TW201938716A - Underlayer film forming composition for imprint, curable composition for imprint, and kit - Google Patents

Abstract

The invention provides an underlayer film-forming composition for imprinting, which comprises a polymer and a solvent. In this composition, when the underlayer film-forming composition for imprinting is made into a film and baked at 80 ° C, the molecular weight is 210 or more. Specific compounds are released from the above polymers. Furthermore, the present invention relates to a hardenable composition for imprinting and a kit using the same, the underlayer film-forming composition for imprinting.

Description

Underlayer film-forming composition for imprint, curable composition for imprint, kit

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

The imprint method is a method in which a fine pattern is transferred by pressing a mold to a curable composition and curing the composition, and then peeling the mold. Attempts are being made to apply this method to precision processing fields such as the manufacture of semiconductor integrated circuits. The imprint method does not require expensive microfabrication equipment such as a segmenter or an electron beam. Since it is possible to reduce manufacturing costs, simple steps, high resolution, and high throughput, research on mass production of devices has been actively conducted 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 and a light-transmitting mold is combined 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 use the pattern as an insulating member or as a mask for further processing. A person using ultraviolet (UV: Ultraviolet) as the light to be irradiated is sometimes called a UV nanoimprint method. The photonanoimprinting method typified by this UV nanoimprinting method is different from the thermal nanoimprinting method which requires heating using a thermosetting resin composition, and can process at room temperature. Therefore, it can be widely used as a technology for realizing high quality in manufacturing heat-repellent semiconductor devices and the like.

In the photonanoimprinting method using a photosensitive resin composition, a technique using an underlayer film has been proposed (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) acryloxy group, an alkoxycarbonyl group, and a member selected from the group consisting of epoxyethyl group and oxetan group. At least one type of group; a nonionic surfactant; and a solvent. In addition, it is described that the variation in the thickness of the residual film after the extrusion of the mold is small, and the variation in the line width distribution of the pattern after pressing is unlikely to occur.
[Prior technical literature]
[Patent Literature]

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

As described above, compared with the technology based on photolithography, the formation of micropatterns based on imprinting has excellent efficiency, which can greatly improve the manufacturing cost and productivity of manufacturing semiconductor devices. Furthermore, with the advancement of semiconductor technology, there is a demand for miniaturization of patterns and further improvement in manufacturing quality. For example, in the manufacturing process based on imprinting, in order to improve the adhesion between the substrate and the curable composition for imprinting, the use of an underlayer film-forming composition for imprinting to study a coating film of the above-mentioned imprinting underlayer film-forming composition has been studied. A film is formed on the surface by applying a curable composition for imprinting, and the wettability of the film is required to be further improved. Also, of course, the adhesion between the underlayer film and the embossed layer formed from these compositions is also required.
Therefore, an object of the present invention is to provide a hardenable composition for imprinting, which has better wettability than a coating film of an underlayer film-forming composition for imprinting, and forms an underlayer film and imprinting from these compositions. An underlayer film-forming composition for imprint, a curable composition for imprint, and a kit using the same, which are excellent in adhesion of the layers.

Based on the above-mentioned problems, the present inventors have conducted studies, and as a result, they have found that the above-mentioned problems can be solved by using a polymer capable of generating a specific release component in the underlayer film-forming composition for imprint. Specifically, the above-mentioned problem is solved by the following method <1>, preferably by <2> to <27>.
<1> An underlayer film-forming composition for imprinting comprising a polymer and a solvent. In the composition, when the above-mentioned underlayer film-forming composition for imprinting is made into a film shape and baked at 80 ° C., the following is performed: A compound represented by formula (r1) or (r2) and having a molecular weight of 210 or more is detached from the polymer,
[Chemical Formula 1]

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, and 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 imprinting according to <1>, wherein the compound represented by the above formula (r1) or (r2) is represented by the formula (r1-1),
[Chemical Formula 2]

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 underlayer film-forming composition for imprinting according to <1> or <2>, wherein the polymer includes a group represented by any one of the following formulae (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 position to be bonded to the polymer's main chain.
<4> The underlayer film-forming composition for imprinting according to <3>, wherein the CO bond in the formula includes a substituent represented by any one of the formulae (R-1) to (R-4). The polymer is decomposed, and the compound represented by the formula (r1) or (r2) and having a molecular weight of 210 or more is detached from the polymer.
<5> The underlayer film-forming composition for imprinting according to any one of <1> to <4>, wherein the polymer contains a polymerizable group.
<6> The underlayer film-forming composition for imprinting according to <5>, wherein the polymerizable group includes a (meth) acrylfluorenyl group.
<7> The underlayer film-forming composition for imprinting according to any one of <1> to <6>, wherein the polymer includes an aromatic ring.
<8> The underlayer film-forming composition for imprinting according to any one of <1> to <7>, wherein the polymer includes one represented by any one of the following formulae (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 removing a compound represented by formula (r1) or (r2).
<9> The composition for forming an underlayer film for imprinting according to any one of <1> to <8>, wherein the compound represented by the above formula (r1) or (r2) contains an aromatic ring.
<10> The underlayer film-forming composition for imprinting according to any one of <1> to <9>, wherein the compound represented by the formula (r1) or (r2) contains a polymerizable group.
<11> The underlayer film-forming composition for imprinting according to <10>, wherein the polymerizable group includes a (meth) acrylfluorenyl group.
<12> The underlayer film-forming composition for imprinting according to any one of <1> to <11>, wherein at least one of R ^r1 and R ^r2 in the above formula (r1) and (r2) At least one of R ^r4 to R ^r6 contains a polymerizable group.
<13> The underlayer film-forming composition for imprinting according to any one of <1> to <12>, wherein the molecular weight of the compound represented by the formula (r1) or (r2) is 1,000 or less.
<14> The underlayer film-forming composition for imprinting according to any one of <1> to <13>, further comprising a release reaction accelerator or a precursor thereof.
<15> The underlayer film-forming composition for imprinting according to any one of <1> to <14>, further comprising a photopolymerization initiator.
<16> The underlayer film-forming composition for imprinting according to any one of <1> to <15>, wherein the surface tension of the compound represented by the above formula (r1) or (r2) is 35 to 55 mN / m .
<17> The underlayer film-forming composition for imprinting 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 composition for imprint, which contains a polymerizable compound and is used in combination with the imprint lower-layer film-forming composition according to any one of <1> to <17>.
<19> A kit comprising the underlayer film-forming composition for imprinting according to any one of <1> to <17> and a curable composition for imprinting containing a polymerizable compound.
<20> The kit according to <19>, which is based on the Hansen solubility parameter of the compound represented by the above formula (r1) or (r2) and the Hansen solubility parameter of the hardening composition for imprinting described below. The ΔHSP value calculated by the mathematical formula (H1) is 5 or less,
ΔHSP = (4.0 × ΔD ² + ΔP ² + ΔH ² ) ^0.5 …… (H1)
The ΔD is the difference between the dispersion term component of the Hansen solubility parameter vector of the hardening composition for imprinting and the dispersion term component of the Hansen solubility parameter vector of the compound represented by formula (r1) or (r2), and the ΔP is The difference between the polar term component of the Hansen solubility parameter vector of the hardening composition for printing and the polar term component of the Hansen solubility parameter vector of the compound represented by the formula (r1) or (r2). The difference between the hydrogen bond term component of the Hansen solubility parameter vector of the composition and the hydrogen bond term component of the Hanson solubility parameter vector of the compound represented by formula (r1) or (r2).
<21> An underlayer film formed from the underlayer film-forming composition according to any one of <1> to <17>.
<22> A laminated body formed of the kit according to <19> or <20>, the laminated body having: an underlayer film formed of the above-mentioned underlayer film forming composition for imprint; and an imprint layer formed of the above The embossing curable composition is formed on the surface of the underlayer film.
<23> A method for manufacturing a laminated body, which uses the kit described in <19> or <20> to manufacture a laminated body, wherein the manufacturing method includes forming a surface of an underlayer film from the above-mentioned underlayer film forming composition for imprinting Suitable for hardening composition for imprinting.
<24> The method for producing a laminated body according to <23>, wherein the curable composition for imprint is applied to the surface of the underlayer film by an inkjet method.
<25> The method for manufacturing a laminated body according to <23> or <24>, wherein the manufacturing method further includes applying the above-mentioned underlayer film-forming composition for imprinting to a substrate on a substrate as a layered process, and the method is included in 80 Heating at ~ 250 ° C is suitable for the process of forming the above-mentioned layered underlayer film-forming composition for imprinting.
<26> A method for manufacturing a hardened pattern, which uses the kit described in <19> or <20> to produce a hardened pattern. The method for manufacturing the hardened pattern includes a lower-layer film forming process and applying imprinting on a substrate. The underlayer film is used to form a composition to form an underlayer film; a process is applied, and a hardening composition for imprinting is applied to the surface of the underlayer film; Contacting the mold of the pattern; a light irradiation process to irradiate the hardening composition for imprint with light to form a hardened object; and a demolding process to separate the hardened object from the mold.
<27> A method for manufacturing a circuit board, comprising a process of obtaining a hardened pattern by the manufacturing method described in <26>.
[Inventive effect]

According to the present invention, the wettability of the hardening composition for imprinting with respect to the coating film of the underlayer film-forming composition for imprinting and the adhesion between the underlayer film and the imprinting layer formed from these compositions can be improved. Furthermore, it is possible to provide an underlayer film-forming composition for imprinting, a curable composition for imprinting, and a kit to which these are applied.

