TWI795536B - Composition for forming underlayer film for imprint, kit, composition for forming underlayer film for imprint, underlayer film, laminate and method for producing same, method for producing pattern of hardened product, and method for producing circuit board - Google Patents

Abstract

The present invention provides a composition for forming an underlayer film for imprinting, which includes a polymer and a solvent, In this composition, when the composition for forming an underlayer film for imprint is made into a film and baked at 80° C., a specific compound having a molecular weight of 210 or more is released from the polymer. Furthermore, the present invention relates to a curable composition for imprint related to the underlayer film-forming composition for imprint and a kit using the same.

Description

Underlayer film forming composition for imprint, kit, underlayer film forming set for imprint Product, underlayer film, laminate, method for manufacturing same, method for manufacturing cured product pattern, and method for manufacturing circuit board

The present invention relates to an underlayer film-forming composition for imprinting, a curable composition for imprinting, and a kit.

The imprint method transfers a fine pattern by pressing a mold onto a curable composition, hardening the composition, and peeling off the mold. Attempts are being made to apply this method to precision processing fields such as the manufacture of semiconductor integrated circuits. Due to the embossing method, expensive microfabrication devices such as segmenters or electron beams are not required. Since reduction in manufacturing cost, simple steps, high resolution, and high throughput can be achieved, mass production of devices is being actively studied in various fields.

In the imprint method, there is a technique in which a photosensitive resin composition is used as a material suitable for patterning, combined with a light-transmitting mold, and processed. In this manufacturing method, light is irradiated through a mold to form a pattern on a cured film of a photosensitive resin composition disposed on a substrate, and this is used as an insulating member or a mask for further processing. In some cases, ultraviolet light (UV: Ultraviolet) is used as the light to be irradiated, and it is especially called UV nanoimprint method. The optical nanoimprint method represented by the UV nanoimprint method is different from the thermal nanoimprint method which requires heating using a thermosetting resin composition, and can process at room temperature. Therefore, in the manufacture of heat-repelling semiconductor devices, etc., it can be widely used as a technology for realizing high quality.

In the photonanoimprint method using a photosensitive resin composition, it is proposed to use the underlayer film technology (see Patent Document 1). For example, Patent Document 1 discloses a resin composition for forming an underlayer film, which contains: a resin having a (meth)acryloyloxy group, an alkoxycarbonyl group, and a resin selected from the group consisting of oxiranyl and oxetane at least one group in the group; a nonionic surfactant; and a solvent. In addition, it is described that the variation in residual film thickness after die extrusion is small, and the line width distribution of the pattern after pressurization is less prone to variation.

[Prior Art Literature] [Patent Document]

[Patent Document 1] International Publication No. 2016/027843

As mentioned above, compared with the technology based on photolithography, the formation of fine patterns by imprint is extremely efficient, and can greatly improve the manufacturing cost and productivity of manufacturing semiconductor devices. Furthermore, with the advancement of semiconductor technology, miniaturization of patterns and further improvement in manufacturing quality are required. For example, in order to improve the adhesiveness between the substrate and the curable composition for imprint in the manufacturing process by imprint, the method of using the underlayer film-forming composition for imprint to coat the underlayer film-forming composition for imprint is studied. The wettability of a film formed by applying a curable composition for imprinting to the surface is required to be further improved. Also, of course, the adhesiveness between the underlayer film formed of these compositions and the imprint layer is also required.

Therefore, it is an object of the present invention to provide a curable composition for imprints that is more excellent in wettability of a coating film than an underlayer film-forming composition for imprints, and to provide an underlayer film formed from these compositions that is compatible with imprints. An underlayer film-forming composition for imprints excellent in layer adhesion, a curable composition for imprints, and a kit using them.

Based on the above-mentioned problems, the inventors of the present invention conducted research and found that by using a polymer capable of producing a specific detachment component in the underlayer film-forming composition for imprint, it is possible to solve the problem. resolve the above issues. Specifically, the above-mentioned problems are solved by the following method <1>, preferably <2> to <27>.

<1> An underlayer film-forming composition for imprint, comprising a polymer and a solvent, in which, when the above-mentioned underlayer film-forming composition for imprint is made into a film and baked at 80°C, the following The compound represented by the formula (r1) or (r2) and having a molecular weight of 210 or more is released from the polymer,

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

<2> The underlayer film-forming composition for imprint according to <1>, wherein the compound represented by the above formula (r1) or (r2) is represented by the formula (r1-1),

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

<3> The imprint underlayer film-forming composition according to <1> or <2>, wherein the polymer contains a group represented by any one of the following formulas (R-1) to (R-4) group, [chemical formula 3]

In the formula, R ¹ to R ³ are each independently a monovalent substituent, R ⁴ to R ¹² are each independently a hydrogen atom or a monovalent substituent, and X represents a bonding position to the main chain of the polymer.

<4> The underlayer film-forming composition for imprint according to <3>, wherein the C-O bond in the formula is selected from substituents represented by any one of the above formulas (R-1) to (R-4). The polymer is decomposed, and the compound represented by the above-mentioned formula (r1) or (r2) and having a molecular weight of 210 or more is detached from the above-mentioned polymer.

<5> The composition for forming an underlayer film for imprint according to any one of <1> to <4>, wherein the polymer contains a polymerizable group.

<6> The composition for forming an underlayer film for imprint according to <5>, wherein the polymerizable group includes a (meth)acryl group.

<7> The composition for forming an underlayer film for imprint according to any one of <1> to <6>, wherein the polymer contains an aromatic ring.

<8> The imprint underlayer film-forming composition according to any one of <1> to <7>, wherein the polymer is represented by any one of the following formulas (1) to (6). At least one of the constituent units.

[chemical formula 4]

In the formula, R ^P4 is a hydrogen atom or a methyl group, and R ^P1 represents a group capable of detaching the compound represented by the formula (r1) or (r2).

<9> The imprint underlayer film-forming composition according to any one of <1> to <8>, wherein the compound represented by the above formula (r1) or (r2) contains an aromatic ring.

<10> The imprint underlayer film-forming composition according to any one of <1> to <9>, wherein the compound represented by the above formula (r1) or (r2) contains a polymerizable group.

<11> The composition for forming an underlayer film for imprint according to <10>, wherein the polymerizable group includes a (meth)acryl group.

<12> The composition for forming an underlayer film for imprint according to any one of <1> to <11>, wherein at least one of R ^r1 and R ^r2 of the above formula (r1) is the same as that of the formula (r2) At least one of R ^r4 to R ^r6 contains a polymerizable group.

<13> The imprint underlayer film-forming composition according to any one of <1> to <12>, wherein the compound represented by the above formula (r1) or (r2) has a molecular weight of 1000 or less.

<14> The composition for forming an underlayer film for imprint according to any one of <1> to <13>, further comprising a release reaction accelerator or a precursor thereof.

<15> The composition for forming an underlayer film for imprint according to any one of <1> to <14>, which is A photopolymerization initiator is also included.

<16> The imprint underlayer film-forming composition according to any one of <1> to <15>, wherein the compound represented by the above formula (r1) or (r2) has a surface tension of 35 to 55 mN/m .

<17> The imprint underlayer film-forming composition according to any one of <1> to <16>, wherein the solvent is contained in a proportion of 95.0% by mass or more.

<18> A curable imprint composition containing a polymerizable compound, used in combination with the underlayer film-forming composition for imprint according to any one of <1> to <17>.

<19> A kit comprising the imprint underlayer film-forming composition according to any one of <1> to <17> and a curable imprint composition containing a polymerizable compound.

<20> The kit according to <19>, wherein the Hansen solubility parameter of the compound represented by the above-mentioned formula (r1) or (r2) and the Hansen solubility parameter of the above-mentioned hardening composition for imprinting are determined as follows: The △HSP value calculated by the above mathematical formula (H1) is less than 5, △HSP=(4.0×△D ² +△P ² +△H ² ) ^0.5 ......(H1)

The above ΔD is the difference between the dispersion term component of the Hansen solubility parameter vector of the curable composition for imprinting and the dispersion term component of the Hansen solubility parameter vector of the compound represented by the formula (r1) or (r2), and the above ΔP is the difference between the polar term component of the Hansen solubility parameter vector of the curable composition for imprinting and the polar term component of the Hansen solubility parameter vector of the compound represented by formula (r1) or (r2), and the above ΔH is the imprint The difference between the hydrogen bond component of the Hansen solubility parameter vector of the curable composition and the hydrogen bond component of the Hansen solubility parameter vector of the compound represented by formula (r1) or (r2).

<21> An underlayer film formed of the underlayer film-forming composition according to any one of <1> to <17>.

<22> A laminate formed from the kit described in <19> or <20>, the laminate comprising: an underlayer film formed of the above-mentioned underlayer film-forming composition for imprinting; and an imprint layer composed of the above-mentioned The emboss is formed of a curable composition and located on the surface of the lower layer film.

<23> A method for producing a laminate using the kit described in <19> or <20>, wherein the production method includes forming a surface of an underlayer film formed of the above imprint underlayer film-forming composition Suitable for hardening compositions for imprinting.

<24> The method for producing a laminate according to <23>, wherein the curable composition for imprinting is applied to the surface of the underlayer film by an inkjet method.

<25> The method for producing a laminate according to <23> or <24>, wherein the production method further includes a process of applying the imprint underlayer film-forming composition on a substrate in a layered form, and the step of 80 Heating at ~250°C is suitable for the process of forming the above layered underlayer film-forming composition for imprinting.

<26> A method for manufacturing a cured product pattern, which uses the kit described in <19> or <20> to manufacture a cured product pattern, and the method for manufacturing a cured product pattern includes: a lower layer film forming process, and applying embossing on a substrate An underlayer film is formed by using an underlayer film forming composition; an application process is applied to the surface of the above underlayer film with a curable composition for imprinting; a mold contact process is used to combine the above curable composition for imprint with a shape for transferring a pattern The mold contact of the pattern; the light irradiation process, irradiating light to the curable composition for imprint to form a cured product; and the demoulding process, separating the cured product from the mold.

<27> A method for manufacturing a circuit board, including a process of obtaining a cured product pattern by the method described in <26>.

According to the present invention, it is possible to improve the wettability of the imprint curable composition to the coating film of the imprint underlayer film-forming composition and the adhesion between the underlayer film and the imprint layer formed of the composition. In addition, an underlayer film-forming composition for imprint, a curable composition for imprint, and a kit for applying the same can be provided.

1: Substrate

2: Lower film

3: Hardening composition for imprinting

4: Molding

21: Lower film

22: Hardening composition for imprinting

22a, 22b, 22c: film-like curable imprint composition

23: Area without membrane

FIG. 1 is a process explanatory diagram showing an example of a manufacturing step when forming a cured product pattern and using the obtained cured product pattern for processing a substrate by etching.

Fig. 2 is a plan view schematically showing the state of wetting and spreading of the curable composition for imprint when the curable composition for imprint is coated on the surface of the underlayer film with low wettability by the inkjet method.

Hereinafter, the content of the present invention will be described in detail. In addition, in this specification, "~" is used in the meaning which includes 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 this specification, "imprinting" refers to transfer printing of a pattern preferably having a size of 1 nm to 10 mm, more preferably transfer printing of a pattern having a size of about 10 nm to 100 μm (nanoimprinting).

In the notation of a group (atomic group) in the present specification, the notation of substitution and unsubstituted notation includes those not having a substituent and those having a substituent. For example, "alkyl" includes not only unsubstituted alkyl (unsubstituted alkyl), but also substituted alkyl (substituted alkyl).

In this specification, "light" includes not only light or electromagnetic waves having wavelengths in ultraviolet, near ultraviolet, far ultraviolet, visible, infrared, and other regions, 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, or a 172 nm excimer laser can also be used. Such light may be monochromatic light (single-wavelength light) passed through an optical filter, or may be light having a plurality of different wavelengths (composite light).

The temperature in the present invention is set to 23° C. when there is no particular description.

The boiling point in the present invention refers to the boiling point in 1 atmospheric pressure (1atm=1013.25hPa).

The underlayer film-forming composition for imprint of the present invention is characterized in that it contains a polymer and a solvent. When the underlayer film-forming composition for imprint is made into a film and baked at 80° C., the following formula (r1) or ( The compound represented by r2) (hereinafter, may be referred to as a detachment component) desorbs from the polymer. Thereby, the wettability of the imprint curable composition to the coating film of the imprint underlayer film-forming composition during imprinting is improved, and the adhesiveness between the underlayer film and the imprint layer formed of these compositions is improved. improve. The reason for this can be presumed as follows. That is, it is considered that the generation of low-molecular components leads to a decrease in the interfacial tension on the surface of the underlayer film, thereby improving wettability. In addition, it is considered that a diffusion path is generated in the underlayer film, whereby the curable component of the curable composition for imprint penetrates into the region where the low molecular component exists in the underlayer film, and a part of it is cured, thereby forming a gap between the underlayer film and the cured product. The adhesion is improved.

<Underlayer Film Forming Composition for Imprint>

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

<<Departure ingredients>>

The release component is a component that makes the imprint underlayer film-forming composition into a film and releases from the polymer when baked at 80° C., and is a compound having a predetermined structure and a molecular weight of 210 or more.

The desorbed component in the first embodiment of the present invention is represented by the following formula (r1) or (r2). If the release component is a compound represented by formula (r1) or (r2), the polymerization initiator in the curable composition for imprint also diffuses into the underlayer film-forming composition for imprint, and the curable composition for imprint When curing, the underlayer film-forming composition for imprint is also cured at the same time, so that the adhesiveness between the curable composition for imprint and the underlayer film is further improved.

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

The compound represented by formula (r1) or (r2) is preferably represented by the following formula (r1-1).

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

The detached component (the compound represented by the formula (r1) or (r2) or the compound represented by the formula (r1-1)) preferably contains an aromatic ring (preferably the following ring aCy or hCy).

In particular, at least one of R ^r1 and R ^r2 of formula (r1), at least one of R ^r4 to R ^r6 of formula (r2), at least one of R ^r1 and R ^r2 of formula (r1-1) One containing an aromatic ring is preferred. The aromatic ring is preferably the following ring aCy or hCy.

