacted at 90° C. for 8 hours, and it was confirmed that acrylic acid disappeared from H-NMR by the reaction, thereby obtaining an aqueous solution of resin . The reaction scheme is shown below. 1N hydrochloric acid was added to the above-mentioned aqueous solution, and the precipitate was purified by washing with water to obtain a powder of resin A-1/B-1. The other copolymers are also synthesized in the same manner.

磷酸二鈉2-丙烯醯氧乙基（分子量254.2）[Chemical formula 4]

Disodium phosphate 2-propenyloxyethyl (molecular weight 254.2)

[Chemical formula 5]

The above resin was dissolved in PGMEA to obtain a PGMEA solution. The weight average molecular weight (Mw, in terms of polystyrene) determined by gel permeation chromatography (GPC) of the obtained resin was 20,000, and the degree of dispersion (Mw/Mn)=2.2. <Measurement method of molecular weight> The weight-average molecular weight (Mw) of the resin is defined as a polystyrene conversion value according to gel permeation chromatography (GPC measurement). As the apparatus, HLC-8220 (manufactured by TOSOH CORPORATION) was used, and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) were used as columns. As the eluent, THF (tetrahydrofuran) was used. Detection was performed using an RI detector.

<Preparation of an underlayer film-forming composition> Solutions were prepared containing the ingredients shown in the table below. This was filtered through a 0.02 μm nylon filter and a 0.010 μm PTFE (polytetrafluoroethylene) filter to prepare the preparation of the lower layer film-forming composition shown in the preparation examples and comparative examples.

<Preparation of curable composition for imprint> Various compounds described in the following table were mixed, and 4-hydroxy-2,2,6,6-tetramethyl as a polymerization inhibitor was further added so that the total amount of the polymerizable compounds was 200 mass ppm (0.02 mass %). It was prepared by using a base piperidine-1-oxyl radical (manufactured by Tokyo Chemical Industry Co., Ltd.). This was filtered through a 0.02 μm nylon filter and a 0.001 μm PTFE filter to prepare a curable composition for imprinting.

＜Calculation of pKa＞ Obtained by calculation using the following package software. Software package: Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs)

<Formation of Underlayer Film/Evaluation of Film Thickness> On the substrates shown in the table below, the underlayer film forming composition for imprinting described in the table was spin-coated, and the underlayer film was formed by heating with a hot plate under the baking conditions described in the table. The film thickness of the underlayer film was measured by an ellipsometer.

<Evaluation of Adhesion Strength> On the surface of the underlayer film obtained as described above, using an ink jet printer DMP-2831 manufactured by FUJIFILM Dimatix Co., Ltd., the discharge temperature was adjusted to 23° C. for a droplet volume of 6 pL per nozzle. The composition was applied so as to form a square array of about 100 μm intervals on the underlayer film by applying droplets to form a patterning layer. Next, in a He environment (a substitution rate of 90% or more), a quartz wafer with the composition for forming an adhesion layer according to Example 6 of Japanese Patent Laid-Open No. 2014-024322 was spin-coated on the pattern forming layer, And the curable composition for imprinting is sealed. At a time point of 10 seconds after sealing, exposure was performed under the condition of 150 mJ/cm ² using a high-pressure mercury lamp from the mold side. The force required to peel off the exposed sample was measured, and the adhesion force of the underlayer film was set to F. A: F≥30N B: 25N≤F＜30N C: 20N≤F＜25N D: F＜20N