Hereinafter, the content of this invention is demonstrated in detail. In addition, in this specification, "-" means using the value contained before and after as a lower limit value and an upper limit value.
In this specification, "(meth) acrylate" means an acrylate and a methacrylate.

In this specification, "imprint" means a pattern transfer having a size of preferably 1 nm to 10 mm, and more preferably means a pattern transfer having a size of approximately 10 nm to 100 µm (nano imprint).
In the description of the group (atomic group) in the present specification, the unrepresented and unsubstituted marks include those having no substituent and those having a substituent. For example, "alkyl" includes not only alkyl groups (unsubstituted alkyl groups) having no substituents, but also alkyl groups (substituted alkyl groups) having substituents.
In this specification, "light" includes not only light or electromagnetic waves with wavelengths in the ultraviolet, near-ultraviolet, far-ultraviolet, visible, or infrared regions, but also radiation. The radiation includes, for example, microwaves, electron beams, extreme ultraviolet (EUV), and X-rays. In addition, laser light such as a 248 nm excimer laser, a 193 nm excimer laser, and a 172 nm excimer laser can also be used. The light may be a monochromatic light (single-wavelength light) passing through a filter or a light (composite light) having a plurality of different wavelengths.
When the temperature in the present invention is not particularly described, it is set to 23 ° C.
The boiling point in the present invention refers to the boiling point in 1 atmosphere (1atm = 1013.25hPa).

The underlayer film-forming composition for imprinting of the present invention includes a polymer and a solvent, and when the underlayer film-forming composition for imprinting is formed into a film shape and baked at 80 ° C., the following formula (r1) or ( The compound represented by r2) (hereinafter, sometimes referred to as a release component) is released from the polymer. Thereby, the wettability of the hardenable composition for imprinting during imprinting is improved with respect to the coating film of the underlayer film-forming composition for imprinting, and the adhesion between the lower layer film and the imprinting layer is formed from these compositions. improve. The reason can be inferred as follows. That is, it is considered that the generation of the low-molecular component causes the interfacial tension on the surface of the lower film to decrease, and the wettability increases accordingly. In addition, it is thought that a diffusion path is generated in the underlayer film, so that the hardening component of the hardening composition for imprinting is immersed in the area where the low-molecular component exists in the underlayer film, and a part of it is hardened, thereby being between the underlayer film and the hardened material The adhesion is improved.

<Underlayer film-forming composition for imprinting>
In the present invention, when the underlayer film-forming composition for imprinting is formed into a film shape and baked at 80 ° C., a compound represented by the following formula (r1) or (r2) and having a molecular weight of 210 or more is detached from the polymer. Hereinafter, in this specification, the said compound is called a release component.

＜＜ detached ingredient ＞＞
The release component is a component which makes the underlayer film-forming composition for imprinting into a film shape and is released 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 detached component in the first embodiment of the present invention is represented by the following formula (r1) or (r2). When the release component is a compound represented by the formula (r1) or (r2), the polymerization initiator in the hardening composition for imprinting also diffuses into the lower film forming composition for imprinting, and the hardening composition for imprinting At the time of hardening, the underlayer film-forming composition for imprinting is also hardened at the same time, so that the adhesion between the hardening composition for imprinting and the underlayer film is more excellent.
[Chemical Formula 5]

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, and 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 the formula (r1) or (r2) is preferably represented by the following formula (r1-1).
[Chemical Formula 6]

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

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 fluorene ring, a fluorene ring, a pinene ring, a biphenyl ring, a terphenyl ring, an indene ring, and a diphenyl ring. Indane ring, bitriphenylene ring, tetraphenylene ring, perylene ring, chrysene ring, fluorene ring, tetralin ring, etc. The aromatic ring may have a structure in which plural rings are connected with or without a linking group L, and examples thereof include a biphenyl ring, a diphenylmethane ring and a triphenylmethane ring. Alternatively, including a part of the examples exemplified above, as a structure in which a plurality of benzene rings are connected, those having the following formulae Ar1 to Ar5 are mentioned. A straight line drawn from the vicinity of the center of the benzene ring in the formula represents a bonding bond. It refers to bonding to an arbitrary linking group via the single bond, or bonding to the main chain of L ¹ , L ² , P or a polymer of the following formula (T1) with or without the single bond. A ¹ is a divalent linking group, and examples of the linking group L are preferred. The alkylene group may be substituted by a fluorine atom (carbon number 1 to 12 is preferred, 1 to 6 is more preferred, and 1 to 3 is further preferred. ), A carbonyl group, an oxygen atom, a sulfofluorenyl group, a sulfinamilide group, and -NR ^N -are more preferred. A ² means a trivalent linking group or a methine group containing a nitrogen atom and a phosphorus atom. In the expressions Ar1 to Ar5, there are two or three bonding bonds arbitrarily, which means that the bonding can be performed at a desired portion according to the required number of connections. For example, a state in which two bonds are extended from one benzene ring can also be cited as a preferred aspect of the present invention. In addition, an aspect in which Ar2 having three rings is a divalent linking group can also be cited as a preferred aspect of the present invention.
[Chemical Formula 7]

Examples of the aromatic ring exemplified herein, including those described above, are referred to as ring aCy.

When the aromatic ring is an aromatic heterocyclic ring, its carbon number is preferably from 1 to 12, more preferably from 1 to 6, and even more preferably from 1 to 5. Specific examples thereof include a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a pyrazole ring, a triazole ring, a tetrazole ring, a thiazole ring, an oxazole ring, a pyridine ring, a piperazine ring, a pyrimidine ring, and a pyridine. Azine ring, tricyclic ring, isoindole ring, indole ring, indazole ring, purine ring, quinazine ring, isoquinoline ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazole A phenoline ring, a cinnoline ring, a carbazole ring, an acridine ring, a phenazine ring, a phenothiazine ring, a phenothiazine ring, and the like.
The aromatic heterocyclic ring may have a structure in which a plurality of ring structures are connected with or without a linking group L.
The aromatic heterocyclic ring shown here is called ring hCy.

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

It is preferable that the release component contains a polymerizable group. Examples of the polymerizable group include groups containing an ethylenically unsaturated group, an epoxy group, an epoxy group, an oxetanyl group, and the like. Examples of the ethylenically unsaturated group include a group containing a vinyl group, an allyl group, a vinyl phenyl group, a (meth) acrylfluorenyl group, and a (meth) acrylfluorenyl group. The polymerizable group exemplified herein is referred to as a polymerizable group Ps. In the present invention, it is preferable that the polymerizable group Ps contains a (meth) acrylfluorenyl group or a (meth) acrylfluorenyl group.
In particular, at least one of R ^r1 and R ^r2 in formula (r1), at least one of R ^r4 to R ^r6 in formula (r2), and at least one of R ^r1 and R ^r2 in formula (r1-1) It is preferable to include a polymerizable group. The polymerizable group is preferably the polymerizable group Ps.
Furthermore, it is preferable that the release component contains an ethylenic double bond. In particular, it is preferable to form an ethylenic double bond by detaching from the polymer. By performing such detachment, the effect of close contact force is exerted.

In formula (r1) or (r2) or formula (r1-1), when R ^r1 , R ^r2 , R ^r4 , R ^r5 , and R ^r6 are substituents, examples of the substituent include the substituent T described later. For example, among them, each is independently an alkyl group (carbon number 1 to 12 is preferred, 1 to 6 is more preferred, and 1 to 3 is more preferred), an alkenyl group (carbon number 2 to 12 is preferred, 2 to 2 6 is more preferred, 2 to 3 are further preferred), aryl (6 to 22 carbons is preferred, 6 to 18 is more preferred, 6 to 10 is more preferred), aralkyl (7 to 6 carbons) 23 is preferable, 7 to 19 is more preferable, and 7 to 11 is more preferable) or a group represented by the following formula (RL-1) is more preferable. Furthermore, in formulae (r1) and (r2), it is particularly preferable that at least R ^r2 or R ^r6 is a group represented by the following formula (RL-1).

[Chemical Formula 8]

L ^R1 and L ^R2 each independently a single bond or a linking group, Ar ^R is a linking group comprising aromatic rings, P ^R is a group having the polymerizable group. nr is an integer from 0 to 8, and mr is an integer from 1 to 4.

L ^R1 is a 1 + mr valence aromatic ring (the examples of aCy or hCy above are preferred), alicyclic rings (the examples of alicyclic fCy below are preferred), linear or branched alkane-structured groups (carbon number 1 to 40 is preferred, 1 to 30 is more preferred, and 1 to 20 is further preferred), a linear or branched olefin structure group (carbon number of 2 to 40 is preferred, 2 to 30 is more preferred, 2 to 20 is more preferred) or a linear or branched alkyne structure group (2 to 40 carbons is preferred, 2 to 30 is more preferred, 2 to 20 is more preferred) is more preferred.