(chrysene)環、苝環、四氫萘環等。芳香族環可採取經由或不經由連結基L複數個連結而成之結構，例如，可舉出聯苯環、二苯甲烷環、三苯甲烷環。或者，還包括一部分上述中例示者在內，作為複數個苯環連結而成之結構可舉出下述式Ar1~Ar5者。式中從苯環的中心附近向外描繪之直線表示鍵結鍵。係指經由該單鍵與任意連結基鍵結，或者經由或不經由該單鍵與下述式(T1)的L¹、L²、P或聚合物的主鏈鍵結。A¹為2價的連結基，連結基L的例為較佳，可由氟原子取代之伸烷基(碳數1~12為較佳，1~6為更佳，1~3為進一步較佳)、羰基、氧原子、磺醯基、亞磺醯基、-NR^N-為更佳。A²係指包含氮原子、磷原子之3價的連結基或次甲基。表示式Ar1~Ar5中，鍵結鍵任意存在2個或3個，係指依據所需的連結數在所需的部分鍵結即可。例如，從1個苯環延伸有2個鍵結鍵之態樣亦能夠作為本發明的較佳態樣而舉出。又，具有3個環之Ar2為2價的連結基之態樣亦能夠作為本發明的較佳態樣而舉出。 Specific examples when the aromatic ring is an aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a phenanthrene ring, a fenene ring, an acenaphthylene ring, a biphenyl ring, a terphenyl ring, an indene ring, a biphenyl ring, Hydroindene ring, three phenylene rings, tetraphenylene rings, pyrene rings,

(chrysene) ring, perylene ring, tetrahydronaphthalene ring, etc. The aromatic ring may have a structure in which a plurality of links are connected via or not via a linking group L, for example, a biphenyl ring, a diphenylmethane ring, and a triphenylmethane ring. Alternatively, including some of those exemplified above, the structure in which a plurality of benzene rings are linked includes those of the following formulas Ar1 to Ar5. In the formula, a straight line drawn outward from near the center of the benzene ring indicates a bonding bond. It means bonding to any linking group via the single bond, or bonding to L ¹ , L ² , P of the following formula (T1) or the main chain of the polymer via the single bond or not. A ¹ is a divalent linking group, the example of the linking group L is preferred, and an alkylene group that can be substituted by a fluorine atom (1~12 carbons is more preferable, 1~6 is more preferable, 1~3 is further preferable ), carbonyl, oxygen atom, sulfonyl, sulfinyl, -NR ^N - are more preferred. A ² means a trivalent linking group or a methine group including a nitrogen atom and a phosphorus atom. In the expressions Ar1~Ar5, there are optionally 2 or 3 bonding bonds, which means that the bonding may be at the required part according to the required number of connections. For example, an aspect in which two bonds extend from one benzene ring can also be mentioned as a preferred aspect of the present invention. Moreover, the aspect in which Ar2 which has 3 rings is a divalent linking group can also be mentioned as a preferable aspect of this invention.

[chemical formula 7]

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

環、異吲哚環、吲哚環、吲唑環、嘌呤環、喹嗪環、異喹啉環、喹啉環、酚嗪環、萘啶環、喹噁啉環、喹唑啉環、噌啉(cinnoline)環、咔唑環、吖啶環、啡嗪(phenazine)環、啡噻嗪(phenothiazine)環、啡

環等。 When the aromatic ring is an aromatic heterocyclic ring, its carbon number is preferably 1-12, more preferably 1-6, and still more preferably 1-5. Specific examples thereof include thiophene ring, furan ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, oxazole ring, pyridine ring, piperazine ring, pyrimidine ring, Oxyzine ring, three

ring, isoindole ring, indole ring, indazole ring, purine ring, quinazine ring, isoquinoline ring, quinoline ring, phenazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnamon Cinnoline (cinnoline) ring, carbazole ring, acridine ring, phenazine (phenazine) ring, phenothiazine (phenothiazine) ring,

Ring etc.

The aromatic heterocycle may be a structure in which a plurality of ring structures are linked via a linking group L or not.

The aromatic heterocycle shown here is called ring hCy.

As the aromatic ring contained in the release component, a benzene ring is preferable among them.

An aromatic ring may have a substituent T within the range which exhibits the effect of this invention. When there are plural substituents T, they may be bonded to each other, or may be bonded to the ring in the formula via or not via the linking group L to form a ring. For example, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, etc. may be further substituted with a halogen atom (preferably a fluorine atom).

Moreover, it is preferable that a release component contains a polymerizable group. As a polymeric group, the group containing an ethylenically unsaturated group, an epoxy group, a glycidyl group, an oxetanyl group etc. is mentioned, for example. Examples of the ethylenically unsaturated group include groups containing vinyl, allyl, vinylphenyl, (meth)acryl, and (meth)acryloxy. The polymerizable group exemplified here is called polymerizable group Ps. In the present invention, among them, it is preferable that the polymerizable group Ps contains a (meth)acryl group or a (meth)acryloxy group.

In particular, at least one of R ^r1 and R ^r2 of formula (r1), at least one of R ^r4 to R ^r6 of formula (r2), at least one of R ^r1 and R ^r2 of formula (r1-1) One containing a polymerizable group is preferred. As the polymerizable group, the aforementioned polymerizable group Ps is preferable.

Furthermore, it is preferable that a release component contains an ethylenic double bond. In particular, it is preferable to form an ethylenic double bond by detachment from the polymer. By performing such separation, the effect of adhesion force is exerted.

In formula (r1) or (r2) or formula (r1-1), when R ^r1 , R ^r2 , R ^r4 , R ^r5 , R ^r6 are substituents, examples of the substituents include the substituent T described below. For example, wherein, are independently alkyl (1~12 carbon number is better, 1~6 is better, 1~3 is further better), alkenyl (carbon number 2~12 is better, 2~ 6 is more preferable, 2~3 is further preferable), aryl group (carbon number 6~22 is preferable, 6~18 is more preferable, 6~10 is further preferable), aralkyl group (carbon number 7~ 23 is preferable, 7-19 is more preferable, 7-11 is still more preferable) or a group represented by the following formula (RL-1) is preferable. Furthermore, in formulas (r1) and (r2), at least R ^r2 or R ^r6 is particularly preferably a group represented by the following formula (RL-1).

^LR1 and ^LR2 are each independently a single bond or a linking group, Ar ^R is a linking group including an aromatic ring, and ^PR is a group having a polymerizable group. nr is an integer of 0~8, and mr is an integer of 1~4.

L ^R1 is 1+mr valence aromatic ring (the example of above-mentioned aCy or hCy is better), alicyclic (the example of following alicyclic fCy is better), straight chain or branched alkane structure group (carbon number 1-40 is better, 1-30 is better, 1-20 is further better), straight-chain or branched olefin structure group (carbon number 2-40 is better, 2-30 is better, 2-20 is further preferred), or a linear or branched alkyne structure group (2-40 carbons is preferred, 2-30 is more preferred, 2-20 is further preferred) is preferred.

It is preferable that the linking group of L ^R2 is a linking group Lh including the following linking group L or the following heteroatom. Among them, alkylene group (preferably 1~12 carbon number, more preferably 1~6, further preferably 1~3), arylylene group (preferably 6~22 carbon number, more preferably 6~18 , 6~10 is further preferred), (oligomeric) alkylene group (the carbon number of the alkylene group in 1 constituent unit is 1~12 is better, 1~6 is more preferably, 1~3 is It is further preferred; the number of repetitions is 1-50 is preferred, 1-40 is more preferred, 1-30 is further preferred), carbonyl group, oxygen atom or a combination thereof are preferred.

^LR2 may be bonded to ^LR1 via or not via a linker L to form a ring.

Ar ^R is a linking group including an aromatic ring. However, when nr is 0, Ar ^R is a substituent including an aromatic ring. As the aromatic ring, the aforementioned ring aCy or hCy is preferable. When Ar ^R contains a substituent other than an aromatic ring, examples of the linking group L include the following linking group L, wherein an alkylene group (preferably 1 to 24 carbons, more preferably 1 to 12 carbons, 1~6 is further preferred), alkenylene group (2~12 carbon number is preferred, 2~6 is more preferred, 2~3 is further preferred), alkynylene group (carbon number 2~12 is preferred , 2~6 is more preferable, 2~3 is further preferable), (oligomeric) alkylene group (the carbon number of the alkylene group in 1 constituent unit is 1~12 is better, 1~6 is More preferably, 1~3 is further more preferable; repeat number is 1~50 is more preferable, 1~40 is more preferable, 1~30 is further more preferable), extended aryl group (carbon number 6~22 is preferable, 6-18 are more preferred, 6-10 are further preferred) or a combination thereof. Ar ^R may be bonded to ^LR1 , ^LR2 or PR via a linker L or not via a linker ^L to form a ring.

^PR is a group having a polymerizable group, and the example in which the polymerizable group is the above-mentioned polymerizable group Ps is preferable. ^PR may be bonded to ^LR1 and ^LR2 via a linker L or not via a linker L to form a ring.

^LR1 , ^LR2 , Ar ^R , and ^PR may have a substituent T within the range in which the effects of the present invention are exhibited. For example, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, etc. may be further substituted with a halogen atom (preferably a fluorine atom).

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

Examples of the divalent substituent of R ^r3 include CH ₂ (second embodiment described below), CHR ^r8 or C(R ^r9 ) ₂ . Wherein, R ^r8 and R ^r9 are respectively independently the substituent T described later, wherein, alkyl (carbon number 1~12 is better, 1~6 is more preferable, 1~3 is further preferable), alkenyl ( Carbon number 2~12 is better, 2~6 is better, 2~3 is further better), alkynyl (carbon number 2~12 is better, 2~6 is better, 2~3 is further better) preferably), aryl (preferably 6-22 carbons, more preferably 6-18, further preferably 6-10), aralkyl (preferably 7-23 carbons, more preferably 7-19 , 7~11 is further preferred) is preferred. Two R ^r9 of C(R ^r9 ) ₂ may be the same as or different from each other.

Examples of the linking group Lh containing a heteroatom include an oxygen atom, a sulfur atom, a carbonyl group, a thiocarbonyl group, a sulfonyl group, a sulfinyl group, -NR ^N -, (oligo)alkoxyl (one constituent unit) The carbon number of the alkylene group is preferably 1~12, more preferably 1~6, and further preferably 1~3; the number of repetitions is preferably 1~50, more preferably 1~40, 1~ 30 is further preferred) or a linking group formed by a combination of these. The number of atoms constituting the linking group Lh including heteroatoms is preferably 1-100, more preferably 1-70, and most preferably 1-50, excluding hydrogen atoms. The number of linking atoms of Lh is preferably 1-25, more preferably 1-20, still more preferably 1-15, and still more preferably 1-10. Furthermore, the (oligomeric) alkyleneoxy group may be an alkyleneoxy group or an oligomeric alkyleneoxy group. The above-mentioned (oligo)alkyleneoxy group may be chain or cyclic, straight chain or branched. When the linking group is a group capable of forming a salt such as -NR ^N- or a carboxyl group substituted, the group can form a salt.

Examples of the substituent T include alkyl (preferably 1 to 24 carbons, more preferably 1 to 12, further preferably 1 to 6), arylalkyl (preferably 7 to 21 carbons, 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 more preferable, 2~3 is further preferable), hydroxyl group, amino group (carbon number 0~24 is preferable, 0~12 is more preferable, 0~6 is further preferable ), thiol, carboxyl, aryl (preferably 6-22 carbons, more preferably 6-18, further preferably 6-10), alkoxy (preferably 1-12 carbons, 1 ~6 is more preferable, 1~3 is further preferable), aryloxy group (6~22 carbon number is preferable, 6~18 is more preferable, 6~10 is further preferable), acyl group (carbon number 2 ~12 is better, 2~6 is more preferable, 2~3 is further preferable), acyloxy group (carbon number 2~12 is preferable, 2~6 is more preferable, 2~3 is further preferable) , Aryl (preferably 7~23 carbons, more preferably 7~19, further preferably 7~11), aryloxy (preferably 7~23 carbons, more preferably 7~19 , 7-11 is further preferred), carbamoyl (carbon number 1-12 is better, 1-6 is more preferred, 1-3 is further preferred), sulfamoyl group (carbon number 0-12 preferably, 0~6 is more preferable, 0~3 is further preferable), sulfonic acid group, alkylsulfonyl group (carbon number 1~12 is preferable, 1~6 is more preferable, 1~3 is more preferably), arylsulfonyl (6~22 carbons is more preferable, 6~18 is more preferable, 6~10 is more preferable), heterocyclyl (1~12 carbons is preferable, 1 ~8 is more preferred, 2~5 is further preferred, comprising 5-membered ring or 6-membered ring is preferred), (meth)acryl group, (meth)acryloxy group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), oxo group (=O), imino group (=NR ^N ), alkylene group (=C(R ^N ) ₂ ) and the like. R ^N is a hydrogen atom, an alkyl group (preferably 1-12 carbons, more preferably 1-6, further preferably 1-3), alkenyl (preferably 2-12 carbons, 2-6 More preferably, 2~3 is more preferably), alkenyl (2~12 is more preferably, 2~6 is more preferably, 2~3 is more preferably), aryl (6~22 is more preferably better, 6~18 is better, 6~10 is further better), or aralkyl (carbon number 7~23 is better, 7~19 is better, 7~11 is further better), wherein, Hydrogen atom, methyl group, ethyl group or propyl group are preferred. The alkyl moiety, alkenyl moiety, and alkynyl moiety contained in each substituent may be chain or cyclic, straight chain or branched. When the said substituent T is a group which can obtain a substituent, it may have a substituent T further. For example, the alkyl group may be a halogenated alkyl group, or may be a (meth)acryloxyalkyl group, an aminoalkyl group or a carboxyalkyl group. When the substituent is a group capable of forming a salt such as a carboxyl group or an amine group, the group can form a salt.