<Planar shape (evaluation of peeling defects)> On the surface of the underlayer film obtained as described above, using an ink jet printer DMP-2831 manufactured by FUJIFILM Dimatix Co., Ltd., the discharge temperature was adjusted to a pressure of 25° C. for a droplet volume of 6 pL per nozzle. The curable composition for printing was applied so as to form a square array of droplets on the underlayer film at intervals of about 100 μm to form a patterning layer. Next, a quartz mold (line pattern with a line width of 28 nm and a depth of 60 nm) was covered on the pattern forming layer in a He environment (substitution rate of 90% or more), and the mold was filled with a curable composition for imprinting. After 10 seconds elapsed after sealing, the pattern was transferred to the pattern-forming layer by peeling off the mold after exposure from the mold side using a high-pressure mercury lamp under the condition of 150 mJ/cm ² . The presence or absence of peeling of the transferred pattern was confirmed by optical microscope observation (macro observation) and SEM observation (micro observation). A: No pattern peeling was observed B: No peeling was observed in macroscopic observation, but pattern peeling was observed in microscopic observation C: Peeling was confirmed in a local area (release end) in macroscopic observation D: In macroscopic observation Peeling was confirmed across the front surface of the transfer zone

[表6]

[表7]

摻和量的單位為質量份 沸點的單位為℃（1013.25hPa） [表8]

[表9]

In the following Table 5 and Table 6, A-1/B-1 of a polymer means the copolymer which has the structural unit of A-1 and the structural unit of B-1. 90/10 represents a copolymerization ratio (molar ratio), and refers to the ratio of the constitutional unit on the left and the constitutional unit on the right, respectively. As the pKa of the monomer, the value of the pKa of a monomer having a pKa of 4.0 or less among the monomers constituting the polymer is used. The meanings of the abbreviations in the table are as follows. PGMEA: propylene glycol monomethyl ether acetate PGME: propylene glycol monomethyl ether γBL: γ-butyrolactone Mw: weight average molecular weight [Table 5]

[Table 6]

[Table 7]

The unit of blending amount is mass parts, and the unit of boiling point is °C (1013.25hPa) [Table 8]

[Table 9]

＜Substrate＞ Substrate Si: Silicon wafer with a diameter of 8 inches (1 inch is 2.54 cm) Substrate 1: Spin-coated carbon film ODL-102 (Shin-Etsu Chemical Co., Ltd.) was coated on a silicon wafer with a diameter of 8 inches by spin coating, and baked at 240° C. for 60 seconds , to form the substrate of the SOC (Spin on Carbon) film with a film thickness of 200 nm. Substrate 2: Spin-coating carbon film ODL-50 (Shin-Etsu Chemical Co., Ltd.) was coated on a silicon nitride wafer with a diameter of 8 inches by spin coating, and baked at 240° C. for 60 Seconds, the substrate of the SOC (Spin on Carbon) film with a film thickness of 200 nm is formed. Substrate 3: SOC NCA9053EH (Nissan Chemical Industries, Ltd.) was coated by spin coating on a silicon wafer with a diameter of 8 inches, and was baked at 240° C. for 60 seconds to form SOC (Spin on Carbon) film substrate. Substrate SOG: OCD T-12 (Tokyo Ohka Kogyo Co., Ltd.) was applied by spin coating on a silicon wafer with a diameter of 8 inches, and UV ozone treatment was performed for 120 seconds to form SOG with a film thickness of 200 nm film substrate.

From the above results, it is clear that the curable composition for imprint can be realized by forming the underlayer film from the underlayer film-forming composition for imprint using a polymer derived from a monomer having a pKa of 4.0 or less and a polymerizable group. Excellent adhesion (Examples 1 to 15). In particular, it was found that these imprint underlayer film-forming compositions achieved good adhesion to various substrates such as substrates with different carbon contents and SOG substrates, and were highly versatile. In addition, in the samples of any of the Examples, the imprint layer formed on the surface of the underlayer film had a favorable surface shape. On the other hand, when the above-mentioned specific polymer was not used (Comparative Example 1), the adhesiveness was poor.

1‧‧‧Substrate 2‧‧‧Lower layer film 3‧‧‧Curable composition for imprinting 4‧‧‧Mold

( 1 ) to ( 7 ) of FIG. 1 are process explanatory diagrams showing an example of the manufacturing steps when the cured product pattern is formed and the obtained cured product pattern is used for processing of the substrate by etching.