An example in which the linking group of L ^{R2 is} a linking group Lh containing a linking group L or a hetero atom described below is preferred. Among them, alkylene (carbon number 1 to 12 is preferred, 1 to 6 is more preferred, and 1 to 3 is more preferred), and aryl (carbon number 6 to 22 is preferred, 6 to 18 is more preferred) , 6 to 10 are further preferred), (oligomeric) alkoxy (the carbon number of the alkylene in one constituent unit is preferably 1 to 12, 1 to 6 is more preferred, and 1 to 3 is It is further preferred; the repeat number is preferably from 1 to 50, more preferably from 1 to 40, and even more preferably from 1 to 30), a carbonyl group, an oxygen atom, or a combination thereof.
L ^R2 may form a ring by bonding to L ^R1 with or without a linking group L.

Ar ^R is a linking group containing 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 preferred. When Ar ^R contains a substituent other than an aromatic ring, examples of the linking group include the following linking group L. Among them, alkylene (carbon number of 1 to 24 is preferred, and 1 to 12 is more preferred. 1 to 6 are further preferred), alkenyl (2 to 12 carbons are preferred, 2 to 6 are more preferred, 2 to 3 are more preferred), and alkenyl (2 to 12 carbons are preferred) , 2 to 6 are more preferred, 2 to 3 are more preferred), (oligomeric) alkoxy (the number of carbons of the alkylene in one constituent unit is preferably 1 to 12, and 1 to 6 are More preferably, 1 to 3 are further preferred; repeating number is 1 to 50, more preferred is 1 to 40, more preferred is 1 to 30, further preferred is aryl (carbon number 6 to 22 is preferred, 6 to 18 are more preferred, and 6 to 10 are further preferred) or a combination thereof. ^R2 Ar ^R or P ^R L may be bonded to form a ring via or not via a linking group L and L ^R1,.

P ^R is a group having a polymerizable group, and an example in which the polymerizable group is the polymerizable group Ps is preferable. P ^R may form a ring by bonding to L ^R1 and L ^R2 with or without a linking group L.

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

nr is an integer from 0 to 8, 0 to 6 is preferred, 0 to 4 is more preferred, and 0 to 2 is further preferred. mr is an integer of 1 to 4, and 1 to 2 is preferred.

^Examples of the divalent substituent of R ^r3 include CH ₂ (second embodiment described below), CHR ^r8 or C (R ^r9 ) ₂ . Among them, R ^r8 and R ^r9 are each independently a substituent T described later. Among them, alkyl (more preferably 1 to 12 carbons, more preferably 1 to 6 and even more preferably 1 to 3), alkenyl ( Carbon number 2 to 12 is preferred, 2 to 6 is more preferred, 2 to 3 is further preferred), alkynyl (carbon number 2 to 12 is preferred, 2 to 6 is more preferred, 2 to 3 is further preferred Good), aryl (6 to 22 carbons is preferred, 6 to 18 is more preferred, 6 to 10 is more preferred), aralkyl (7 to 23 carbons is preferred, 7 to 19 is more preferred) , 7 to 11 are further preferred) are more preferred. C (R ^r9) 2 th R ^r9 ₂ may be the same as each other or different.

Examples of the heteroatom-containing linking group Lh include an oxygen atom, a sulfur atom, a carbonyl group, a thiocarbonyl group, a sulfofluorenyl group, a sulfinylsulfenyl group, -NR ^N- , and (oligomeric) alkoxy group (1 constituent unit) The number of carbons in the alkylene group is preferably 1 to 12, 1 to 6 is more preferred, 1 to 3 is even more preferred; 1 to 50 is more preferred, 1 to 40 is more preferred, and 1 to 30 is further preferred) or a linking group formed by a combination of these. The number of atoms constituting the linking group Lh containing a hetero atom is preferably from 1 to 100, more preferably from 1 to 70, and particularly preferably from 1 to 50. The number of connected atoms of Lh is preferably from 1 to 25, more preferably from 1 to 20, even more preferably from 1 to 15, and even more preferably from 1 to 10. Furthermore, the (oligomeric) alkoxy group may be either an alkoxy group or an oligomeric alkoxy group. The (oligomeric) alkoxy group may be linear, cyclic, or linear or branched. When the linking group is a group capable of forming a salt such as -NR ^N- or a carboxyl group is substituted, the group may form a salt.

Examples of the substituent T include an alkyl group (carbon number 1 to 24 is preferred, 1 to 12 is more preferred, and 1 to 6 is more preferred), and an arylalkyl group (carbon number 7 to 21 is preferred, 7 to 15 are more preferred, 7 to 11 are further preferred), alkenyl (2 to 24 carbons are preferred, 2 to 12 are more preferred, 2 to 6 are more preferred), alkynyl (2 to 6 carbons) -12 is preferred, 2-6 is more preferred, 2-3 is more preferred), hydroxyl and amine groups (carbon number 0-24 is preferred, 0-12 is more preferred, 0-6 is further preferred ), Thiol group, carboxyl group, aryl group (carbon number 6 to 22 is preferred, 6 to 18 is more preferred, 6 to 10 is more preferred), alkoxy (carbon number 1 to 12 is preferred, 1 ～ 6 is more preferable, 1-3 is more preferable), aryloxy group (carbon number is 6-22 is preferable, 6-18 is more preferable, 6-10 is more preferable), fluorenyl group (carbon number 2 -12 is preferred, 2-6 is more preferred, 2-3 is more preferred), oxo (carbon number 2-12 is preferred, 2-6 is more preferred, 2-3 is more preferred) Aryl fluorenyl (carbon number 7 to 23 is preferred, 7 to 19 is more preferred, 7 to 11 is more preferred), aryl fluorenyloxy (carbon number 7 to 23 is preferred, 7 to 1) 9 is more preferred, 7 to 11 are further preferred), carbamoyl (carbon number 1 to 12 is preferred, 1 to 6 is more preferred, 1 to 3 is further preferred), sulfamoyl (carbon Numbers 0 to 12 are preferred, 0 to 6 are more preferred, 0 to 3 are more preferred), sulfonic acid groups, and alkylsulfonyl groups (carbon numbers 1 to 12 are preferred, and 1 to 6 are more preferred. 1 to 3 are further preferred), arylsulfonyl (carbon number 6 to 22 is preferred, 6 to 18 is more preferred, 6 to 10 is more preferred), heterocyclic group (carbon number 1 to 12 is Preferably, 1 to 8 are more preferred, 2 to 5 are further preferred, and 5- or 6-membered rings are preferred), (meth) acrylfluorenyl, (meth) acrylfluorenyloxy, and halogen atoms (For example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an oxo group (= O), an imino group (= NR ^N ), an alkylene group (= C (R ^N ) ₂ ), and the like. R ^N is a hydrogen atom, an alkyl group (carbon number 1 to 12 is preferred, 1 to 6 is more preferred, 1 to 3 is more preferred), an alkenyl group (carbon number 2 to 12 is preferred, 2 to 6 is More preferably, 2 to 3 are further preferred), alkenyl (2 to 12 carbons are preferred, 2 to 6 are more preferred, 2 to 3 are more preferred), and aryl (6 to 22 carbons are more preferred) 6 to 18 are more preferred, 6 to 10 are further preferred), or aralkyl (7 to 23 carbons are preferred, 7 to 19 are more preferred, 7 to 11 are further preferred), of which, A hydrogen atom, methyl, ethyl or propyl is preferred. The alkyl moiety, alkenyl moiety, and alkynyl moiety contained in each substituent may be chained, cyclic, or linear or branched. When the substituent T is a group capable of obtaining a substituent, it may further have a substituent T. 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 may form a salt.

Examples of the linking group L include an alkylene group (carbon number 1 to 24 is preferred, 1 to 12 is more preferred, and 1 to 6 is more preferred), and an alkenyl group (carbon number 2 to 12 is more preferred. 2 to 6 is more preferred, 2 to 3 is further preferred), alkynyl (carbon number 2 to 12 is preferred, 2 to 6 is more preferred, 2 to 3 is further preferred), (oligomeric) stretching Alkoxy (The number of carbons of the alkylene group in one constituent unit is preferably 1 to 12, more preferably 1 to 6, more preferably 1 to 3, and the number of repeats is preferably 1 to 50, 1 -40 is more preferred, 1-30 is further preferred), arylene (carbon number 6-22 is preferred, 6-18 is more preferred, 6-10 is further preferred), oxygen atom, sulfur atom, Sulfonyl, carbonyl, thiocarbonyl, -NR ^N- and combinations of these. The alkylene group may have the above-mentioned substituent T. For example, the alkylene group may have a hydroxyl group. The number of atoms contained in the linking group L is preferably 1 to 50 other than a hydrogen atom, more preferably 1 to 40, and still more preferably 1 to 30. The number of connected atoms refers to the number of atoms in the shortest distance in the group of atoms participating in the connection. For example, when -CH _2- (C = O) -O-, the number of atoms participating in the connection is six, and in addition to hydrogen atoms, there are four. On the other hand, the shortest atom participating in the connection is -CCO-, which becomes three. The number of connecting atoms is preferably from 1 to 24, more preferably from 1 to 12, and even more preferably from 1 to 6. The above-mentioned alkylene, alkenyl, alkynyl, and (oligomeric) alkoxy may be linear, cyclic, or linear 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 detached component is 210 or more. It is preferable that the molecular weight is equal to or more than the lower limit value, thereby suppressing volatilization during baking. The molecular weight of the detached component is preferably 210 or more, more preferably 250 or more, and more preferably 300 or more. The upper limit is actually 1000 or less.