As the linking group L, there can be mentioned alkylene (preferably 1-24 carbons, more preferably 1-12, further preferably 1-6), alkenylene (preferably 2-12 carbons, 2~6 is more preferable, 2~3 is further preferable), alkynylene (carbon number 2~12 is preferable, 2~6 is more preferable, 2~3 is further preferable), (oligomeric) stretch Alkoxy (the carbon number of the alkylene group in one constituent unit is preferably 1-12, more preferably 1-6, further preferably 1-3; preferably 1-50 repetitions, 1 ~40 is more preferable, 1~30 is further preferable), extended aryl group (6~22 carbon number is preferable, 6~18 is more preferable, 6~10 is further preferable), oxygen atom, sulfur atom, Linking groups of sulfonyl, carbonyl, thiocarbonyl, -NR ^N- and combinations thereof. The alkylene group may have the substituent T described above. For example, an alkylene group may have a hydroxyl group. The number of atoms contained in the linking group L other than hydrogen atoms is preferably 1-50, more preferably 1-40, and still more preferably 1-30. The number of linked atoms refers to the number of atoms located in the shortest distance among the atomic groups participating in the link. For example, in the case of -CH ₂ -(C=O)-O-, there are 6 atoms participating in the connection, and 4 atoms other than hydrogen atoms. On the other hand, the shortest atoms participating in the connection are -CCO-, which becomes three. As this number of linking atoms, 1-24 are preferable, 1-12 are more preferable, and 1-6 are still more preferable. Furthermore, the above-mentioned alkylene group, alkenylene group, alkynylene group, and (oligo)alkylene group may be chain-like, cyclic, straight-chain, or branched. When the linking group is a group capable of forming a salt such as -NR ^N- , the group can form a salt.

The molecular weight of the released component is 210 or more. It is preferable that the molecular weight is more than the lower limit value so that volatilization during baking is suppressed. The molecular weight of the release component is preferably 210 or more, more preferably 250 or more, and still more preferably 300 or more. As an upper limit, it is actually 1000 or less.

The surface tension of the release component is preferably 28 mN/m or more, more preferably 30 mN/m or more, still more preferably 36 mN/m or more, still more preferably 38 mN/m or more, still more preferably 40 mN/m or more Better, 42 mN/m or more is still more preferable. As an upper limit, 80 mN/m or less is preferable, 60 mN/m or less is more preferable, 50 mN/m or less is still more preferable.

The Hansen Solubility Parameter (HSP) vector from the component: (i) dispersion item component (d component) is 14.0~20.0 is better, 15.0~19.0 is better, 16.0~19.5 is further better; (ii) polarity The item component (p component) is 2.0~9.0 is better, 3.0~6.0 is better, 3.5~5.0 is further better; (iii) the hydrogen bond item component (h component) is 3.0~12.0 is better, 4.7~ 7.0 is more preferable, and 5.0-6.5 is still more preferable.

<<specific polymer>>

Regarding the polymer used in the present invention (hereinafter, the polymer may be referred to as a specific polymer), the imprint underlayer film-forming composition containing the specific polymer is made into a film and the temperature is 80 to 250 When baking at ℃, polymers that detach the detachment component from the polymer can be widely used. More specifically, it is preferable that the specific polymer has a group serving as a detachment component in a side chain.

In the present invention, among all the structural units constituting the polymer, preferably 30% by mass or more, more preferably 40% by mass or more, are structural units capable of detaching the detachment component. The upper limit is not particularly limited, and may be 100% by mass. Furthermore, in the present invention, it is not necessary to detach all the constituent units having a group capable of detachment from the detachment component under heating at 80 to 250° C., as long as at least 70% by mass is detached, preferably 80% by mass or more. It is still more preferable to deviate from 90 mass % or more, and it is still more preferable to deviate from 99 mass % or more.

In addition, in the present invention, preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more of the detachment component of the mass of the specific polymer are desorbed. The upper limit is not particularly limited, but is, for example, 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less.

It is preferable that the specific polymer contains a substituent represented by any one of the following formulas (R-1) to (R-4).

In the formula, R ¹ to R ³ are each independently a monovalent substituent, R ⁴ to R ¹² are each independently a hydrogen atom or a monovalent substituent, and X represents a bonding position to the main chain of the polymer.

In the formulas (R-2)~(R-4), it is preferable that R ⁴ ~R ⁶ , R ⁷ ~R ⁹ , and R ¹⁰ ~R ¹² are not all hydrogen atoms. Contains a carbon atom bonded to the oxygen atom in the formula (R-1), that is, a carbon atom in which R ¹ to R ³ is substituted (hereinafter, the carbon atom at this position is referred to as an α carbon atom in each formula) The group is preferably a secondary or tertiary alkyl group. Also in the formula (R-2), it is preferable that the group containing an α carbon atom is a secondary alkyl group or a tertiary alkyl group. On the other hand, it is preferable that the group containing the α-carbon atom in the formulas (R-3) and (R-4) is a primary or secondary alkyl group.

It is preferable that at least one of R ¹ to R ³ is a substituent, and it is more preferable that at least two are substituents. It is preferable that at least one of R ⁴ to R ⁶ is a substituent, and it is more preferable that at least two are substituents. It is preferable that at least one of R ⁷ to R ⁹ is a substituent, and it is more preferable that two of them are hydrogen atoms and one of them is a substituent. It is preferable that at least one of R ¹⁰ to R ¹² is a substituent, and it is more preferable that two of them are hydrogen atoms and one of them is a substituent. When R ¹ to R ³ , R ⁴ to R ⁶ , R ⁷ to R ⁹ , and R ¹⁰ to R ¹² are substituents, the substituents include groups with the same meaning as R ^r1 above, and the preferred range is also same.

R ¹ to R ³ , R ⁴ to R ⁶ , R ⁷ to R ⁹ , and R ¹⁰ to R ¹² may be bonded to each other to form a ring. When R ¹ to R ¹² are substituents, they may further have a substituent T within the range of exerting the effects of the present invention. For example, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, etc. may be further substituted with a halogen atom (preferably a fluorine atom).

In the present invention, the C-O bond in the formula is decomposed from the polymer comprising the substituent represented by any one of the formulas (R-1) to (R-4), and the formula (r1) or (r2) or the formula (r1 -1) means that a compound with a molecular weight of 210 or more is detached from the polymer.

In particular, the carbon atom substituted by R ^r1 and R ^r2 of the formula (r1) (the carbon atom at the second position when the carbon atom contained in R ^r3 is set as the first position) is the R of the formula (R-1) before leaving ¹ to R ³ are preferably substituted carbon atoms (α carbon atoms). Also, the carbon atom at the 2-position of the formula (r1) is preferably a carbon atom substituted by R ⁴ to R ⁶ of the formula (R-2) before leaving. Regarding formula (r2), the tertiary carbon atoms substituted by R ^r4 ~ R ^r6 are the carbon atoms substituted by R ¹ ~ R ³ of formula (R-1) or formula (R -2) R ⁴ ~ R ⁶ are preferably substituted carbon atoms.

In formula (R-1), at least one of R ¹ to R ³ is an alkyl group in such a way that it decomposes at the position of CO and forms a double bond at the detachment position (position of α carbon atom) on the detachment side of the component (C1-12 is preferred, 1-6 is more preferred, 1-3 is further preferred) is preferred, ethyl is more preferred, and methyl is further preferred. It is also the same in formula (R-2), at least one of ^R4 ~ ^R6 is an alkyl group (preferably 1~12 carbons, more preferably 1~6, more preferably 1~3) is Preferably, ethyl is more preferred, and methyl is further preferred.

Moreover, it is preferable that a specific polymer contains a polymeric group, it is preferable that a polymeric group is a polymeric group Ps, and it is more preferable that it contains a (meth)acryl group. The polymerizable group may be contained in a structural unit having a group capable of releasing a releasing component, or may be contained in another structural unit. In the present invention, it is preferable that at least the structural units other than the structural unit having a group capable of releasing the releasing component have a polymerizable group.

In a specific polymer, the proportion of constituent units having a polymerizable group is preferably 10 to 100 mole % of all constituent units, more preferably 50 to 100 mole %, and further preferably 80 to 100 mole %. better.

Also, it is preferable that the specific polymer contains an aromatic ring, and it is preferable that the aromatic ring is ring aCy or hCy. An aromatic ring may be included in a structural unit having a group capable of releasing a releasing component, or an aromatic ring may be included in another structural unit. In the present invention, at least a structural unit having a group capable of detaching a detachment component preferably has an aromatic ring.

In a specific polymer, the proportion of structural units including an aromatic ring is preferably 10 to 100 mol%, more preferably 40 to 100 mol%, of all the structural units.

The type of specific polymer is not particularly limited, but, for example, (meth)acrylate resin, polyolefin resin, polystyrene resin, phenol resin (novolac resin), cyclo Polyolefin resin, polyamide resin, polyimide resin, polyacetal resin, polycarbonate resin, polyester resin, polyurethane resin and silicone resin, etc.

It is still more preferable that a specific polymer contains at least 1 sort(s) of the structural unit represented by any one of following formula (1) - a formula (6).

R ^P4 is a hydrogen atom or a methyl group.

R ^P1 represents a group capable of leaving a compound represented by formula (r1) or (r2) or a compound represented by formula (r1-1), including groups represented by formulas (R-1) to (R-4) A group of groups is preferred. In R ^P1 , the linking group may be between X of the formulas (R-1)~(R-4) and the atoms of the main chain. As a linking group, the example of linking group L is mentioned. In addition, the linking group at this time may be trivalent or more. In this case, the structural unit to be a polymer is accompanied by a plurality of groups represented by formulas (R-1) to (R-4) via a linking group. As the linking group having a valence of 3 or more, groups having an aromatic ring (aCy, hCy) structure and alkane structure groups (preferably 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, further preferably 1 to 20 carbon atoms) preferably), groups of alkene structure (preferably 2 to 40 carbons, more preferably 2 to 30, further preferably 2 to 20), groups of alkyne structures (preferably 2 to 40 carbons , 2 to 30 are more preferred, 2 to 20 are further preferred) or a combination of these groups or a combination of these and the linking group Lh. The group of alkane structure, the group of alkene structure, and the group of alkyne structure may be chain-like, cyclic, straight-chain or branched. Hereinafter, the linking group having a valence of more than three is referred to as linking group Lm.

In the formulas (1) to (6), the substituent R ^P1 may be substituted with two or more in the same constitutional unit. For example, in formulas (1) and (2), those in which two or more R ^P1 are substituted on the benzene ring can also be cited as preferred embodiments of the present invention.

The main chain and substituent R ^P1 of the polymer in formula (1)-(6) may have a substituent T in the range which exhibits the effect of this invention.

The above-mentioned specific polymer-based copolymers are also preferable. It is preferable that a copolymerization component contains at least 1 sort(s) of the structural unit (it may be called another structural unit hereinafter) represented by any one of following formula (1-1)-(1-6).

In the formulas (1-1) to (1-6), the substituents R ^P2 are each independently a substituent containing a polymerizable group, and R ^P4 is a hydrogen atom or a methyl group. It is preferable that the polymerizable group contained in R ^P2 is the above-mentioned Ps. R ^P2 may have a linking group between the polymerizable group and the main chain. In the case of a divalent linking group, an example of the linking group L is given, and in the case of a trivalent or higher linking group, an example of the linking group Lm is given. When there are two or more R ^P2 in formulas (1-1) to (1-6), that is, when it becomes (R ^P2 ) _n (n is a natural number greater than or equal to 1), a plurality of R ^P2 can be bonded to each other And form a ring. Also, R ^P2 may be bonded to the main chain to form a ring. In addition, substituent T may be substituted on the main chain and substituent R ^P2 of formula (1-1) to formula (1-6) within the range of exerting the effect of the present invention.

As R ^P2 , the following formula (T2) is preferable. The formula weight of R ^P2 is preferably from 80 to 1000, more preferably from 100 to 800, and still more preferably from 150 to 600.

-(L4) _n6 -(P) _n7 ......(T2)

^L4 is the above-mentioned linking group L or Lm, wherein, alkylene, aryl, (oligo)alkoxyl, carbonyl, oxygen atom, group of alkane structure, group of alkene structure, group of aryl structure A group and a linking group of a combination of these are preferred. n6 is an integer of 0~6. P is a polymerizable group Ps. n7 is an integer of 1 to 6, preferably 1 or 2. Furthermore, when n7 is 3 or more, the terminal L ⁴ becomes a linking group having a valency of 4 or more and all Ps may be substituted, but two or more L ^4s may be substituted for P.

When a specific polymer contains the structural unit represented by formula (1), as another structural unit, the structural unit represented by formula (1-1) is preferable. Also about formula (2) - formula (6), it is preferable to contain the structural unit represented by formula (1-2) - formula (1-6) respectively similarly.

It is also preferable that the specific polymer further includes a structural unit having no polymerizable group (sometimes referred to as "another structural unit"). Another structural unit preferably has a skeleton of the formulas (1-1) to (1-6) defined in the above other structural units. However, the substituent R ^P2 is a substituent R ^P3 having no polymerizable group. Two or more of R ^P2 in formulas (1-1), (1-2), (1-4), and (1-6) which are another structural unit may be substituted with a ring structural group. Furthermore, in another structural unit, the substituent T may be substituted in a part of the main chain and R ^P3 within the range in which the effect of the present invention is exhibited.

R ^P3 is preferably the following formula (T3). The formula weight of R ^P3 is preferably from 80 to 1000, more preferably from 100 to 800, and still more preferably from 150 to 600.

-(L5) _n8 -(T1) _n9 ......(T3)

^L5 is the above linking group L or Lm, wherein, alkylene, arylylene, (oligo)alkoxyl, carbonyl, oxygen atom, alkane structure group, alkene structure group, aryl structure group A group and a linking group of a combination of these are preferred. ^T1 is the above-mentioned substituent T, for example, an alkyl group, an aryl group, an alkoxy group, an acyl group, etc. are mentioned. n9 is an integer of 1 to 6, preferably 1 or 2. When n9 is 3 or more, the terminal L ⁵ becomes a linking group having a valency of 4 or more and all T ^1s may be substituted, but T ¹ may be substituted at two or more L ^5s .

In the formulas T2 and T3, L ⁴ , L ⁵ , P, and T ¹ may have the above-mentioned substituent T within the range in which the effects of the present invention are exerted. For example, groups with alkane structure, groups with alkene structure, groups with aryl structure, etc. may be further substituted with halogen atoms (preferably fluorine atoms).

In a specific polymer, the structural unit represented by any one of the formulas (1) to (6) can constitute the entire polymer (a homopolymer with a constituent ratio of 100 mol%), or can be combined with other structural units Or another copolymer of other constituent units.