1‧‧‧Substrate

2‧‧‧Lower layer film

3‧‧‧Curable composition for imprinting

4‧‧‧Mold

Claims (22)

An underlayer film-forming composition for imprint comprising a polymer and a solvent, the polymer comprising a structural unit and a polymerizable group derived from a monomer having a pKa of 4.0 or less. The composition for forming an underlayer film for imprinting as described in claim 1, wherein the polymer is an acrylic resin. The underlayer film-forming composition for imprinting according to claim 1 or claim 2, wherein the polymer has a weight average molecular weight of 2,000 or more. The composition for forming an underlayer film for imprinting according to claim 1 or claim 2, wherein the polymerizable group possessed by the polymer is a (meth)acryloyl group. The underlayer film-forming composition for imprinting according to claim 1 or claim 2, wherein the constituent unit of the polymer derived from a monomer having a pKa of 4.0 or less is derived from a monomer having a pKa of 3.0 or less The building blocks of monomers. The composition for forming an underlayer film for imprinting according to claim 1 or claim 2, wherein the constituent unit derived from a monomer having a pKa of 4.0 or less has a group selected from the group consisting of a hydroxyl group, a carboxyl group, and a thiocarboxylic acid group. , at least one of the group of dithiocarboxylic acid group, sulfonic acid group, phosphoric acid monoester group, phosphoric acid diester group and phosphoric acid group. The composition for forming an underlayer film for imprinting as described in claim 1 or claim 2, wherein 99.0 mass % or more of the underlayer film-forming composition for imprint is a solvent. The underlayer film-forming composition for imprinting according to claim 1 or claim 2, wherein the polymer has a structural unit containing a polymerizable group. An imprint kit, comprising the imprint underlayer film-forming composition and the imprint curable composition described in any one of the first to eighth claims. A curable composition for imprinting, which is used in the imprinting set described in item 9 of the patent application scope. A laminate comprising a substrate, an underlayer film formed from the imprint underlayer film-forming composition described in any one of the claims 1 to 8 of the scope of application, and an underlayer film located on the surface of the substrate An embossing layer formed of a curable composition for embossing on the surface of the film. The laminate according to claim 11, wherein a substrate having an organic layer as an outermost layer is used as the substrate. The layered product according to claim 11 or claim 12, wherein a layer having an alkalinity is used as the substrate as the outermost substrate. A method for manufacturing a laminate, comprising: applying the underlayer film-forming composition for imprinting described in any one of claims 1 to 8 of the scope of application to the surface of a substrate to form an underlayer film for imprinting ; and a process for applying a curable composition for imprinting on the surface of the underlying film. The manufacturing method of the laminated body as described in Claim 14 of Claim 1 which uses the board|substrate which has an organic layer as an outermost layer as this board|substrate. For the method of manufacturing the layered product described in Item 14 or 15 of the scope of the patent application, Among them, as the substrate, a layer having an alkalinity is used as the substrate of the outermost layer. A pattern forming method, comprising: using the underlayer film forming composition for imprinting described in any one of the claims 1 to 8 of the scope of application to form an underlayer film on the surface of a substrate; applying on the underlayer film Process for forming a composition for imprinting underlayer film to form a curable composition layer for imprinting; a process for bringing casting mold into contact with the layer of curable composition for imprinting; A process of exposing the hardening composition layer; and a process of peeling the mold from the exposed curable composition layer for imprinting. The pattern forming method according to claim 17, wherein a substrate having an organic layer as the outermost layer is used as the substrate. The pattern forming method as described in claim 17 or claim 18 of the claimed scope, wherein a layer having an alkalinity is used as the substrate as the outermost substrate. The pattern forming method described in claim 17 or claim 18, wherein the underlayer film-forming composition for imprinting is applied to the surface of the substrate by a spin coating method. The pattern forming method as described in claim 17 or claim 18, wherein the curable composition for imprinting is applied to the underlayer film by an ink jet method. A manufacturing method of a semiconductor device, which includes the pattern forming method described in any one of items 17 to 21 of the patent application scope.

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