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

The detached component of the Hanson solubility parameter (HSP) vector:
(I) The dispersion component (component d) is preferably from 14.0 to 20.0, more preferably from 15.0 to 19.0, and even more preferably from 16.0 to 19.5;
(Ii) The polar component (p component) is preferably 2.0 to 9.0, more preferably 3.0 to 6.0, and more preferably 3.5 to 5.0;
(Iii) The hydrogen bonding term component (component h) is preferably 3.0 to 12.0, more preferably 4.7 to 7.0, and even more preferably 5.0 to 6.5.

<< specific polymer >>
Regarding the polymer used in the present invention (hereinafter, this polymer may be referred to as a specific polymer), the underlayer film-forming composition for imprint containing the specific polymer is formed into a film shape at 80 to 250. When baking at ℃, a polymer that releases a releasing component from a polymer can be widely used. More specifically, it is preferable that the specific polymer is a polymer having a group serving as a release component in a side chain.
In the present invention, among all the constituent units constituting the polymer, 30% by mass or more is more preferable, and 40% by mass or more is a constitutional unit capable of releasing the detached component. The upper limit value is not particularly limited, and may be 100% by mass. Furthermore, in the present invention, it is not necessary to remove all the constituent units having a group capable of detaching a component under heating at 80 to 250 ° C., as long as it is at least 70% by mass, and preferably 80% by mass or more, It is more preferable to depart from 90% by mass or more, and it is more preferable to depart from 99% by mass or more.
In the present invention, the mass of the specific polymer is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more of the detached component. The upper limit value is not particularly limited, but is, for example, 80% by mass or less, 70% by mass or less is preferable, 60% by mass or less is more preferable, and 50% by mass or less is more preferable.
The specific polymer preferably contains a substituent represented by any one of the following formulae (R-1) to (R-4).
[Chemical Formula 9]

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 position to be bonded to the polymer's main chain.

In the formulae (R-2) to (R-4), it is preferable that R ⁴ to R ⁶ , R ⁷ to R ⁹ , and R ¹⁰ to R ^{12 are} not all hydrogen atoms. Contains a carbon atom bonded to an oxygen atom in the formula (R-1), that is, a carbon atom in which R ¹ to R ³ are 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 alkyl group or a tertiary alkyl group. The same applies to the formula (R-2), and it is preferable that the group containing an α carbon atom is a secondary alkyl group or a tertiary alkyl group. In contrast, it is preferable that the group containing the α carbon atom in the formulae (R-3) and (R-4) is a primary alkyl group or a secondary alkyl group.

At least one substituent of R ¹ to R ³ is preferable, and at least two substituents are more preferable. At least one substituent of R ⁴ to R ⁶ is preferable, and at least two substituents are more preferable. At least one of R ⁷ to R ⁹ is preferably a substituent, two is a hydrogen atom, and one is a substituent. At least one of R ¹⁰ to R ¹² is preferably a substituent, two is a hydrogen atom, and one is a substituent. When R ¹ to R ³ , R ⁴ to R ⁶ , R ⁷ to R ⁹ , R ¹⁰ to R ¹² are substituents, examples of the substituent include groups having the same meaning as in the above-mentioned R ^r1 , and the preferred range is also the same.
R ¹ to R ³ , R ⁴ to R ⁶ , R ⁷ to R ⁹ , and R ¹⁰ to R ¹² may be 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 in which the effects of the present invention are exhibited. For example, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, and the like may be further substituted with a halogen atom (a fluorine atom is preferred).

In the present invention, the CO bond in the formula is decomposed from a polymer containing a substituent represented by any one of formulae (R-1) to (R-4), and is represented by formula (r1) or (r2) or formula (r1) It is preferable that the compound represented by -1) has a molecular weight of 210 or more to be released from the polymer.
In particular, the carbon atoms substituted by R ^r1 and R ^{r2 in the} formula (r1) (the carbon atoms in the second position when the carbon atom contained in R ^r3 is set to the first position) are separated from the R of the previous formula (R-1) ¹ to R ³ are preferably substituted carbon atoms (α carbon atoms). The carbon atom at the 2-position of the formula (r1) is preferably a carbon atom substituted with R ⁴ to R ⁶ before the formula (R-2). Regarding formula (r2), the tertiary carbon atoms substituted by R ^r4 to R ^r6 are the above-mentioned α carbon atoms before leaving, that is, the substituted carbon atoms of R ¹ to R ^{3 of} formula (R-1) or formula (R -2) A carbon atom in which R ⁴ to R ⁶ are substituted is preferred.

In the formula (R-1), at least one of R ¹ to R ³ is an alkyl group so that it is decomposed at the position of CO and a double bond is formed at a detached position (position of an α carbon atom) on the component side. (The carbon number is 1-12, more preferred is 1-6, and further preferred is 1-3) is preferred, ethyl is more preferred, and methyl is more preferred. The same applies to formula (R-2). At least one of R ⁴ to R ⁶ is an alkyl group (carbon number 1 to 12 is more preferable, 1 to 6 is more preferable, and 1 to 3 is more preferable). Preferably, ethyl is more preferred, and methyl is further preferred.

The specific polymer preferably contains a polymerizable group, the polymerizable group-based polymerizable group Ps is more preferable, and the (meth) acrylfluorenyl group is more preferable. The structural unit having a group capable of detaching the detached component may have a polymerizable group, or the other structural unit may have a polymerizable group. In the present invention, it is preferred that the constituent units other than the constituent units having a group capable of detaching the detached 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 more preferably 80 to 100 mole%. Better.

In addition, the specific polymer preferably includes an aromatic ring, and the aromatic ring is preferably aCy or hCy. An aromatic ring may be sufficient as the structural unit which has a group which can isolate | separate a detachment component, and an aromatic ring may be provided as another structural unit. In the present invention, it is preferable that the constituent unit having at least a group capable of detaching the detached component has an aromatic ring.
In a specific polymer, the proportion of the constituent units including an aromatic ring is preferably 10 to 100 mol%, and more preferably 40 to 100 mol%.

The type of the specific polymer is not particularly limited, but examples thereof include (meth) acrylate resin, polyolefin resin, polystyrene resin, phenol resin (novolac resin), cyclic polyolefin resin, and polymer Resin resin, polyimide resin, polyacetal resin, polycarbonate resin, polyester resin, polyurethane resin, and silicone resin.

It is more preferable that the specific polymer contains at least one of the constituent units represented by any one of the following formulae (1) to (6).
[Chemical Formula 10]

R ^P4 is a hydrogen atom or a methyl group.
R ^P1 represents a group capable of removing a compound represented by the formula (r1) or (r2) or a compound represented by the formula (r1-1), and includes a group represented by the formulae (R-1) to (R-4) The group of the group is preferable. In R ^P1 , the linking group may be between X in the formulae (R-1) to (R-4) and an atom in the main chain. Examples of the linking group include a linking group L. The linking group at this time may be trivalent or higher. In this case, the structural unit that becomes the polymer is accompanied by a plurality of groups represented by the formulae (R-1) to (R-4) via a linking group. Examples of the trivalent or higher linking group include a group having an aromatic ring (aCy, hCy) structure and a group having an alkane structure (carbon numbers of 1 to 40 are preferred, 1 to 30 are more preferred, and 1 to 20 are further preferred. Preferred), groups with olefin structure (2 to 40 carbons are preferred, 2 to 30 are more preferred, 2 to 20 are more preferred), groups with alkyne structure (2 to 40 carbons are preferred) 2 to 30 are more preferred, and 2 to 20 are further preferred) or a combination of these or a combination of these and a linking group Lh. The group of an alkane structure, the group of an olefin structure, and the group of an alkyne structure may be chained, cyclic, or linear or branched. This trivalent or higher linking group is hereinafter referred to as the linking group Lm.

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

The main chain and the substituent R ^P1 of the polymer in the formulae (1) to (6) may have a substituent T as long as the effect of the present invention is exhibited.

The specific polymer-based copolymers described above are also preferable. The copolymerization component preferably includes at least one of a constituent unit (hereinafter, sometimes referred to as another constituent unit) represented by any one of the following formulae (1-1) to (1-6).
[Chemical Formula 11]

In the formulae (1-1) to (1-6), the substituents R ^{P 2} are each independently a substituent containing a polymerizable group, and R ^P4 is a hydrogen atom or a methyl group. The polymerizable group contained in R ^P2 is preferably the aforementioned Ps. R ^P2 may have a linking group between the polymerizable group and the main chain. Examples of the linking group L include a divalent linking group, and examples of the linking group Lm include a linking group having a trivalent or higher linking group. When there are two or more R ^{P 2} in the formulas (1-1) to (1-6), that is, when (R ^{P 2} ) _n (n is a natural number of 1 or more), a plurality of R ^{P 2} may be Bond to each other to form a ring. R ^P2 may be bonded to the main chain to form a ring. Further, within the range where the effects of the present invention are exerted, the substituent T may be substituted on the main chain of the formulae (1-1) to (1-6) and the substituents R ^P2 .
As R ^{P 2} , the following formula (T2) is preferred. The formula of R ^P2 is more preferably 80 or more and 1000 or less, more preferably 100 or more and 800 or less, and more preferably 150 or more and 600 or less.
-(L4) _n6- (P) _n7 ... (T2)
L ⁴ is the above-mentioned linking group L or Lm, in which an alkylene group, an arylene group, an (oligomeric) alkoxy group, a carbonyl group, an oxygen atom, a group of an alkane structure, a group of an olefin structure, or a group of an aryl structure Groups and combinations of these are preferred. n6 is an integer from 0 to 6. P is a polymerizable group Ps. n7 is an integer of 1 to 6, and 1 or 2 is preferable. When n7 is 3 or more, the terminal L ⁴ becomes a tetravalent or more valent linking group and all P may be substituted, but P may be substituted by two or more L ⁴ .
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. Regarding formulas (2) to (6), it is also preferable to include constituent units represented by formulas (1-2) to (1-6), respectively.