In a specific polymer, on a molar ratio basis, there are structural units (for example, structural units represented by formula (1) to formula (6))/other structural units (with The constituent unit of the polymerizable group)/another constituent unit ratio is 10~100/0~80/0~50 is better, 30~100/0~70/0~30 is more preferable, 50~ 100/0~50/0~10 is more preferable, and may be 50~90/10~50/0~10.

In a specific polymer, only one or two or more structural units having a group capable of releasing a releasing component, another structural unit (a structural unit having a polymerizable group), and another other structural unit may be included. When containing 2 or more types, it is preferable that it becomes the said ratio in total.

In addition, in the present invention, it is also preferable to have a structure that does not actually include a structural unit having a group capable of releasing a releasing component and another structural unit other than a structural unit having a polymerizable group. Substantially not containing means, for example, 5% by mass or less of all structural units, preferably 3% by mass or less, and more preferably 1% by mass or less.

The weight average molecular weight of the specific polymer is preferably 4,000 or more, and 5,000 or more is More preferably, 7,000 or more is still more preferable, and 10,000 or more is still more preferable. The upper limit is preferably at most 2,000,000, more preferably at most 1,500,000, and further preferably at most 1,000,000. The measurement method of the weight average molecular weight is set by the method shown by the following example.

The content of the specific polymer in the underlayer film-forming composition for imprinting is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1.0% by mass or more, and more preferably 1.5% by mass or more . The upper limit is preferably at most 10% by mass, more preferably at most 7% by mass, still more preferably at most 5% by mass, still more preferably at most 4% by mass, and still more preferably at most 3% by mass. By making this amount more than the said lower limit, the effect by blending a polymer can be exhibited suitably, and it becomes easy to manufacture a uniform thin film. On the other hand, by making it below the said upper limit, the effect of using a solvent is exhibited suitably, and it becomes easy to form a uniform film over a wide area.

In addition, the content of the specific polymer relative to the non-volatile component (referring to the solid content excluding the solvent in the composition) in the imprint underlayer film-forming composition is preferably 90% by mass or more, and 95% by mass The above is more preferable, and 99 mass % or more is still more preferable. As an upper limit, it is 100 mass %. By making this amount more than the said lower limit, the effect by blending a polymer can be exhibited suitably, and it becomes easy to manufacture a uniform thin film. On the other hand, by making it below the said upper limit, the effect of using a solvent is exhibited suitably, and it becomes easy to form a uniform film over a wide area.

Only 1 type may be used for a specific polymer, and 2 or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.

In the above-mentioned polymer, the substituent R ^P1 that forms the detachment component can be introduced into the main chain by a conventional method.

<<Detachment reaction accelerator or its precursor>>

By co-existing with a specific polymer in the system, the detachment reaction accelerator can pass through the given A compound that acts on a specific polymer to promote a reaction in which a detachment component is detached from a specific polymer. The detachment reaction accelerator is a compound having an acidic functional group or a basic functional group. It is preferable that the desorption reaction accelerator exists as its precursor in the composition. As a precursor, for example, a compound that reacts by applying external energy such as heat or light, and converts into a compound that is released from a reaction accelerator compound is mentioned. Specifically, thermal acid generators, photoacid generators, thermal base generators, photobase generators, etc. are mentioned, thermal acid generators and photoacid generators are preferable, and thermal acid generators are more preferable.

When the detachment accelerator has an acidic functional group, the pKa of the detachment accelerator is preferably 2 or less, more preferably 1 or less, and still more preferably 0 or less. Although it does not specifically limit as a lower limit, For example, -10 or more may be sufficient. When having a basic functional group, the pKa of the conjugate acid is preferably 5 or more, more preferably 7 or more, and still more preferably 8 or more. Although it does not specifically limit as an upper limit, For example, it may be 15 or less.

In the present invention, as specific examples of the desorption reaction accelerator or its precursor, the acid proliferators described in paragraphs 0012, 0017, 0026 to 0037 of JP-A-2014-047329 , and the photoproliferators described in 0038 to 0040 can be used. Acid generators, thermal acid generators described in paragraph 0041, photobase multiplying agents described in paragraphs 0029 to 0066 of JP-A-2012-237776, photobase generators described in paragraphs 0073 to 0087, and photobase generators described in paragraphs 0087 to 0090 Thermal base generators described in paragraphs, photoacid generators described in paragraphs 0012 to 0015 and 0023 to 0029 of Japanese Patent No. 5687442, base generators described in paragraphs 0033 to 0075 of International Publication No. 2009/123122 , the base generating agent described in 0038-0069 of JP-A-2011-236416, and these contents are incorporated in this specification.

The content of the detachment reaction accelerator or its precursor is 0.1% by mass of the non-volatile components The above is preferable, 1.0 mass % or more is more preferable, and 2.0 mass % or more is still more preferable. As an upper limit, it is actually 10.0 mass % or less, and may be 5.0 mass % or less.

The desorption reaction accelerator or its precursor may be used only by 1 type, and may use 2 or more types. When using 2 or more types, it is preferable that a total amount becomes the said range.

<<Alkylene glycol compound>>

The composition for forming an underlayer film for imprint may contain an alkylene glycol compound. The alkylene glycol compound preferably has 3 to 1,000 alkylene glycol constituent units, more preferably 4 to 500, still more preferably 5 to 100, and more preferably 5 to 50 . The weight average molecular weight (Mw) of the alkylene glycol compound is preferably 150 to 10,000, more preferably 200 to 5,000, further preferably 300 to 3,000, and still more preferably 300 to 1,000.

The alkylene glycol compound is exemplified by polyethylene glycol, polypropylene glycol, such mono or dimethyl ether, mono or dioctyl ether, mono or dinonyl ether, mono or didecyl ether, monostearate, Monoacid esters, monoadipate, monosuccinate, polyethylene glycol and polypropylene glycol are preferred.

The surface tension of the alkylene glycol compound at 23°C is preferably at least 38.0 mN/m, more preferably at least 40.0 mN/m. Although the upper limit of surface tension is not specifically limited, For example, it is 48.0 mN/m or less. By blending the above compounds, the wettability of the imprint curable composition provided directly above the underlayer film can be improved.

When containing an alkylene glycol compound, it is 40 mass % or less of a nonvolatile component, Preferably it is 30 mass % or less, More preferably, it is 20 mass % or less, More preferably, it is 1-15 mass %.

The alkylene glycol compound may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes the said range.

<<polymerization initiator>>

A polymerization initiator may be contained as a nonvolatile component. Examples of the polymerization initiator include thermal polymerization initiators and photopolymerization initiators, but from the viewpoint of improving crosslinking reactivity with the curable composition for imprints, photopolymerization initiators are preferred. good. As a photopolymerization initiator, a radical polymerization initiator and a cationic polymerization initiator are preferable, and a radical polymerization initiator is more preferable. Moreover, in this invention, several types of photoinitiators can be used together.

骨架之化合物、包含噁二唑骨架之化合物、包含三鹵化甲基之化合物等)、醯基膦氧化物等醯基膦化合物、六芳基雙咪唑、肟衍生物等肟化合物、有機過氧化物、硫化合物(thio compound)、酮化合物、芳香族鎓鹽、酮肟醚、胺基苯乙酮化合物、羥基苯乙酮、偶氮系化合物、疊氮化合物、茂金屬化合物、有機硼化合物、鐵-芳烴錯合物等。該等中肟化合物為較佳。關於該等的詳細內容，能夠參閱日本特開2016-027357號公報的0165~0182段的記載，該內容編入本說明書中。 As the photopolymerization initiator, any known compound can be used arbitrarily. For example, halogenated hydrocarbon derivatives (for example, containing three

Skeleton compounds, compounds containing oxadiazole skeletons, compounds containing trihalogenated methyl groups, etc.), acylphosphine compounds such as acylphosphine oxides, hexaarylbiimidazoles, oxime compounds such as oxime derivatives, organic peroxides , sulfur compound (thio compound), ketone compound, aromatic onium salt, ketoxime ether, aminoacetophenone compound, hydroxyacetophenone, azo compound, azide compound, metallocene compound, organoboron compound, iron - Aromatic complexes, etc. Among these oxime compounds are preferred. For details of these, the description in paragraphs 0165 to 0182 of JP-A-2016-027357 can be referred to, and the content is incorporated in this specification.

Examples of the acylphosphine compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like. Moreover, commercially available IRGACURE-819, IRGACURE1173, and IRGACURE-TPO (product names: both are made by BASF Corporation) can be used.

When blending the content of the photopolymerization initiator used in the underlayer film-forming composition for imprinting, it is, for example, 0.01 to 15% by mass, preferably 0.1 to 12% by mass in the non-volatile components, and further preferably Preferably, it is 0.2 to 7% by mass. When using 2 or more types of photoinitiators, the total amount will be the said range.

<<polymerization inhibitor>>

A polymerization inhibitor may be contained as a nonvolatile component. Polymerization inhibitor (B) of this embodiment It is a compound that has the ability to trap free radicals generated by the hardening main agent (A) before causing growth reactions. Thereby, the polymerization inhibitor (B) acts to suppress the polymerization of the curable main agent (A).

The polymerization inhibitor (B) can be any one of hydroquinones, catechols, phenanthiazine, and phenoxazine. Specific examples of the polymerization inhibitor (B) include 4-methoxyphenol, 4-methoxy-1-naphthol, 4-tertiary butylcatechol, 2,6-di-tertiary Butylphenol, 2,6-di-tertiary butyl-p-cresol, 2-tertiary butyl-4,6-dimethylphenol, 2,4,6-tri-tertiary butylphenol, hydroquinone, Phenolic compounds such as tertiary butylhydroquinone. Specific examples of the polymerization inhibitor (B) include quinone compounds such as naphthoquinone and benzoquinone. Specific examples of the polymerization inhibitor (B) include amine compounds such as phenanthiazine, phenoxazine, and 4-hydroxy-2,2,6,6-tetramethylpiperidine. Specific examples of the polymerization inhibitor (B) include 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine N-oxyl compounds such as pyridine-N-oxyl. The compounds listed here are merely examples, and the polymerization inhibitor (B) may be other compounds.

The content of the polymerization inhibitor is preferably from 0.0001% by mass to 10.0% by mass of the solid content, more preferably from 0.001% by mass to 1.0% by mass, still more preferably from 0.005% by mass to 0.1% by mass. Only 1 type may be used for a polymerization inhibitor, and 2 or more types may be used. When using 2 or more types, it is preferable that these total amounts are in the said range.

<<Other ingredients>>

As a non-volatile component blended into the underlayer film-forming composition for imprint, one or more kinds of thermal polymerization initiators, antioxidants, leveling agents, tackifiers, interface Active agents, etc.

Regarding the thermal polymerization initiator etc., JP 2013-036027 A, JP Components described in KOKAI Publication No. 2014-090133 and JP-A No. 2013-189537. Regarding the content and the like, the description in the above publication can also be referred to.

In addition, in the present invention, the composition for forming an underlayer film for imprint can also be configured to substantially not contain a surfactant. Substantially not contained is 0.1% by mass or less of the non-volatile components in the underlayer film-forming composition for imprint.

<<Solvent for lower film>>

The imprint underlayer film-forming composition contains a solvent. The solvent preferably contains, for example, a compound that is liquid at 23° C. and has a boiling point of 250° C. or lower (solvent for the lower layer film) in a proportion of 70.0% by mass or more. Typically, the non-volatile components end up forming the underlying film. The composition for forming an underlayer film for imprinting preferably contains at least 80.0% by mass of the solvent for the underlayer film, more preferably at least 90.0% by mass, more preferably at least 93.0% by mass, still more preferably at least 94.0% by mass, and may be 95.0% by mass. Mass % or more, 98.0 mass % or more, 99.0 mass % or more.

The solvent may be contained in the underlayer film-forming composition for imprint only by 1 type, or may contain 2 or more types. When containing 2 or more types, it is preferable that a total amount becomes the said range.

The boiling point of the solvent for the lower layer film is preferably 230°C or lower, more preferably 200°C or lower, still more preferably 180°C or lower, still more preferably 160°C or lower, still more preferably 130°C or lower. The lower limit is 23°C, but actually it is 60°C or higher. Since the solvent can be easily removed from the lower layer film by making a boiling point into the said range, it is preferable.

The solvent-based organic solvent for the lower film is preferred. It is preferable that the solvent contains any one or more of ester group, carbonyl group, hydroxyl group and ether group. Among them, it is preferable to use an aprotic polar solvent.

As specific examples, select alkoxy alcohol, propylene glycol monoalkyl ether carboxylate, propylene glycol mono Alkyl ethers, lactates, acetates, alkoxypropionates, chain ketones, cyclic ketones, lactones and alkylene carbonates.

Examples of alkoxy alcohols include methoxyethanol, ethoxyethanol, methoxypropanol (for example, 1-methoxy-2-propanol), ethoxypropanol (for example, 1-ethoxy 2-propanol), propoxypropanol (for example, 1-propoxy-2-propanol), methoxybutanol (for example, 1-methoxy-2-butanol, 1-methyl oxy-3-butanol), ethoxybutanol (for example, 1-ethoxy-2-butanol, 1-ethoxy-3-butanol), methylpentanol (for example, 4-methyl base-2-pentanol), etc.

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

Moreover, propylene glycol monomethyl ether or propylene glycol monoethyl ether is preferable as propylene glycol monoalkyl ether.

As the lactate, ethyl lactate, butyl lactate or propyl lactate is preferable.

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) is preferred.

As chain ketones, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, phenylacetone , methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, acetonyl acetone, ionone, diacetone alcohol, acetyl methanol, acetophenone, methyl naphthyl ketone, methyl penta Ketones are preferred.

As the cyclic ketone, methylcyclohexanone, isophorone or cyclohexanone is preferred.

As the lactone, γ-butyrolactone is preferred.

As the alkylene carbonate, propylene carbonate is preferred.

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

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

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

As a solvent for the lower film, and as a preferred solvent, it is selected from water, 1-methoxy-2-propanol, propylene glycol monomethyl ether acetate (PGMEA), ethoxyethyl propionate, cyclic At least one selected from the group consisting of hexanone, 2-heptanone, γ-butyrolactone, butyl acetate, propylene glycol monomethyl ether (PGME), ethyl lactate and 4-methyl-2-pentanol At least one selected from the group consisting of 1-methoxy-2-propanol, PGMEA, and butyl acetate is further preferred.

A conventionally known container can be used as the container for the imprint underlayer film-forming composition. Also, as a storage container, for the purpose of suppressing the mixing of impurities into the raw material or composition, a multi-layer bottle whose inner wall is composed of 6 kinds of 6-layer resins or a bottle with 6 kinds of resins as a 7-layer structure is used Also better. As such a container, the container described in Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

<Curable composition for imprint>

<<polymeric compound>>

The curable imprint composition preferably contains a polymerizable compound, and preferably contains a polymerizable compound having an aromatic ring. The polymerizable compound may be a monofunctional polymerizable compound or a polyfunctional polymerizable compound. Moreover, it is preferable to contain both a monofunctional polymeric compound and a polyfunctional polymeric compound.

<<<Monofunctional polymeric compound>>>

The molecular weight of the monofunctional polymerizable compound used in the curable composition for imprints is preferably at least 50, more preferably at least 100, and still more preferably at least 150. Moreover, the molecular weight is preferably 1,000 or less, more preferably 800 or less, still more preferably 300 or less, and still more preferably 270 or less. Volatility tends to be suppressed by making molecular weight more than the said lower limit. There exists a tendency for a viscosity to be able to be reduced by making molecular weight below the said upper limit.

The boiling point of the monofunctional polymerizable compound used in the curable composition for imprint is preferably 85°C or higher, more preferably 110°C or higher, still more preferably 130°C or higher. Volatility can be suppressed by making a boiling point more than the said lower limit. Although it does not specifically limit about the upper limit of a boiling point, For example, a boiling point can be made into 350 degreeC or less.

The type of polymerizable group contained in the monofunctional polymerizable compound used in the imprint curable composition is not particularly limited, but examples include ethylenically unsaturated groups, epoxy groups, etc., and ethylenically unsaturated groups are more preferred. good. As the ethylenically unsaturated group, a (meth)acryl group is preferable, and an acryl group is more preferable.

The type of atoms constituting the monofunctional polymerizable compound used in the imprint curable composition is not particularly limited, but it is preferably composed of only atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, and halogen atoms. It is more preferably composed of atoms selected from carbon atoms, oxygen atoms and hydrogen atoms.

A preferred first embodiment of the monofunctional polymerizable compound used in the curable composition for imprint is a compound having a straight or branched hydrocarbon chain having 4 or more carbon atoms.

The hydrocarbon chain in the present invention means an alkane chain, an alkene chain, and an alkyne chain, and an alkane chain and an alkene chain are preferable, and an alkane chain is more preferable.

In the present invention, the alkyl chain means an alkyl group and an alkylene group. Likewise, an alkene chain represents an alkenyl group and an alkenylene group, and an alkyn chain represents an alkynyl group and an alkynylene group. Among these, straight-chain or branched alkyl and alkenyl groups are more preferable, straight-chain or branched alkyl groups are further preferable, and straight-chain alkyl groups are even more preferable.

The above-mentioned linear or branched hydrocarbon chain (preferably an alkyl group) has a carbon number of 4 or more, preferably a carbon number of 6 or more, more preferably a carbon number of 8 or more, further preferably a carbon number of 10 or more, and a carbon number of 12 or more for better. The upper limit of the carbon number is not particularly limited, but, for example, it can be 25 or less.

The aforementioned straight or branched hydrocarbon chain may contain an ether group (—O—) from the viewpoint of improving mold release properties, but preferably does not contain an ether group.

By using a monofunctional polymerizable compound having such a hydrocarbon chain, the modulus of elasticity of the hardened product (pattern) is lowered and the release property is improved with a relatively small amount of addition. In addition, if a monofunctional polymerizable compound having a linear or branched alkyl group is used, the interface energy between the mold and the cured product (pattern) can be reduced, and the mold releasability can be further improved.

Examples of preferred hydrocarbon groups having a monofunctional polymerizable compound used in curable compositions for imprints include (1) to (3).

(1) Straight-chain alkyl group with 8 or more carbon atoms

(2) Branched alkyl groups with more than 10 carbon atoms

(3) Alicyclic rings, aromatic rings or aromatic heterocyclic rings substituted by linear or branched alkyl groups having 1 or more carbon atoms

(1) Straight-chain alkyl group with 8 or more carbon atoms

The linear alkyl group having 8 or more carbon atoms is more preferably one having 10 or more carbon atoms, further preferably 11 or more carbon atoms, and still more preferably 12 or more carbon atoms. Also, the carbon number is preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, and still more preferably 14 or less.

(2) Branched alkyl groups with more than 10 carbon atoms

The above-mentioned branched alkyl group having 10 or more carbon atoms is preferably one having 10-20 carbon atoms, more preferably 10-16 carbon atoms, further preferably 10-14 carbon atoms, and more preferably 10-12 carbon atoms.

(3) Alicyclic, aromatic or aromatic heterocyclic rings substituted by linear or branched alkyl groups with 1 or more carbon atoms

A linear or branched alkyl group having 1 or more carbon atoms is more preferably a linear alkyl group. The carbon number of the alkyl group is preferably 14 or less, more preferably 12 or less, and still more preferably 10 or less.

The alicyclic ring, aromatic ring or aromatic heterocyclic ring may be a single ring or a condensed ring, but a single ring is preferred. In the case of condensed rings, the number of rings is preferably 2 or 3. The ring is preferably 3-8 membered, more preferably 5-membered or 6-membered, and still more preferably 6-membered. Specific examples of the ring include the example of the ring Cz described later.

It is preferred that the monofunctional polymerizable compound used in the curable composition for imprinting be a linear or branched hydrocarbon chain having 4 or more carbon atoms and a polymerizable group bonded directly or via a linking group, which is the above (1 )~(3) The compound in which any one of the groups in (3) is directly bonded to the polymerizable group is more preferable. As the linking group, -O-, -C(=O)-, -CH ₂ -, or combinations thereof are exemplified. As the monofunctional polymerizable compound used in the present invention, straight-chain alkyl (meth)acrylates directly bonded (1) with a straight-chain alkyl group having 8 or more carbon atoms and a (meth)acryloxyl group are particularly preferred. good.

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

R ¹² represents an alkyl group (preferably 1 to 36 carbons, more preferably 1 to 30, further preferably 1 to 24), alicyclic (preferably 3 to 24 carbons, more preferably 3 to 12 better, 3~6 is more preferable), aromatic ring (6~22 carbon number is better, 6~18 is more preferable, 6~10 is more preferable) and aromatic heterocycle (carbon number 2~12 Preferably, 2 to 6 are more preferred, and 2 to 5 are further preferred) at least one type or a group based on a combination thereof. R ¹¹ represents a hydrogen atom or a methyl group. L ¹¹ represents a single bond or the above-mentioned linking group L, preferably alkylene or alkenylene. R ¹² and L ¹¹ may be bonded through a linking group L or not to form a ring. R ¹² and L ¹¹ may have the substituent T described above. A plurality of substituents T may be bonded to form a ring, or may be bonded to R ¹² or to L ¹¹ to form a ring. When there are plural substituents T, they may be the same as or different from each other. The preferable range of the alicyclic ring, aromatic ring or aromatic heterocyclic ring in ^R12 is the same as that of ring Cz described later.

As the monofunctional polymerizable compound of the first embodiment, the following first group and second group can be illustrated. However, the present invention is not limited to these descriptions. Also, the first group is better than the second group.

Group 1

[chemical formula 13]

Group 2

A preferred second embodiment of the monofunctional polymerizable compound used in the curable composition for imprint is a compound having a ring structure. As a cyclic structure, a monocyclic or condensed ring having 3 to 8 members is preferable. The number of rings constituting the above-mentioned condensed ring is preferably 2 or 3. The ring structure is more preferably a 5-membered ring or a 6-membered ring, and a 6-membered ring is still more preferable. Also, a single ring is more preferable.

The number of cyclic structures in one molecule of the polymerizable compound may be one, or two or more, preferably one or two, and more preferably one. In addition, in the case of a condensed ring, the condensed ring is regarded as one cyclic structure.

As the monofunctional polymerizable compound of the second embodiment, the following compounds can be illustrated. However, the present invention is not limited to these descriptions. Moreover, among the compounds described in the above-mentioned first embodiment, compounds having a ring structure are exemplified as preferred compounds of the present embodiment.

In the present invention, a monofunctional polymerizable compound other than the monofunctional polymerizable compound described above can be used without departing from the gist of the present invention. Examples of the monofunctional polymerizable compounds described in JP-A-2014-170949 Polymer compounds, these contents are included in this specification.

Regarding the content of the monofunctional polymerizable compound used in the curable composition for imprints relative to the total polymerizable compound, when contained, it is preferably 6% by mass or more, more preferably 8% by mass or more, and 10% by mass or more. More preferably, 12% by mass or more is more preferable. Moreover, the said content is more preferably 60 mass % or less, and may be 55 mass % or less.

In the present invention, only one type of monofunctional polymerizable compound may be included, or two or more types may be included. When containing 2 or more types, it is preferable that a total amount becomes the said range.

<<<Multifunctional polymeric compound>>>

The polyfunctional polymerizable compound used in the curable composition for imprint is not particularly limited, but preferably contains at least one of an alicyclic ring, an aromatic ring, and an aromatic heterocyclic ring, and includes an aromatic ring and an aromatic heterocyclic ring. At least one of the rings is more preferred. In the following description, a compound containing at least one of an alicyclic ring, an aromatic ring, and an aromatic heterocyclic ring may be referred to as a ring-containing polyfunctional polymerizable compound.

The molecular weight of the ring-containing polyfunctional polymerizable compound used in the curable composition for imprint is preferably 1,000 or less, more preferably 800 or less, still more preferably 500 or less, and more preferably 350 or less. By setting the upper limit of the molecular weight to 1,000 or less, the viscosity tends to be lowered. Although it does not specifically limit about the lower limit of molecular weight, For example, it can set it as 200 or more.

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

The type of polymerizable group contained in the ring-containing polyfunctional polymerizable compound used in the imprint curable composition is not particularly limited, but examples include ethylenically unsaturated groups, epoxy groups, etc., ethylenically unsaturated base is better. As the ethylenically unsaturated group, a (meth)acryl group is more preferable, and an acryl group is still more preferable. One molecule may contain two or more polymerizable groups, or may contain two or more polymerizable groups of the same type.

The type of atoms constituting the ring-containing polyfunctional polymerizable compound used in the imprint curable composition is not particularly limited, but it is preferably composed of only atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, and halogen atoms. , is more preferably constituted only of atoms selected from carbon atoms, oxygen atoms and hydrogen atoms.

The ring contained in the ring-containing polyfunctional polymerizable compound used in the imprint curable composition may be monocyclic or condensed, but monocyclic is preferred. In the case of condensed rings, the number of rings is preferably 2 or 3. The ring is preferably 3-8 membered, more preferably 5-membered or 6-membered, and still more preferably 6-membered. In addition, the ring may be an alicyclic ring, or may be an aromatic ring or an aromatic heterocyclic ring, but an aromatic ring or an aromatic heterocyclic ring is preferred, and an aromatic ring is still more preferred. Specific examples of the ring include the ring Cz example.

The number of rings used in the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints may be 1 or 2 or more rings, but 1 or 2 rings are preferred, and 1 ring is more preferred . In addition, when it is a condensed ring, the condensed ring is regarded as one.

The structure of the ring-containing polyfunctional polymerizable compound used in the curable composition for imprinting consists of (polymerizable group)-(single bond or divalent linking group)-(divalent group having a ring)-( A single bond or a divalent linking group)-(polymerizable group) is preferred. Among them, an alkylene group is more preferable as a linking group, and an alkylene group having 1 to 3 carbon atoms is still more preferable.

The ring-containing polyfunctional polymerizable compound used in the imprint curable composition is preferably represented by the following formula (I-2).

Q represents a group selected from alicyclic rings (preferably 3~24 carbons, more preferably 3~12, further preferably 3~6), aromatic rings (preferably 6~22 carbons, 6~18 are 1+q valence of at least one of more preferably, 6~10 is more preferable) and aromatic heterocyclic ring (2~12 is more preferable, 2~6 is more preferable, 2~5 is more preferable) group. 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 aforementioned linking group L. Q and ^L21 or ^L22 may or may not be bonded via a linker L to form a ring. Q, L ²¹ and L ²² may have the substituent T described above. A plurality of substituents T may be bonded to form a ring, or may be bonded to Q or to ^L21 or ^L22 to form a ring. When there are plural substituents T, they may be the same as or different from each other. Preferable ranges of the alicyclic ring, aromatic ring or aromatic heterocyclic ring in Q include ring Cz described later. q is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1.

Q may have a structure in which plural alicyclic rings, plural aromatic rings, plural aromatic heterocyclic rings, alicyclic rings and aromatic rings, alicyclic rings and aromatic heterocyclic rings, or aromatic rings and aromatic heterocyclic rings are bonded. Examples of the structure to which the aromatic rings are linked include structures of the above-mentioned formulas Ar1 to Ar5.

As the polyfunctional polymerizable compound used in the curable composition for imprints, the following first group and second group can be exemplified. However, the present invention is not limited to these descriptions. Group 1 is better.

Group 1

Group 2

[chemical formula 18]

The curable composition for imprint may contain other polyfunctional polymerizable compounds other than the above-mentioned ring-containing polyfunctional polymerizable compounds. As another polyfunctional polymerizable compound, a compound represented by the following formula (I-3) is preferable.

^L30 represents a group selected from a straight chain or branched alkane structure (1 to 12 carbons is preferred, 1 to 6 is more preferred, and 1 to 3 is further preferred), a straight chain or branched alkene structure Group (2~12 carbon number is preferred, 2~6 is more preferred, 2~3 is further preferred), linear or branched alkyne structure group (carbon number 2~12 is preferred, 2 ~6 is more preferred, and 2~3 is further preferred) at least one 1+r-valent group. R ²⁵ and R ²⁶ each independently represent a hydrogen atom or a methyl group. L ²⁵ and L ²⁶ each independently represent a single bond or the linking group L described above. L ³⁰ and L ²⁵ or L ²⁶ may be bonded via a linker L or not to form a ring. L ²⁵ , L ²⁶ and L ³⁰ may have the substituent T described above. A plurality of substituents T may be bonded to form a ring, or may be bonded to other linking groups to form a ring. When there are plural substituents T, they may be the same as or different from each other. r is an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1. Furthermore, L ³⁰ may have a hetero linking group (O, S, ^NRN ). The number of intervening hetero linking groups is preferably 1 when L ³⁰ has 1 to 6 carbons.