It is also preferable that the specific polymer further includes a constitutional unit (sometimes referred to as "another constitutional unit") having no polymerizable group. It is preferable that the other structural unit has a skeleton of the formulae (1-1) to (1-6) specified in the other structural unit. However, the substituent R ^P2 is a substituent R ^P3 having no polymerizable group. As another other constituent unit, two or more of R ^P2 in the formulae (1-1), (1-2), (1-4), and (1-6) may be substituted as a ring structure group. Furthermore, in another other constitutional unit, the substituent T may be substituted in a part of the main chain and R ^P3 within the range where the effect of the present invention is exhibited.
R ^P3 is preferably the following formula (T3). The formula of R ^P3 is more preferably 80 or more and 1000 or less, more preferably 100 or more and 800 or less, and more preferably 150 or more and 600 or less.
-(L5) _n8- (T1) _n9 ... (T3)
L ⁵ is the above-mentioned linking group L or Lm, in which an alkylene group, an arylene group, an (oligomeric) alkoxy group, a carbonyl group, an oxygen atom, a group of an alkane structure, a group of an olefin structure, or a group of an aryl structure Groups and combinations of these are preferred. T ¹ is the above-mentioned substituent T, and examples thereof include an alkyl group, an aryl group, an alkoxy group, and a fluorenyl group. n9 is an integer of 1 to 6, and 1 or 2 is preferable. When n9 is 3 or more, L ⁵ end becomes more tetravalent linking group and all may be substituted with a T ^1, T ¹ but may be replaced by two or more of L ^5.

In the formulas T2 and T3, L ⁴ , L ⁵ , P, and T ¹ may have the above-mentioned substituent T as long as the effects of the present invention are exhibited. For example, a group having an alkane structure, a group having an olefin structure, a group having an aryl structure, and the like may be further substituted with a halogen atom (a fluorine atom is preferred).

In the specific polymer, the structural unit represented by any one of the formulae (1) to (6) may constitute the entire polymer (a homopolymer having a composition ratio of 100 mole%), or may be a unit with other structural units. Or a copolymer of another constituent unit.

In a specific polymer, a constituent unit (for example, a constituent unit represented by formula (1) to formula (6)) having a group capable of detaching a detached component based on a molar ratio (other than a constituent unit having The constituent ratio of the polymerizable group) / another constituent unit is preferably 10 to 100/0 to 80/0 to 50, more preferably 30 to 100/0 to 70/0 to 30, and 50 to 100/0 to 50/0 to 10 is more preferable, and 50 to 90/10 to 50/0 to 10 may be used.
The specific polymer may include only one kind or two or more kinds of constituent units having a group capable of detaching a detached component, other constituent units (constituent units having a polymerizable group), and another constituent unit. When two or more kinds are included, it is preferable that the total ratio is the above ratio.
In addition, in the present invention, it is also preferable to adopt a structure that does not substantially include a structural unit having a group capable of detaching a detached component and a structural unit other than a structural unit having a polymerizable group. In fact, it does not mean, for example, that it is 5 mass% or less of all the constituent units, 3 mass% or less is more preferable, and 1 mass% or less is more preferable.

The weight average molecular weight of the specific polymer is preferably 4,000 or more, more preferably 5,000 or more, even more preferably 7,000 or more, and even more preferably 10,000 or more. As an upper limit, it is preferably below 2,000,000, more preferably below 1,500,000, and even more preferably below 1,000,000. The measurement method of the weight average molecular weight is a method represented 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, more preferably 1.0% by mass or more, and more preferably 1.5% by mass or more . As an upper limit, 10% by mass or less is preferable, 7% by mass or less is more preferable, 5% by mass or less is further preferable, 4% by mass or less is more preferable, and 3% by mass or less is further more preferable. By setting the amount to be equal to or more than the above-mentioned lower limit value, the effect due to the polymer blend can be appropriately exhibited, and a uniform film can be easily produced. On the other hand, by setting it to the above-mentioned upper limit value or less, the effect of using a solvent is appropriately exhibited, and a uniform film is easily formed over a wide area.
In addition, the content of the specific polymer with respect to the nonvolatile component (referring to the solid content of the solvent in the composition) in the underlayer film-forming composition for imprint is preferably 90% by mass or more, and 95% by mass The above is more preferable, and more than 99% by mass is more preferable. The upper limit is 100% by mass. By setting the amount to be equal to or more than the above-mentioned lower limit value, the effect due to the polymer blend can be appropriately exhibited, and a uniform film can be easily produced. On the other hand, by setting it to the above-mentioned upper limit value or less, the effect of using a solvent is appropriately exhibited, and a uniform film is easily formed over a wide area.
The specific polymer may be used alone or in combination of two or more. When two or more kinds are used, it is preferable that the total measurement falls within the above range.

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

<<< Separation reaction accelerator or its precursor >>
A release reaction promoter is a compound that promotes the reaction of detaching a detached component from a specific polymer by coexisting with a specific polymer in the system and acting on a specific polymer by a predetermined opportunity. The release reaction promoter is a compound having an acidic functional group or a basic functional group. It is preferred that the release reaction promoter is present as a precursor in the composition. Examples of the precursor include compounds that are converted into a deactivation-reaction promoter compound by reacting with external energy such as heat or light. Specific examples include thermal acid generators, photoacid generators, thermal base generators, and photobase generators. Thermal acid generators and photoacid generators are preferred, and thermal acid generators are more preferred.
When the release reaction accelerator has an acidic functional group, the pKa of the release accelerator is preferably 2 or less, more preferably 1 or less, and even more preferably 0 or less. The lower limit value is not particularly limited, but may be, for example, -10 or more. When having a basic functional group, the pKa of the conjugate acid is preferably 5 or more, more preferably 7 or more, and more preferably 8 or more. The upper limit value is not particularly limited, but may be, for example, 15 or less.
In the present invention, as specific examples of the release reaction accelerator or its precursor, the acid proliferation agents described in Japanese Patent Application Laid-Open No. 2014-047329, paragraphs 0012, 0017, 0026 to 0037, and light described in 0038 to 0040 can be used Acid generator, thermal acid generator described in paragraph 0041, photobase multiplication agent described in paragraphs 0029 to 0066 of JP 2012-237776, photobase generator described in paragraphs 0073 to 0087, and 0087 to 0090. The hot alkali generators described in paragraphs, the photo acid generators described in paragraphs 0012 to 0015 and 023 to 0029 of Japanese Patent No. 5876442, and the alkali generators described in paragraphs 0033 to 0075 of international publication 2009/123122. The alkali generators described in Japanese Patent Application Laid-Open No. 2011-236416 Nos. 0038 to 0069 are incorporated into this specification.

The content of the release reaction accelerator or its precursor is preferably 0.1% by mass or more of the nonvolatile component, more preferably 1.0% by mass or more, and even more preferably 2.0% by mass or more. The upper limit is actually 10.0% by mass or less, and may be 5.0% by mass or less.
As the deactivation accelerator or its precursor, only one species may be used, or two or more species may be used. When two or more kinds are used, it is preferable that the total measurement falls within the above range.

<<< Alkanyl glycol compound >>
The underlayer film-forming composition for imprint may include an alkylene glycol compound. The alkylene glycol compound preferably has 3 to 1,000 alkylene glycol constituent units, more preferably 4 to 500 units, more preferably 5 to 100 units, and even more preferably 5 to 50 units. . The weight average molecular weight (Mw) of the alkylene glycol compound is preferably from 150 to 10,000, more preferably from 200 to 5,000, more preferably from 300 to 3,000, and even more preferably from 300 to 1,000.
The alkylene glycol compound is exemplified by polyethylene glycol, polypropylene glycol, such mono- or dimethyl ethers, mono- or dioctyl ether, mono- or dinonyl ether, mono- or didecyl ether, monostearate, Monoesters, monoadipates, and monosuccinates are preferred. Polyethylene glycol and polypropylene glycol are preferred.
The surface tension of the alkylene glycol compound at 23 ° C is preferably 38.0 mN / m or more, and more preferably 40.0 mN / m or more. The upper limit of the surface tension is not particularly limited, and is, for example, 48.0 mN / m or less. By blending the compounds as described above, the wettability of the hardening composition for imprint provided directly above the lower film can be improved.

When the alkylene glycol compound is contained, it is 40% by mass or less of the nonvolatile component, 30% by mass or less is preferable, 20% by mass or less is more preferable, and 1 to 15% by mass is further more preferable.
The alkylene glycol compound may be used alone or in combination of two or more. When two or more kinds are used, it is preferable that the total measurement falls within the above range.

<< polymerization initiator
The non-volatile component may include a polymerization initiator. Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator. From the viewpoint of improving the crosslinking reactivity with the curable composition for imprint, the photopolymerization initiator is more suitable. good. As the photopolymerization initiator, a radical polymerization initiator and a cationic polymerization initiator are preferable, and a radical polymerization initiator is more preferable. In the present invention, a plurality of photopolymerization initiators may be used in combination.

As the photopolymerization initiator, a known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, compounds containing a triskeleton, compounds containing an oxadiazole skeleton, compounds containing a trihalomethyl group, etc.), fluorenylphosphine compounds such as a fluorenylphosphine oxide, and hexaaryl Oxime compounds such as bisimidazole, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds , Azide compounds, metallocene compounds, organoboron compounds, iron-arene complexes, and the like. Among these, oxime compounds are preferred. For details of these, refer to the descriptions in paragraphs 0165 to 0182 of Japanese Patent Application Laid-Open No. 2016-027357, which are incorporated into this specification.
Examples of the fluorenylphosphine compound include 2,4,6-trimethylbenzylfluorenyl-diphenyl-phosphine oxide and the like. In addition, IRGACURE-819, IRGACURE1173, and IRGACURE-TPO (product names: all manufactured by BASF) can be used as commercially available products.

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

<< polymerization inhibitors >>
The non-volatile component may include a polymerization inhibitor. The polymerization inhibitor (B) of the present embodiment is a compound having the ability to capture the free radicals generated by the hardening main agent (A) before causing a growth reaction. Thereby, the polymerization inhibitor (B) functions to suppress the polymerization of the curable main agent (A).

The polymerization inhibitor (B) may be any of hydroquinones, catechols, phenothiazines, and phenoxazines. Specific examples of the polymerization inhibitor (B) include 4-methoxyphenol, 4-methoxy-1-naphthol, 4-tert-butylcatechol, and 2,6-di-tertiary Butylphenol, 2,6-tertiary-butyl-p-cresol, 2-tertiary-butyl-4,6-dimethylphenol, 2,4,6-tri-tertiary-butylphenol, hydroquinone, Phenolic compounds such as tertiary butyl hydroquinone. Specific examples of the polymerization inhibitor (B) include quinone compounds such as naphthoquinone and benzoquinone. Specific examples of the polymerization inhibitor (B) include amine compounds such as phenothiazine, phenoxazine, and 4-hydroxy-2,2,6,6-tetramethylpiperidine. Specific examples of the polymerization inhibitor (B) include 2,2,6,6-tetramethylpiperidine-N-oxy and 4-hydroxy-2,2,6,6-tetramethylpiperidine. N-oxyl compounds such as pyridine-N-oxy. The compounds listed here are only examples, and the polymerization inhibitor (B) may be another compound.

The content of the polymerization inhibitor is preferably 0.0001% by mass or more and 10.0% by mass or less, more preferably 0.001% by mass or more and 1.0% by mass or less, and more preferably 0.005% by mass or more and 0.1% by mass or less. The polymerization inhibitor may be used alone or in combination of two or more. When two or more kinds are used, it is preferable that these total measurements fall within the above range.

＜＜ Other Ingredients ＞＞
As a non-volatile component to be incorporated into the underlayer film-forming composition for imprint, in addition to the above-mentioned compounds, it may contain one or two or more thermal polymerization initiators, antioxidants, leveling agents, tackifiers, and interfaces. Active agent etc.
Regarding the thermal polymerization initiator, the components described in Japanese Patent Application Laid-Open No. 2013-036027, Japanese Patent Application Laid-Open No. 2014-090133, and Japanese Patent Application Laid-Open No. 2013-189537 can be used. Regarding the content and the like, it is also possible to refer to the description in the aforementioned publication.
Moreover, in this invention, it can also be set as the structure which does not contain a surfactant substantially for an underlayer film formation composition for imprints. It does not substantially contain 0.1% by mass or less of nonvolatile components in the underlayer film-forming composition for imprint.

<<< Solvent for lower film >>
The underlayer film-forming composition for imprint contains a solvent. The solvent preferably contains, for example, a compound (solvent for an underlayer film) that is liquid at 23 ° C. and has a boiling point of 250 ° C. or less at a ratio of 70.0% by mass or more. Generally, the non-volatile components eventually form an underlayer film. The underlayer film-forming composition for imprinting preferably contains 80.0% by mass or more of the solvent for the underlayer film, more preferably 90.0% by mass or more, more preferably 93.0% by mass or more, and more preferably 94.0% by mass or more, and may be 95.0 Above mass%, above 98.0 mass%, above 99.0 mass%.
The solvent may contain only one kind in the underlayer film-forming composition for imprint, or two or more kinds. When two or more kinds are included, the total measurement is preferably within the above range.
The boiling point of the solvent for the lower film is preferably 230 ° C or lower, more preferably 200 ° C or lower, more preferably 180 ° C or lower, more preferably 160 ° C or lower, and 130 ° C or lower. The lower limit is 23 ° C, but it is actually 60 ° C or higher. By setting the boiling point to the above range, the solvent can be easily removed from the lower layer film, which is preferable.

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

As specific examples, alkoxy alcohol, propylene glycol monoalkyl ether carboxylate, propylene glycol monoalkyl ether, lactate, acetate, alkoxypropionate, chain ketone, cyclic ketone, and lactone are selected. And alkylene carbonate.

Examples of the alkoxy alcohol include methoxyethanol, ethoxyethanol, methoxypropanol (for example, 1-methoxy-2-propanol), and 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 2-pentyl alcohol) and the like.

The propylene glycol monoalkyl ether carboxylic acid ester is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate. Methyl ether acetate is particularly preferred.

As the propylene glycol monoalkyl ether, propylene glycol monomethyl ether or propylene glycol monoethyl ether is preferred.
As the lactate, ethyl lactate, butyl lactate or propyl lactate is preferred.
As the 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 the chain ketone, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutanone, phenylacetone , Methyl ethyl ketone, methyl isobutyl ketone, acetoacetone, acetone acetone, ionone, diacetone alcohol, acetomethanol, acetophenone, methylnaphthyl ketone, methylpentyl 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 preferable.

In addition to the above components, it is preferable to use an ester-based solvent having a carbon number of 7 or more (7 to 14 is preferred, 7 to 12 is more preferred, 7 to 10 is more preferred) and a hetero atom number is 2 or less.

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

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 a component, propylene glycol monomethyl ether (fp: 47 ° C), ethyl lactate (fp: 53 ° C), ethyl 3-ethoxypropionate (fp: 49 ° C), and methylpentyl 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, amyl acetate, or cyclohexanone is more preferable, and propylene glycol monoethyl ether or ethyl lactate is particularly preferable.

As the solvent for the lower layer film, and as a preferable solvent among them, it is selected from the group consisting of water, 1-methoxy-2-propanol, propylene glycol monomethyl ether acetate (PGMEA), ethoxyethyl propionate, and cyclic At least one member 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.

As a storage container for the underlayer film-forming composition for imprint, a conventionally known storage container can be used. In addition, as a storage container, in order to prevent impurities from being mixed into the raw materials or the composition, it is also preferable to use a multi-layer bottle composed of six kinds of six-layer resin or a bottle having six resins in a seven-layer structure. As such a container, the container described in Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

＜ curable composition for imprinting ＞
<<< Polymerizable Compound >>
The curable composition for imprint preferably contains a polymerizable compound, and more 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 include both a monofunctional polymerizable compound and a polyfunctional polymerizable compound.

<<< monofunctional polymerizable compound >>
The molecular weight of the monofunctional polymerizable compound used in the curable composition for imprint is preferably 50 or more, more preferably 100 or more, and more preferably 150 or more. The molecular weight is preferably 1,000 or less, more preferably 800 or less, more preferably 300 or less, and even more preferably 270 or less. When the molecular weight is at least the above-mentioned lower limit value, there is a tendency that the volatility can be suppressed. When the molecular weight is equal to or less than the above upper limit, the viscosity tends to be reduced.
The boiling point of the monofunctional polymerizable compound used for the curable composition for imprint is preferably 85 ° C or higher, more preferably 110 ° C or higher, and more preferably 130 ° C or higher. By setting the boiling point to be at least the above lower limit value, volatility can be suppressed. The upper limit of the boiling point is not particularly limited, and for example, the boiling point can be set to 350 ° C or lower.

The type of the polymerizable group of the monofunctional polymerizable compound used in the curable composition for imprint is not particularly limited, but examples thereof include ethylenically unsaturated groups, epoxy groups, and the like. good. As the ethylenically unsaturated group, a (meth) acrylfluorenyl group is more preferable, and acrylfluorenyl group is more preferable.