Examples of other polyfunctional polymerizable compounds used in the curable composition for imprints include polyfunctional polymerizable compounds that do not have a ring among the polymerizable compounds described in JP-A-2014-170949, which are included in this manual. More specifically, for example, the following compounds are exemplified.

As the ring Cz, the following aromatic rings, aromatic heterocyclic rings and alicyclic rings are exemplified.

(chrysene)環、苝環、四氫萘環等。其中，苯環或萘環為較佳，苯環為更佳。芳香族環可取連結有複數個之結構，例如，可舉出聯苯環、聯二苯環。 As an aromatic ring contained in the compound containing an aromatic ring, those with 6-22 carbon atoms are preferable, 6-18 are more preferable, and 6-10 are still more preferable. Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a phenanthrene ring, a fenene ring, an acenaphthylene ring, a biphenyl ring, an indene ring, a dihydroindene ring, and a biphenylene ring. , pyrene ring,

(chrysene) ring, perylene ring, tetrahydronaphthalene ring, etc. Among them, a benzene ring or a naphthalene ring is preferred, and a benzene ring is more preferred. The aromatic ring may have a structure in which a plurality of them are connected, for example, a biphenyl ring and a biphenyl ring are mentioned.

環等。 As the aromatic heterocyclic ring, one having 1 to 12 carbon atoms is preferable, 1 to 6 carbon atoms are more preferable, and 1 to 5 carbon atoms are still more preferable. Specific examples thereof include thiophene ring, furan ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, oxazole ring, pyridine ring, pyrimidine ring, pyridazine ring, iso Indole ring, indazole ring, purine ring, quinozine ring, isoquinoline ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline (cinnoline) ring, carba Azole ring, acridine ring, phenazine ring, phenothiazine ring, phenanthrene

Ring etc.

The alicyclic ring preferably has 3 to 22 carbon atoms, more preferably 4 to 18 carbon atoms, and still more preferably 6 to 10 carbon atoms. Specific examples thereof include a cyclopropane ring, a cyclobutane ring, a cyclobutene ring, a cyclopentane ring, a cyclohexane ring, a cyclohexene ring, a cycloheptane ring, a cyclooctane ring, and a dicyclopentane ring. Diene ring, tetrahydrodicyclopentadiene ring, octahydronaphthalene ring, decahydronaphthalene ring, hexahydroindan ring, camphane ring, norbornane ring, norbornene ring, isonorbornane ring, three Cyclodecane ring, tetracyclododecane ring, adamantane ring, etc.

The polyfunctional polymeric compound is preferably contained in an amount of at least 30% by mass, more preferably at least 45% by mass, more preferably at least 50% by mass, and at least 55% by mass, based on the total polymerizable compound in the curable composition for imprint. More preferably, it may be at least 60% by mass, and may be further at least 70% by mass. Also, the upper limit is preferably less than 95% by mass, more preferably 90% by mass or less, and can be set to 85% by mass or less.

The curable imprint composition may contain only one type of polyfunctional polymerizable compound, or may contain two or more types. When containing 2 or more types, it is preferable that a total amount becomes the said range.

The curable composition for imprint used in the present invention is 85% by mass or less of the composition The above polymeric compound is preferable, more than 90% by mass of the polymerizable compound is more preferable, and 93% by mass or more of the polymerizable compound is still more preferable.

The Hansen solubility parameter (HSP) vector of the curable composition for imprinting: (i) The dispersion component (d component) is preferably 14.0 to 20.0, more preferably 15.0 to 19.0, and more preferably 16.0 to 18.5 ; (ii) the polar component (p component) is 3.5 ~ 8.0 is better, 3.8 ~ 6.0 is better, 4.0 ~ 5.0 is further better; (iii) the hydrogen bond component (h component) is 4.0 ~ 8.0 is More preferable, 4.7-7.0 is more preferable, 5.2-6.5 is still more preferable.

The dispersion-term component, polar-term component, and hydrogen-bond-term component of the HSP vector of the curable composition for imprints are respectively set by methods described in Examples described later.

<<Other ingredients>>

The curable imprint composition may contain additives other than the polymerizable compound. As other additives, polymerization initiators, surfactants, sensitizers, release agents, antioxidants, polymerization inhibitors, and the like may be contained.

Specific examples of curable imprint compositions that can be used in the present invention include those described in JP-A-2013-036027, JP-A-2014-090133, and JP-A-2013-189537. Composition, and these contents are compiled into this manual. Also, regarding the preparation of the curable composition for imprint and the method of forming the film (pattern forming layer), reference can also be made to the descriptions in the above-mentioned gazettes, and these contents are incorporated into the present specification.

<<Physical properties, etc.>>

The viscosity of the curable composition for imprinting was 20.0 mPa. Below s is better, 15.0mPa. below s For better, it can be 11.0mPa. s or less, it can be further 9.0mPa. below s. The lower limit of the above-mentioned viscosity is not particularly limited, but, for example, it is 4.0 mPa. The above can be further set to 5.0 mPa. s or more.

The surface tension (γResist) of the curable composition for imprinting is preferably at least 29.0 mN/m, more preferably at least 30.0 mN/m, and still more preferably at least 31.0 mN/m. By using a curable composition for imprint with a high surface tension, the capillary force is increased, and high-speed filling of the curable composition for imprint into the mold pattern can be performed. The upper limit of the surface tension is not particularly limited, but it is preferably 42.0 mN/m or less, more preferably 40.0 mN/m or less, from the viewpoint of imparting a relationship with the underlayer film and inkjet suitability. It can be 38.0mN/m or less.

The Ohnishi parameter of the curable composition for imprint is preferably 5.0 or less, more preferably 4.0 or less, and still more preferably 3.7 or less. The lower limit of the Ohnishi parameter of the curable composition for imprints is not particularly limited, and may be, for example, 1.0 or more, further 2.0 or more.

For the polymerizable compound of the curable imprint composition, the Ohnishi parameter can be obtained by substituting the numbers of carbon atoms, hydrogen atoms, and oxygen atoms of all constituent components into the following formula.

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)

The Hansen solubility parameter (HSP) vector of the polymerizable compound contained in the curable composition for imprinting: (i) dispersive component (d component) is preferably 14.0 to 20.0, more preferably 15.0 to 19.0, 16.0~18.5 is more preferable; (ii) the polar component (p component) is 3.5~8.0 is better, 3.8~6.0 is better, 4.0~5.0 is further better; (iii) The hydrogen bond item component (h component) is preferably 4.0 to 8.0, more preferably 4.7 to 7.0, and still more preferably 5.2 to 6.5.

The dispersion term component, the polar term component, and the hydrogen bond term component of the HSP vector are respectively set by methods described in Examples described later. When calculating the HSP vector, when there are plural components, at least one of them preferably satisfies the above-mentioned range, and more preferably the largest number of components satisfies the above-mentioned range.

In the present invention, the content of the solvent in the curable imprint composition is preferably not more than 5% by mass, more preferably not more than 3% by mass, and still more preferably not more than 1% by mass of the curable imprint composition.

The imprint curable composition can also be substantially free of polymers (preferably polymers with a weight average molecular weight of more than 1,000, more preferably more than 2,000, and more preferably polymers with a weight average molecular weight of more than 10,000) the state of mind. Substantially not containing a polymer means, for example, that the polymer content is 0.01% by mass or less, preferably 0.005% by mass or less, and more preferably not contained at all, of the curable imprint curable composition.

As a storage container for the imprint curable composition used in the present invention, conventionally known storage containers can be used. Also, as a storage container, for the purpose of preventing impurities from mixing into the raw material or composition, it is also preferable to use a multi-layer bottle whose inner wall is composed of 6 types of 6-layer resins or a bottle with 6 types of resins as a 7-layer structure. As such a container, the container described in Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

<kit>

The present invention discloses a kit comprising a composition for forming an underlayer film for imprinting and a curable composition for imprinting containing a polymeric compound.

In the kit of the present invention, according to the disengaged component (the compound represented by formula (r1) or (r2) Or the Hansen solubility parameter of the compound represented by the formula (r1-1) and the Hansen solubility parameter of the curable composition for imprinting, and the ΔHSP value calculated from the following mathematical formula (H1) is preferably 5 or less , 7.0 or less is more preferable, 5.0 or less is more preferable, and 4.0 or less is more preferable. Although 0 may be sufficient as a lower limit value, it is actually 0.1 or more.

△HSP=(4.0×△D ² +△P ² +△H ² ) ^0.5 ......(H1)

ΔD is the difference between the dispersion term component of the Hansen solubility parameter vector of the imprint curable composition and the dispersion term component of the Hansen solubility parameter vector of the detachment component.

ΔP is the difference between the polar term component of the Hansen solubility parameter vector of the imprint curable composition and the polar term component of the Hansen solubility parameter vector of the detached component.

ΔH is the difference between the hydrogen bond term component of the Hansen solubility parameter vector of the imprint curable composition and the hydrogen bond term component of the Hansen solubility parameter vector of the detached component.

<Laminated body and its manufacturing method>

A preferred embodiment of the kit of the present invention includes a laminate formed from the kit. The laminate according to this embodiment preferably has an underlayer film formed of the above-mentioned imprint underlayer film-forming composition and an imprint layer formed of the above-mentioned curable composition for imprint and located on the surface of the above-mentioned underlayer film. The production method is not particularly limited, but examples include a production method comprising applying the imprint curable composition to the surface of the underlayer film formed from the imprint underlayer film-forming composition using the above-mentioned kit. In this case, it is preferable to apply the curable composition for imprint to the surface of the underlayer film by the inkjet method (IJ method). Furthermore, the method for producing a laminate includes a process of applying the above-mentioned underlayer film-forming composition for imprinting on a substrate in a layered form, and includes applying the above-mentioned underlayer film-forming composition for imprinting at a temperature of 80 to 250° C. (150~250°C is better) (process temperature) heating (baking) process is better.

<Pattern of cured product and its manufacturing method>

A method for producing a pattern of a cured product according to a preferred embodiment of the present invention uses the above-mentioned kit to manufacture a pattern of a cured product. The method includes: an underlayer film forming process, applying an underlayer film forming composition for imprinting to a substrate to form an underlayer film; The process of applying a curable composition for imprinting to the surface of the above-mentioned underlayer film; the mold contact process of bringing the above-mentioned curable composition for imprint into contact with a mold having a pattern for transferring the shape of the pattern; The curable composition for imprinting is irradiated with light to form a cured product; and the mold release process is to separate the cured product from the casting mold.

Hereinafter, a method of forming a cured product pattern (a method of manufacturing a cured product pattern) will be described with reference to FIG. 1 . It is obvious that the structure of the present invention is not limited to the illustrations.

<<Underlayer Film Formation Process>>

In the underlayer film forming process, as shown in (1) and (2) in FIG. 1 , an underlayer film 2 is formed on the substrate 1 . The underlayer film is preferably formed by applying the underlayer film-forming composition for imprint in a layered form on the substrate.

The method of applying the imprint underlayer film-forming composition to the substrate is not particularly limited, and generally known applicable methods can be employed. Specifically, as the applicable method, for example, dip coating method, pneumatic coating method, curtain coating method, wire bar coating method (wire bar coat), gravure coating method, extrusion coating method, spin coating method, etc. Coating method, slit scanning method or inkjet method, spin coating method is preferred.

Also, after applying the composition for forming an underlayer film for imprint in a layered form on a substrate, 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 at least 2 nm, more preferably at least 3 nm, more preferably at least 4 nm, may be at least 5 nm, and may be at least 7 nm. Also, the thickness of the underlayer film is preferably 40 nm or less, more preferably 30 nm or less, more preferably 20 nm or less, and may be 15 nm. It may be less than or equal to 10 nm or less. By making the film thickness not less than the above lower limit, the spreadability (wettability) of the curable composition for imprint on the underlayer film is improved, and a uniform residual film after imprinting can be formed. By making the film thickness below the above-mentioned upper limit, the remaining film after imprinting becomes thinner, the film thickness unevenness is less likely to occur, and the uniformity of the remaining film tends to be improved.

The material of the substrate is not particularly limited, and reference can be made to the description in paragraph 0103 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 specification), and such contents are incorporated herein. manual. 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 GaAsP, GaP , AlGaAs, InGaN, GaN, AlGaN, ZnSe, AlGa, InP or ZnO substrates. 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 is preferred.

<<Applicable process>>

In the applied process, for example, as shown in (3) in FIG. 1 , a curable composition 3 for imprint is applied to the surface of the above-mentioned underlayer film 2 .

The application method of 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. 2011/0199592 specification). The contents are incorporated into this instruction manual. It is preferable that the above-mentioned curable composition for imprint is applied to the surface of the above-mentioned underlayer film by an inkjet method. Also, the coating of the curable composition for imprint can be performed by multiple coating. In the method of arranging liquid droplets on the surface of the lower film by an inkjet method or the like, the amount of the liquid droplets is preferably about 1 to 20 pL, and the droplets are preferably arranged at intervals on the surface of the lower film. As the droplet interval, an interval of 10 to 1000 μm is preferable. for In the case of the inkjet method, the droplet interval is the arrangement interval of nozzles for inkjet.

Furthermore, the volume ratio of the lower film 2 to the film-like imprint curable composition 3 applied on the lower film is preferably 1:1 to 500, more preferably 1:10 to 300, and 1:50 to 200. for further improvement.

In addition, the method for producing a laminate according to a preferred embodiment of the present invention is a method for producing a laminate using the kit of the present invention, and the method includes applying an embossing agent for imprinting to the surface of the underlayer film formed from the above-mentioned underlayer film-forming composition for imprinting. The process of hardening composition. Furthermore, the method of manufacturing a laminate according to a preferred embodiment of the present invention includes a process of applying the above-mentioned underlayer film-forming composition for imprinting on a substrate in a layered form, and includes a temperature of 80 to 250° C. It is preferable to apply underheating (baking) to the layered underlayer film-forming composition for imprinting as described below. The heating time can be set to 30 seconds to 5 minutes.