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

A preferred first embodiment of the monofunctional polymerizable compound used in the curable composition for imprint is a compound having a straight or branched hydrocarbon chain having 4 or more carbon atoms.
The hydrocarbon chain in the present invention means an alkane chain, an olefin chain, an alkyne chain, an alkane chain and an alkene chain are preferred, and an alkane chain is more preferred.
In the present invention, an alkane chain means an alkyl group and an alkylene group. Similarly, an alkenyl chain represents an alkenyl group and an alkenyl group, and an alkynyl chain represents an alkynyl group and an alkenyl group. Among these, a linear or branched alkyl group or alkenyl group is more preferred, a linear or branched alkyl group is more preferred, and a linear alkyl group is more preferred.
The above straight or branched hydrocarbon chain (alkyl is preferred) is 4 or more carbons, 6 or more carbons is preferred, 8 or more carbons is more preferred, 10 or more carbons is more preferred, and 12 or more carbons are preferred For better. The upper limit value of the carbon number is not particularly limited, but it can be set to, for example, 25 or less.
From the viewpoint of improving the mold release property, the linear or branched hydrocarbon chain may include an ether group (-O-), but it is preferable not to include an ether group.
By using a monofunctional polymerizable compound having such a hydrocarbon chain, the elasticity coefficient of the cured product (pattern) is reduced with a relatively small amount of addition, and the releasability is improved. In addition, when 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 releasability can be further improved.
Preferred monofunctional polymerizable compounds having a curable composition for imprint are hydrocarbon groups, and examples thereof include (1) to (3).
(1) Linear alkyl group having 8 or more carbon atoms (2) Branched alkyl group having 10 or more carbon atoms (3) Alicyclic ring, aromatic ring or aromatic group substituted with linear or branched alkyl group having 1 or more carbon atoms Heterocyclic

(1) A linear alkyl group having 8 or more carbons and a linear alkyl group having 8 or more carbons are more preferred, a carbon number of 11 or more is more preferred, and a carbon number of 12 or more is more preferred. Further, a carbon number of 20 or less is preferred, a carbon number of 18 or less is more preferred, a carbon number of 16 or less is further preferred, and a carbon number of 14 or less is more preferred.
(2) A branched alkyl group having 10 or more carbons The branched alkyl system having 10 or more carbons is preferably 10 to 20 carbons, more preferably 10 to 16 carbons, and more preferably 10 to 14 carbons. The number of carbon atoms is more preferably 10 to 12.
(3) An alicyclic ring, an aromatic ring, or an aromatic heterocyclic ring substituted with a linear or branched alkyl group having 1 or more carbon atoms and a linear or branched alkyl system having a carbon number of 1 or more is more preferred. . The carbon number of the alkyl group is preferably 14 or less, more preferably 12 or less, and even more preferably 10 or less.
The ring of an alicyclic ring, an aromatic ring or an aromatic heterocyclic ring may be a monocyclic ring or a condensed ring, but a monocyclic ring is preferred. When it is a condensed ring, the number of rings is preferably two or three. A ring of 3 to 8 members is preferred, a ring of 5 or 6 members is more preferred, and a ring of 6 members is even more preferred. Specific examples of the ring include an example of a ring Cz described later.

The monofunctional polymerizable compound used for the hardenable composition for imprinting is a compound having a straight or branched hydrocarbon chain having 4 or more carbon atoms and a polymerizable group bonded directly or via a linking group. A compound in which any one of the groups) to (3) is directly bonded to a polymerizable group is more preferred. Examples of the linking group include -O-, -C (= O)-, -CH _2- , and combinations thereof. As the monofunctional polymerizable compound used in the present invention, (1) a straight-chain alkyl group having 8 or more carbon atoms and a (meth) acryloxyoxy straight-chain alkyl (meth) acrylate is specifically bonded good.

The monofunctional polymerizable compound is preferably a compound represented by the following formula (I-1).
[Chemical Formula 12]

R ¹² represents an alkyl group (carbon number 1 to 36 is preferred, 1 to 30 is more preferred, 1 to 24 is more preferred), alicyclic (carbon number 3 to 24 is preferred, 3 to 12 is more preferred) 3 to 6 are more preferred), aromatic rings (6 to 22 carbons are preferred, 6 to 18 are more preferred, 6 to 10 are more preferred) and aromatic heterocycles (2 to 12 carbons) For the sake of preference, 2 to 6 are more preferred, and 2 to 5 are further preferred) at least one kind or a group based on these. R ¹¹ represents a hydrogen atom or a methyl group. L ¹¹ represents a single bond or the above-mentioned linking group L, and an alkylene or an alkylene group is preferred. R ¹² and L ¹¹ may form a ring by bonding with or without a linking group L. R ¹² and L ¹¹ may have the above-mentioned substituent T. A plurality of substituents T may be bonded to form a ring, or may be bonded to R ¹² or L ¹¹ to form a ring. When there are a plurality of substituents T, they may be the same as or different from each other. The preferable range of the alicyclic ring, aromatic ring, or aromatic heterocyclic ring in R ¹² is the same as the ring Cz mentioned later.

As the monofunctional polymerizable compound of the first embodiment, the following first group and second group can be exemplified. However, the present invention is not limited to such self-explanatory. The first group is better than the second group.
Group 1
[Chemical Formula 13]

Group 2
[Chemical Formula 14]

A preferred second embodiment of the monofunctional polymerizable compound used in the curable composition for imprint is a compound having a cyclic structure. As the cyclic structure, a single ring or a condensed ring of 3 to 8 member rings is preferred. The number of rings constituting the condensed ring is preferably two or three. The ring structure is more preferably a 5-member ring or a 6-member ring, and a 6-member ring is more preferable. A single ring is more preferable.
The number of cyclic structures in one molecule of the polymerizable compound may be one, or may be two or more, one or two is more preferred, and one is more preferred. When it is a condensed ring, the condensed ring is regarded as a cyclic structure.

As the monofunctional polymerizable compound of the second embodiment, the following compounds can be exemplified. However, the present invention is not limited to such self-explanatory. In addition, among the compounds described in the first embodiment, a compound having a cyclic structure is exemplified as a preferable compound in this embodiment.
[Chemical Formula 15]

In the present invention, monofunctional polymerizable compounds other than the above-mentioned monofunctional polymerizable compounds can be used without departing from the gist of the present invention. Examples of the monofunctional polymerizable compounds described in Japanese Patent Application Laid-Open No. 2014-170949 are exemplified. A polymerizable compound is included in this specification.

Regarding the content of the monofunctional polymerizable compound used in the curable composition for imprinting relative to the total polymerizable compound, when contained, 6 mass% or more is preferable, 8 mass% or more is more preferable, and 10 mass% or more is It is more preferably, and more preferably 12% by mass or more. The content is more preferably 60% by mass or less, and may be 55% by mass or less.
The present invention may include only one type of monofunctional polymerizable compound, or may include two or more types. When two or more kinds are included, the total measurement is preferably within the above range.

<<< Multifunctional Polymerizable Compound >>
The polyfunctional polymerizable compound used for the curable composition for imprinting 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 preferable. 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, even more preferably 500 or less, and more preferably 350 or less. When the upper limit of the molecular weight is 1,000 or less, the viscosity tends to be reduced. The lower limit of the molecular weight is not particularly limited, but can be set to 200 or more, for example.

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

The type of the polymerizable group of the ring-containing polyfunctional polymerizable compound used for the imprintable curable composition is not particularly limited, but examples thereof include ethylenically unsaturated groups, epoxy groups, and the like, and ethylenic unsaturated groups. Basis is better. As the ethylenically unsaturated group, a (meth) acrylfluorenyl group is more preferable, and acrylfluorenyl group is more preferable. One molecule may include two or more kinds of polymerizable groups, and may also include two or more kinds of polymerizable groups of the same type.

The type of the atom constituting the ring-containing polyfunctional polymerizable compound used in the curable composition for imprint is not particularly limited, but it is preferably composed only of an atom selected from a carbon atom, an oxygen atom, a hydrogen atom, and a halogen atom. It is more preferable to be composed only of an atom selected from a carbon atom, an oxygen atom, and a hydrogen atom.

The ring contained in the ring-containing polyfunctional polymerizable compound used for the imprintable curable composition may be a single ring or a condensed ring, but a single ring is preferred. When it is a condensed ring, the number of rings is preferably two or three. A ring of 3 to 8 members is preferred, a ring of 5 or 6 members is more preferred, and a ring of 6 members is even more preferred. The ring may be an alicyclic ring, or an aromatic ring or an aromatic heterocyclic ring, but an aromatic ring or an aromatic heterocyclic ring is preferred, and an aromatic ring is further preferred. Specific examples of the ring include an example of a ring Cz.
The number of rings in the ring-containing polyfunctional polymerizable compound used in the curable composition for imprinting may be one, or may be two or more, but one or two is preferable, and one is more preferable. . 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 is composed of (polymerizable group)-(single bond or divalent linking group)-(divalent group having ring)-( A single bond or a divalent linking group)-(polymerizable group) is preferably represented. Among them, as the linking group, an alkylene group is more preferable, and an alkylene group having 1 to 3 carbon atoms is more preferable.