<<Mold contact process>>

For example, as shown in (4) in FIG. 1 , in the mold contact process, the above curable composition for imprint 3 is brought into contact with a mold 4 having a pattern for transferring the shape of the pattern. By going through such a process, a desired cured product pattern (imprint pattern) is obtained.

Specifically, in order to transfer a desired pattern to the film-like curable imprint composition, the surface of the film-like curable imprint composition 3 is covered with a mold 4 .

The casting mold may be a light-transmitting mold or a non-light-transmitting mold. When using a light-transmitting mold, it is preferable to irradiate the curable imprint composition 3 with light from the side of the mold. On the other hand, when using a non-light-transmitting mold, it is preferable to use a light-transmitting substrate as the substrate and to irradiate light from the substrate side. In the present invention, it is more preferable to use a light-transmitting mold and to irradiate light from the side of the mold.

A casting mold that can be used in the present invention is a casting mold having a pattern for transfer. The pattern of the above-mentioned mold can be processed according to the desired processing accuracy by photolithography or electron beam scanning, for example. Formed, but in the present invention, the mold pattern manufacturing method is not particularly limited. Moreover, the pattern formed by the hardened|cured material pattern manufacturing method of the preferable 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 include light-transmitting resins such as glass, quartz, polymethylmethacrylate (PMMA), and polycarbonate resins, transparent metal vapor-deposited films, and polycarbonate resins. Soft films such as dimethyl siloxane, photohardening films, metal films, etc., preferably quartz.

The non-light-transmitting molding material used when the light-transmitting substrate is used in the present invention is not particularly limited as long as it has a predetermined strength. Specifically, examples include ceramic materials, vapor-deposited films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, substrates such as SiC, silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon. It is not particularly limited.

In the above method of producing a cured product pattern, when imprint lithography is performed using the curable composition for imprint, it is preferable to set the mold pressure to 10 atmospheres or less. By setting the mold pressure to 10 atmospheres or less, the mold or the substrate is less likely to be deformed, and pattern accuracy tends to be improved. Moreover, it is also preferable from the viewpoint that there is a tendency to reduce the size of the device due to low pressurization. The mold pressure is preferably selected from a range in which the residual film of the curable composition for imprint that touches the convex portion of the mold is reduced and the uniformity of the mold transfer can be ensured.

In addition, it is also preferable to contact the curable composition for imprint with 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 curable imprint composition to form a cured product. The irradiation amount of light irradiation in the photoirradiation process should just be sufficiently larger than the minimum irradiation amount required for hardening. Irradiation dose required for curing by investigating the consumption of unsaturated bonds in the curable composition for imprint Wait and make a determination as appropriate.

The type of light to be irradiated is not particularly limited, and ultraviolet light is exemplified.

In addition, in the imprint lithography applied to the present invention, the temperature of the substrate during light irradiation is usually room temperature, but light irradiation may be performed while heating in order to improve reactivity. As a preparatory stage for light irradiation, if it is in a vacuum state, it is effective in preventing air bubbles from being mixed in, suppressing a decrease in reactivity due to oxygen being mixed in, and improving the adhesion between the mold and the curable composition for imprinting. Light irradiation was performed in a vacuum state. In addition, in the above-mentioned method for producing a cured product pattern, a preferable vacuum degree during light irradiation is in the range of 10 ⁻¹ Pa to normal pressure.

When performing exposure, the exposure illuminance is preferably in the range of 1 to 500 mW/cm ² , 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 5~1000mJ/cm ² , more preferably in the range of 10~500mJ/cm ² .

In the above method of producing a pattern of a cured product, after curing the film-like curable composition for imprint (pattern forming layer) by irradiation with light, a process of heating and further curing the cured pattern may be included as necessary. As a temperature for heating and hardening the curable composition for imprints after light irradiation, 150-280 degreeC is preferable, and 200-250 degreeC is more preferable. In addition, the time for applying heat is preferably 5 to 60 minutes, more preferably 15 to 45 minutes.

<<Demolding process>>

In the demoulding process, the above-mentioned cured product and the above-mentioned mold are separated ((5) in FIG. 1 ). The obtained cured product pattern can be utilized for various purposes as described later.

That is, the present invention discloses a laminate having, on the surface of the above-mentioned underlayer film, a cured product pattern formed of a curable composition for imprinting. In addition, the embossing hardener used in the present invention includes The film thickness of the pattern-forming layer of the active composition varies depending on the application, but is about 0.01 μm to 30 μm.

In addition, as described later, etching and the like can also be performed.

<Hardened pattern and its application>

As described above, the cured product pattern formed by the above-mentioned method for producing a 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 (mask for lithography) for semiconductor element production. ).

In particular, the present invention discloses a method of manufacturing a circuit board including a process of obtaining a cured product pattern by the method of manufacturing a cured product pattern according to a preferred embodiment of the present invention. Furthermore, in the method of manufacturing a circuit board 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-mentioned method of manufacturing a cured product pattern as a mask. Manufacturing process of electronic components. It is preferable that the above-mentioned circuit board is a semiconductor element. Furthermore, the present invention discloses a method of manufacturing an electronic device, which includes a process for obtaining a circuit board by the method for manufacturing the circuit board and a process for connecting the circuit board to a control mechanism that controls the circuit board.

In addition, by using the pattern formed by the above-mentioned cured product pattern manufacturing method to form a grid pattern on the glass substrate of the liquid crystal display device, it is possible to cheaply manufacture a large screen size (for example, 55 inches, greater than 60 inches) with less reflection or absorption. inches) polarizer. For example, a polarizing plate described in JP-A-2015-132825 or WO2011/132649 can be produced. Furthermore, 1 inch is 25.4mm.

As shown in (6) in FIG. 1 and (7) in FIG. 1 , the cured product pattern formed by the present invention is also useful as an etching resist (mask for lithography). When using a cured product pattern as an etching resist, first, use a silicon substrate (silicon wafer, etc.) on which a thin film such as SiO ₂ is formed as a substrate, and form, for example, a nano Or a micron-level fine hardened pattern. In the present invention, it is particularly effective in that it is possible to form a fine pattern on the nanometer order, and furthermore, a pattern with a size of 50 nm or less, especially 30 nm or less, can be formed. The lower limit of the size of the cured product pattern formed by the above-mentioned cured product pattern manufacturing method is not particularly limited, for example, it can be set to 1 nm or more.

As a preferred embodiment, there are also examples of an imprint mold having a process of obtaining a cured product pattern on a substrate by a method of producing a cured product pattern and a process of etching the above substrate using the obtained cured product pattern. Manufacturing method.

Etching using hydrogen fluoride or the like during wet etching and etching using an etching gas such as _CF4 during dry etching can form a desired cured product pattern on the substrate. The hardened pattern has good etching resistance especially to dry etching. That is, the pattern formed by the above-mentioned hardened product pattern manufacturing method is preferably used as a mask for lithography.

Fig. 2 is a plan view schematically showing the wetting and spreading state of the curable imprint composition when the curable imprint composition is applied to the surface of the underlayer film by an inkjet method. When the curable composition for imprint is applied by the inkjet (IJ) method, for example, as shown in FIG. (a) in 2). If the mold is contacted here, the above-mentioned droplet spreads on the lower layer film 21, thereby forming film-like imprint curable compositions 22a, 22b, 22c ((b) in FIG. 2, (c) in FIG. 2 , (d) in Figure 2). However, the curable composition for imprint does not spread uniformly. For example, if the wetting and spreading stops in (c) in FIG. Fully expanded membrane. That is, there may be a region 23 where the film thickness is thin or there is no film. in this way, Then, a part where the imprint curable composition is not sufficiently filled occurs on the pattern of the mold, resulting in a part without a pattern in the imprint layer. For example, when etching is carried out using the pattern of the above imprint layer with partial defects or insufficient thickness as a mask, the area from the thinner film thickness to the film-free area 23 and the other areas are etched. Etching unevenness occurs in the region 22b, making it difficult to uniformly etch and transfer a desired pattern shape over the entire imprint region.

On the other hand, according to the imprint underlayer film-forming composition of the present invention, the surface tension between the underlayer film and the imprint curable composition is improved, and the wettability is improved. Therefore, the imprint curable composition 22c is more reliably spread to every corner of the state of (d) in FIG. 2 . As a result, the curable composition for imprint is reliably and sufficiently filled in the mold throughout the entirety, and in the formed imprint layer, good patterning without unevenness in thickness can be realized. In addition, high-speed imprinting can be performed by improving the fillability, which in turn leads to an improvement in throughput.

In addition, in the above description, the example of applying the curable composition for imprint on the underlayer film by the inkjet method was used to describe the mechanism of action of the preferred embodiment of the present invention, but the present invention is not limited thereto. And explain. For example, in screen coating, spin coating, etc., good wettability and excellent fillability are also related to advantages in processing and product quality, and can appropriately exert the effects of the invention.

Specifically, the pattern formed by the present invention can be preferably used in the production of a guide pattern for fine pattern formation (directed self-assembly, DSA (directed self-assembly) using the following self-organization, etc. ), 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 holograms, optical waveguides, optical filters, microlens arrays, thin film transistors, organic transistors, color filters, antireflection films, polarizers, polarizing elements, optical films, pillars, and other components for flat panel displays , Nanobiological devices, immunoassay chips, deoxyribonucleic acid (DNA) separation chips, microreactors, photonic liquid crystals, block copolymers.

[Example]

The following examples are given to further describe the present invention in detail. Materials, usage amounts, proportions, processing contents, processing procedures and the like shown in the following examples can be appropriately changed unless 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 Example of Polymer G-1>

Methanol (MeOH) (300 g), 5-Bromoisophthalic Acid (5-bromoisophthalic acid) (manufactured by Tokyo Chemical Industry Co., Ltd., 10 g), concentrated sulfuric acid (1 mL) were added to a three-necked flask flowing with N ₂ , and It heated to 90 degreeC, and performed aging for 4 hours. Thereafter, concentration under reduced pressure was performed. The concentrate, ethyl acetate (500 g), and 3% aqueous sodium bicarbonate solution (300 g) were put into a separating funnel, and stirred. The target compound (intermediate G-1A) was synthesized by concentrating the organic layer.

Tetrahydrofuran (THF) (300 g) and G-1A (10 g) were charged into a three-necked flask flowing with N ₂ , cooled to 0° C., and LiAlH ₄ (manufactured by FUJIFILM Wako Pure Chemical Corporation, 3 g) was added little by little, and Aging was carried out for 2 hours. Then, water (3 g), 15% sodium hydroxide aqueous solution (3 g), and water (9 g) were added, and aging was performed for 1 hour. After that, the target compound (intermediate G-1B) was synthesized by performing filtration and concentrating the filtrate.

Add DMF (300 g), imidazole (8 g), and G-1B (10 g) to a three-necked flask flowing with _N , cool to 0° C. and add tert-Butyldimethylchlorosilane (manufactured by Tokyo Chemical Industry Co., Ltd.) little by little. , 18g), and aged for 2 hours. Thereafter, concentration under pressure was carried out. The concentrate, ethyl acetate (500 g), and 3% aqueous sodium bicarbonate solution (300 g) were put into a separating funnel, and stirred. The organic layer was concentrated and purified by silica gel chromatography to synthesize the target compound (intermediate G-1C).

Mg (1 g), G-1C (10 g), and THF (100 g) were charged into a three-necked flask flowing with N ₂ , cooled to 0° C., and aged for 1 hour. Thereafter, acetone (2 g) was added little by little, and aging was performed for 2 hours. Thereafter, concentration under reduced pressure was performed. The concentrate, ethyl acetate (500 g), and 3% aqueous sodium bicarbonate solution (300 g) were put into a separating funnel, and stirred. The organic layer was concentrated and purified by silica gel chromatography to synthesize the target compound (intermediate G-1D).

Add G-1D (10 g) and cyclohexane (100 g) to a three-necked flask flowing with N ₂ , cool to 0° C., and dropwise add 20% butyllithium cyclohexane solution (manufactured by Tokyo Chemical Industry Co., Ltd. , 12mL) and aged for 1 hour. Thereafter, methacryl chloride (manufactured by Tokyo Chemical Industry Co., Ltd., 3 g) was added dropwise, followed by aging for 1 hour. Thereafter, THF (100 g) and 1M aqueous HCl solution were added, followed by aging for 5 hours. Then, ethyl acetate (1000g) and 3% sodium bicarbonate aqueous solution (300g) were added and stirred. The organic layer was concentrated and purified by silica gel chromatography to synthesize the target compound (intermediate G-1E).

PGMEA (30 g) was added to a three-necked flask flowing with N ₂ and heated to 60°C. Dissolve 2-Hydroxyethyl Methacrylate (2-hydroxyethyl methacrylate) (manufactured by Tokyo Chemical Industry Co., Ltd., 13g, 100mmol), G-1E (26g, 100.0mmol), photoradical in PGMEA (70g) A polymerization initiator (manufactured by FUJIFILM Wako Pure Chemical Corporation, V-65, 1.0 g, 4.0 mmol), and the obtained mixture was added dropwise at a temperature at which the internal temperature of the above-mentioned flask did not exceed 65° C. over 2 hours, and at 90 The aging was carried out at ℃ for 4 hours. Afterwards, it was cooled to 25°C. Diisopropyl ether (435.5g) and hexane (186.6g) were added to another three-necked flask, and it cooled to 0 degreeC and stirred. The reaction solution in the above-mentioned flask was added dropwise to the mixed solution in another three-necked flask at a temperature not exceeding 5° C. over 30 minutes, and stirred for 1 hour. Thereafter, it was left still for 1 hour, and filtered under reduced pressure. The target compound (Intermediate G-1F) was synthesized by drying the obtained powder under reduced pressure.

PGMEA (45.38 g), intermediate G-1F (19.7 g, 100.0 mmol), and triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd., 15 g, 150.0 mmol) were charged into a three-necked flask flowing with N ₂ , and cooled to 0°C. PGMEA (45.38g) and Acryloyl Choride (acryloyl chloride) (14g, 150.0mmol) were mixed and added dropwise over 2 hours while the internal temperature of the above-mentioned flask did not exceed 10°C, and was carried out at 20°C for 4 hours. mature. Afterwards, it was cooled to 0°C. Diisopropyl ether (435.5g) and hexane (186.6g) were added to another three-necked flask, and it cooled to 0 degreeC and stirred. The reaction solution in the above-mentioned flask was added dropwise to the mixed solution in another three-necked flask at a temperature not exceeding 5° C. over 30 minutes, and stirred for 1 hour. Thereafter, it was left still for 1 hour, and filtered under reduced pressure. The obtained powder was washed with water and dried under reduced pressure to synthesize target compound G-1.

Other polymers were synthesized following the above-mentioned synthesis examples.

<Preparation of Underlayer Film Forming Composition>

The ingredients are blended as shown in Tables 1 to 4 below, and two-stage filtration is performed using a polytetrafluoroethylene (PTFE) filter with a pore size of 0.1 μm and a UPE filter (ultra-high molecular weight polyethylene) with a pore size of 0.003 μm to prepare The composition for forming the underlayer film for imprint in Examples and Comparative Examples. In Tables 1 to 4, mark the serial numbers of the curable imprint compositions used in combination.

<Confirmation of detached components when baked at 80°C>

The underlayer film-forming composition for imprinting was spin-coated on a silicon wafer (diameter 8 inches). Afterwards, under the baking conditions of 80°C, 3 minutes, and air atmosphere, a heating plate was used to form a lower layer on the wafer. layer film. The thickness of the obtained underlayer film was about 10 nm. The obtained lower film was immersed in tetrahydrofuran (THF) for 30 minutes, and the obtained THF solution was analyzed by LC/MS.

In this way, it was confirmed whether or not a compound represented by formula (r1) or (r2) or formula (r1-1) and having a molecular weight of 210 or more was detected.

Compounds surrounded by dotted lines below the polymers described later are compounds that have undergone detachment. With regard to polymers H-1 to H-3, detachment of a compound having a molecular weight of 210 or more was not confirmed. Regarding polymer H-3, detachment of the compound represented by formula (r1) or (r2) or the compound represented by formula (r1-1) was not confirmed.

<Preparation of Curable Composition for Imprint>

The compounds shown in Table 5 were mixed, and 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl radical (manufactured by Tokyo Chemical Industry Co., Ltd.) The total amount of the polymerizable compound among the compounds shown in the table was added so as to be 200 mass ppm (0.02 mass %), and the curable composition for imprint was obtained. For this purpose, two-stage filtration was performed using a polytetrafluoroethylene (PTFE) filter with a pore size of 0.1 μm and a UPE (ultrahigh molecular weight polyethylene) filter with a pore size of 0.003 μm.

<surface tension>

The surface tension was measured at 23° C. using a glass plate using a surface tensiometer SURFACE TENS-IOMETER CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd. The unit is represented by mN/m. Two samples were prepared per one level, and each was measured three times, and the arithmetic mean value of the six times in total was adopted as an evaluation value.

<Calculation of distance between Hansen solubility parameters (△HSP)>

Hansen solubility parameters were calculated using the HSP calculation software HSPiP.

The structural formula of each compound was input into the above-mentioned software in the SMILES format, thereby calculating each component (d component, p component, h component) of the Hansen solubility parameter. Regarding the calculated Hansen solubility parameters, the Hansen solubility parameter inter-distances (ΔHSP: ΔD, ΔP, ΔH) between components are calculated as necessary.

△HSP=(4.0×△D ² +△P ² +△H ² ) ^0.5 ......(H1)

When there are multiple compounds in each calculation target component (for example, when there are two or more detached components, etc.), the Hansen solubility parameter adopts the value of the largest component (mass basis) in the compound. In addition, when there are 2 or more types of components in the maximum quantity, it shall be (the average value based on a mixing ratio).

Tables 1 to 4 show the distance (ΔHSP) between the disengaged component and the Hansen solubility parameter of the curable composition calculated from the formula (H1).

<Measuring method of molecular weight>

The weight average molecular weight (Mw) of the polymer is defined as a polystyrene-equivalent value based on gel permeation chromatography (GPC measurement). HLC-8220 (manufactured by TOSOH CORPORATION) was used as an apparatus, 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 an eluent, THF (tetrahydrofuran) was used. Detection uses a wavelength 254nm detector of UV rays (ultraviolet rays).

<Adhesiveness>

An underlayer film-forming composition for imprint was spin-coated on a silicon wafer (8 inches in diameter). Thereafter, under baking conditions of 150° C., 3 minutes, and an air atmosphere, heating was performed using a hot plate to form an underlayer film on the wafer. The thickness of the obtained underlayer film was about 10 nm.

On the surface of the lower film, use the inkjet printer DMP- 2831, a curable imprint composition adjusted to a temperature of 23°C was discharged at a droplet volume of 1 pL per nozzle, and the droplet was coated in a square array at intervals of about 100 μm on the above-mentioned underlayer film.

A quartz mold (rectangular line/space pattern (1/1), line width 40nm, groove depth 100nm, line edge roughness 3.5nm) was mounted on it so as to be in contact with the curable composition layer for imprinting. The wafer side was exposed at 300mJ/cm ² using a high pressure mercury lamp. After the exposure, the quartz wafer was separated, and the peeling force at that time was measured.

This peeling force corresponds to the adhesion force F (unit: N). The peel force was measured according to the method of measuring the peel force of the comparative example described in paragraphs 0102 to 0107 of JP-A-2011-206977. That is, it carried out according to peeling steps 1-6 and 16-18 of FIG. 5 of said publication.

45N A:F

45N

30N B: 45N>F

30N

20N C: 30N>F

20N

D: 20N>F

<Evaluation of wettability>

A silicon wafer (8 inches in diameter) was spin-coated with an underlayer film-forming composition for imprinting. Thereafter, an underlayer film was formed on the adhesive layer by heating with a hot plate under baking conditions of 150° C., 3 minutes, and an air atmosphere. The thickness of the obtained underlayer film was about 10 nm.

On the surface of the lower layer film, using the inkjet printer DMP-2831 manufactured by FUJIFILM Dimatix Co., Ltd., a curable composition for imprinting adjusted to a temperature of 23° C. was ejected at a droplet volume of 1 pL per nozzle, and the liquid was sprayed on the lower layer film. The droplets are applied in a square array at intervals of approximately 100 μm.

After coating, the droplet shape after 3 seconds was photographed, and the droplet diameter was measured. Use per 1 level Two samples were collected and measured three times respectively. And the arithmetic mean value of 6 times in total was adopted as an evaluation value. The results are shown in Tables 1 to 4.

A: The average diameter of IJ droplets > 500 μm

500μm B: Average diameter of 400μm<IJ droplet

500μm

400μm C: Average diameter of 320μm<IJ droplet

400μm

320μm D: Average diameter of IJ droplets

320μm

polymer

[chemical formula 21]

The dotted line shows the detached components after detachment (same below)

Molecular Weight refers to the molecular weight.

[chemical formula 22]

[chemical formula 27]

[chemical formula 29]

Detachment reaction accelerator or its precursor

T-1, T-4, T-5, T-6 and T-7 are photoacid generators. T-2 is a thermal base generator. T-3 is a thermal acid generator.

Photopolymerization initiator

From the above results, it is clear that the underlayer film-forming composition for imprint of the present invention contains a polymer free from a specific release component, and when used in combination with a curable composition for imprint, it exhibits excellent wettability and good adhesion. (Example 1~21). On the other hand, it can be seen that the wettability or adhesiveness is poor when the detachment component is not detachable or the specific chemical structure cannot be obtained even if the detachment component is detachable (Comparative Examples 1 to 3).

The film of the imprint curable composition produced in each example was brought into contact with a quartz mold patterned with a width of 500 nm. Thereafter, the film was cured by irradiating ultraviolet rays from the mold side. Next, the mold is separated to obtain a pattern of a cured product on which the pattern of the mold is transferred. As a result, it was confirmed that a good pattern can be formed in any cured product.

1: Substrate

2: Lower film

3: Hardening composition for imprinting

4: Molding

Claims (24)

An underlayer film-forming composition for imprinting, which includes a polymer and a solvent, in which, when the underlayer film-forming composition for imprinting is made into a film and baked at 80° C., the following formula (r1 -1) or a compound represented by formula (r2) and having a molecular weight of 210 to 1000 is released from the polymer,

In the formula, R ^r1 and R ^r2 are independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a group represented by the following formula (RL-1), and at least one of R ^r1 and R ^r2 One is an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a group represented by the following formula (RL-1), R ^r4 , R ^r5 and R ^r6 are aryl groups,

In the formula (RL-1), ^LR1 and ^LR2 are independently a single bond or a linking group L, Ar ^R is a linking group L containing an aromatic ring, ^PR is a group having a polymerizable group, and nr is 0 An integer of ~4, mr is an integer of 1~2, and the linking group L is an alkylene group, an alkenyl group, an alkynyl group, (oligomeric) alkoxyl group, an aryl group, an oxygen atom, a carbonyl group or a combination of the Wait for the group. The composition for forming an underlayer film for imprint according to claim 1, wherein the polymer contains a group represented by any one of the following formula (R-1) to formula (R-4),

In the formula, R ¹ to R ³ are each independently a monovalent substituent, R ⁴ to R ¹² are each independently a hydrogen atom or a monovalent substituent, and X represents a bonding position to the main chain of the polymer. The composition for forming an underlayer film for imprint according to claim 2, wherein the C-O bond in the formula contains a substituent represented by any one of the formulas (R-1) to (R-4) The polymer decomposes, and the compound represented by the formula (r1-1) or the formula (r2) and having a molecular weight of 210 to 1000 is detached from the polymer. The composition for forming an underlayer film for imprint according to claim 1, wherein the polymer contains a polymerizable group. The composition for forming an underlayer film for imprint according to claim 4, wherein the polymerizable group contains an acryl group or a methacryl group. The composition for forming an underlayer film for imprint according to claim 1, wherein the polymer contains an aromatic ring. The composition for forming an underlayer film for imprint according to claim 1, wherein the polymer contains at least one structural unit represented by any one of the following formulas (1) to (6),

In the formula, R ^P4 is a hydrogen atom or a methyl group, and R ^P1 represents a group capable of detaching the compound represented by formula (r1-1) or formula (r2). The composition for forming an underlayer film for imprint according to claim 1, wherein the compound represented by the formula (r1-1) or formula (r2) contains an aromatic ring. The composition for forming an underlayer film for imprint according to claim 1, wherein the compound represented by the formula (r1-1) or formula (r2) contains a polymerizable group. The composition for forming an underlayer film for imprint according to claim 9, wherein the polymerizable group contains an acryl group or a methacryl group. The composition for forming an underlayer film for imprint as described in item 1 of the patent claims, wherein at least one of R ^r1 and R ^r2 of the formula (r1-1) and R ^r4 to R ^r6 of the formula (r2) at least one of which contains a polymerizable group. The composition for forming an underlayer film for imprint according to claim 1, further comprising a detachment reaction accelerator or its precursor. The composition for forming an underlayer film for imprint according to claim 1, further comprising a photopolymerization initiator. The composition for forming an underlayer film for imprint according to claim 1, wherein the compound represented by the formula (r1-1) or formula (r2) has a surface tension of 35mN/m~55mN/m. The composition for forming an underlayer film for imprint according to claim 1, wherein The solvent is contained in a ratio of 95.0% by mass or more. A kit comprising the imprint underlayer film-forming composition described in any one of the first to fifteenth claims of the patent application and a hardening composition for imprint including a polymerizable compound. The kit according to claim 16 of the patent application, wherein the Hansen solubility parameter of the compound represented by the formula (r1-1) or formula (r2) and the Hansen solubility parameter of the hardening composition for imprinting are used And the △HSP value calculated by the following mathematical formula (H1) is 5 or less, △HSP=(4.0×△D ² +△P ² +△H ² ) ^0.5 ...(H1) The above △D is The difference between the dispersion term component of the Hansen solubility parameter vector of the curable composition for imprinting and the dispersion term component of the Hansen solubility parameter vector of the compound represented by formula (r1-1) or formula (r2), the ΔP is The difference between the polar term component of the Hansen solubility parameter vector of the curable composition for imprinting and the polar term component of the Hansen solubility parameter vector of the compound represented by formula (r1-1) or formula (r2), the ΔH is The difference between the hydrogen bond term component of the Hansen solubility parameter vector of the curable composition for imprinting and the hydrogen bond term component of the Hansen solubility parameter vector of the compound represented by formula (r1-1) or formula (r2). An underlayer film formed from the underlayer film-forming composition described in any one of the first to fifteenth claims of the patent application. A laminate formed from the kit described in claim 16 or claim 17 of the scope of the patent application, the laminate comprising: an underlayer film formed from the underlayer film forming composition for imprinting; and an embossing layer formed from the The imprint is formed with a curable composition and is located on the surface of the lower film. A method for manufacturing a laminate, which uses the 16th or 17th item in the scope of the patent application The kit for producing a laminate according to the above item includes a process of applying a hardening composition for imprinting to the surface of the underlayer film formed from the underlayer film-forming composition for imprinting. The method for producing a laminate as described in claim 20, wherein the curable composition for imprinting is applied to the surface of the underlayer film by an inkjet method. The manufacturing method of the laminated body described in the 20th or 21st claim of the patent application, the manufacturing method further includes the process of applying the underlayer film-forming composition for imprinting on the substrate into a layered process, and includes Heating at ~250°C is suitable for the process of forming the layered underlayer film-forming composition for imprinting. A method for manufacturing a pattern of a hardened object, which uses the kit described in item 16 or item 17 of the scope of the patent application to manufacture a pattern of a hardened object, the method comprising: an underlayer film forming process, and a composition for forming an underlayer film for imprinting on a substrate material to form an underlayer film; application process, applying a curable composition for imprinting on the surface of the underlayer film; mold contact process, making the curable composition for imprint contact with a mold having a pattern for transferring the shape of the pattern a light irradiation process of irradiating light to the curable composition for imprinting to form a cured product; and a demoulding process of separating the cured product from the mold. A method of manufacturing a circuit board, which includes the process of obtaining a cured product pattern through the manufacturing method described in claim 23 of the patent application.

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