The ring-containing polyfunctional polymerizable compound used in the curable composition for imprint is preferably represented by the following formula (I-2).
[Chemical Formula 16]

Q represents a ring selected from an alicyclic ring (carbon number 3 to 24 is preferred, 3 to 12 is more preferred, 3 to 6 is more preferred), an aromatic ring (carbon number 6 to 22 is preferred, 6 to 18 is More preferably, 6 to 10 is further preferred) and aromatic heterocycles (carbon numbers of 2 to 12 are preferred, 2 to 6 are more preferred, and 2 to 5 are further preferred) at least one of the 1 + q valences Group. R ^{2 1} and R ^{2 2} each independently represent a hydrogen atom or a methyl group. L ²¹ and L ²² each independently represent a single bond or the above-mentioned linking group L. Q and L ²¹ or L ²² may form a ring by bonding with or without a linking group L. Q, L ²¹ and L ²² may have the above-mentioned substituent T. A plurality of substituents T may be bonded to form a ring, or may be bonded to Q or L ²¹ or L ²² to form a ring. When there are a plurality of substituents T, they may be the same as or different from each other. A preferable range of the alicyclic ring, aromatic ring, or aromatic heterocyclic ring in Q includes a ring Cz described later. q is an integer of 1 to 5, an integer of 1 to 3 is preferred, 1 or 2 is more preferred, and 1 is further preferred.
Q may have a structure in which a plurality of alicyclic rings, a plurality of aromatic rings, a plurality of aromatic heterocyclic rings, an alicyclic ring and an aromatic ring, an alicyclic ring and an aromatic heterocyclic ring, and an aromatic ring and an aromatic heterocyclic ring are bonded. As a structure to which an aromatic ring is connected, the structure of said Formula Ar1-Ar5 is mentioned.

As a polyfunctional polymerizable compound used for the curable composition for imprint, the following 1st group and 2nd group can be illustrated. However, the present invention is not limited to such self-explanatory. Group 1 is better.
Group 1
[Chemical Formula 17]

Group 2
[Chemical Formula 18]

The curable composition for imprint may contain a polyfunctional polymerizable compound other than the above-mentioned ring-containing polyfunctional polymerizable compound. As another polyfunctional polymerizable compound, the compound represented by following formula (I-3) is preferable.
[Chemical Formula 19]

L ³⁰ represents a group having a linear or branched alkane structure (carbon number 1 to 12 is preferred, 1 to 6 is more preferred, 1 to 3 is more preferred), a linear or branched alkene structure Group (carbon number 2-12 is preferred, 2-6 is more preferred, 2-3 is more preferred), linear or branched alkyne structure group (carbon number 2-12 is preferred, 2 ~ 6 is more preferred, and 2 ~ 3 is more preferred) at least one kind of 1 + r valence 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 aforementioned linking group L. L ³⁰ and L ²⁵ or L ²⁶ may form a ring by bonding with or without a linking group L. L ²⁵ , L ²⁶ and L ³⁰ may have the above-mentioned substituent T. A plurality of substituents T may be bonded to form a ring, or may be bonded to another linking group to form a ring. When there are a plurality of substituents T, they may be the same as or different from each other. r is an integer of 1 to 4, an integer of 1 to 3 is preferred, 1 or 2 is more preferred, and 1 is further preferred. Furthermore, L ³⁰ may have a hetero linking group (O, S, NR ^N ). It is preferable that the number of the intermedium linking groups is 1 when the carbon number of L ³⁰ is 1 to 6.

Examples of other polyfunctional polymerizable compounds used in the curable composition for imprint include polyfunctional polymerizable compounds having no ring among the polymerizable compounds described in Japanese Patent Application Laid-Open No. 2014-170949. These contents are included in This manual. More specifically, for example, the following compounds are exemplified.
[Chemical Formula 20]

Examples of the ring Cz include the following aromatic rings, aromatic heterocyclic rings, and alicyclic rings.
As the aromatic ring contained in the compound containing an aromatic ring, those having 6 to 22 carbon atoms are preferred, 6 to 18 are more preferred, and 6 to 10 are further preferred. Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a fluorene ring, a pinene ring, a biphenyl ring, an indene ring, a dihydroindene ring, and a bitriphenylene ring. , Embedded dinaphthalene ring, chrysene ring, fluorene ring, tetrahydronaphthalene ring and so on. Among them, a benzene ring or a naphthalene ring is preferable, and a benzene ring is more preferable. The aromatic ring may have a structure in which a plurality of them are connected, and examples thereof include a biphenyl ring and a biphenyl ring.
As the aromatic heterocyclic ring, those having 1 to 12 carbon atoms are preferable, 1 to 6 are more preferable, and 1 to 5 are 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, isopropyl Indole ring, indazole ring, purine ring, quinazine ring, isoquinoline ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, An azole ring, an acridine ring, a phenazine ring, a phenothiazine ring, a morphine ring, and the like.
As the alicyclic ring, a carbon number of 3 to 22 is more preferable, 4 to 18 is more preferable, and 6 to 10 is further more preferable. 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 dicyclopentane. Diene ring, tetrahydrodicyclopentadiene ring, octahydronaphthalene ring, decahydronaphthalene ring, hexahydroindane ring, pinane ring, norbornane ring, norbornene ring, isonorbornene ring, three Cyclodecane ring, tetracyclododecane ring, adamantane ring and the like.

The polyfunctional polymerizable compound is preferably contained in an amount of 30% by mass or more, more preferably 45% by mass or more, more preferably 50% by mass or more, and 55% by mass or more with respect to the total polymerizable compound in the curable composition for imprinting. It is more preferably 60% by mass or more, and further 70% by mass or more. The upper limit value is preferably less than 95% by mass, more preferably 90% by mass or less, and can be 85% by mass or less.
The curable composition for imprint may contain only one kind of polyfunctional polymerizable compound, or may contain two or more kinds. When two or more kinds are included, the total measurement is preferably within the above range.

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

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

＜＜ Other Ingredients ＞＞
The curable composition for imprint may contain additives other than a polymerizable compound. Other additives may include a polymerization initiator, a surfactant, a sensitizer, a release agent, an antioxidant, a polymerization inhibitor, and the like.
Specific examples of the hardenable composition for imprint that can be used in the present invention are described in Japanese Patent Application Laid-Open No. 2013-036027, Japanese Patent Application Laid-Open No. 2014-090133, and Japanese Patent Application Laid-Open No. 2013-189537. Composition, and incorporate those contents into this manual. Regarding the preparation of the curable composition for imprint and the method for forming the film (pattern-forming layer), it is also possible to refer to the description of the above-mentioned publication and incorporate the contents into this specification.

＜ Physical properties and other values ＞＞
The viscosity of the curable composition for imprinting is preferably 20.0 mPa ･ s or less, more preferably 15.0 mPa ･ s or less, and may be 11.0 mPa ･ s or less, and further may be 9.0 mPa ･ s or less. The lower limit of the viscosity is not particularly limited, but is, for example, 4.0 mPa ･ s or more, and can be further set to 5.0 mPa ･ s or more.

The surface tension (γResist) of the hardening composition for imprint is preferably 29.0 mN / m or more, more preferably 30.0 mN / m or more, and further preferably 31.0 mN / m or more. By using a hardenable composition for imprint having a high surface tension, the capillary force is increased, and high-speed filling of the hardenable composition for imprint into a mold pattern can be performed. The upper limit value of the surface tension is not particularly limited. From the viewpoint of imparting the relationship with the underlayer film and the inkjet adaptability, 42.0 mN / m or less is more preferable, and 40.0 mN / m or less is more preferable. Can be 38.0mN / m or less.

The Ohnishi parameter of the hardenable composition for imprint is preferably 5.0 or less, more preferably 4.0 or less, and even more preferably 3.7 or less. The lower limit value of the Ohnishi parameter of the hardening composition for imprint is not particularly limited, and may be, for example, 1.0 or more, and further 2.0 or more.
For the polymerizable compound of the curable composition for imprint, the number of carbon atoms, hydrogen atoms, and oxygen atoms of all constituent components can be substituted into the following formula to obtain the Ohnishi parameter.
Ohnishi parameter = sum of the number of carbon atoms, hydrogen atoms and oxygen atoms / (number of carbon atoms-number of oxygen atoms)

The Hansen solubility parameter (HSP) vector of the polymerizable compound contained in the hardening composition for imprint:
(I) The dispersion component (component d) is preferably 14.0 to 20.0, more preferably 15.0 to 19.0, and even more preferably 16.0 to 18.5;
(Ii) The polar component (p component) is preferably 3.5 to 8.0, more preferably 3.8 to 6.0, and more preferably 4.0 to 5.0;
(Iii) The hydrogen bonding term component (component h) is preferably 4.0 to 8.0, more preferably 4.7 to 7.0, and even 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 set by methods described in the examples described later. When calculating the HSP vector, when the component is plural, it is better that at least one kind satisfies the above range, and the maximum amount component satisfies the above range.

In the present invention, the content of the solvent in the embossable curable composition is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less.
The curable composition for imprinting can also be made substantially free of polymers (preferably having a weight average molecular weight greater than 1,000, more preferably having a weight average molecular weight greater than 2,000, and even more preferably a polymer having a weight average molecular weight greater than 10,000) Like this. The fact that the polymer is not substantially contained means, for example, that the content of the polymer is 0.01% by mass or less of the curable composition for imprint, preferably 0.005% by mass or less, and more preferably not contained at all.

As a storage container for the imprintable curable composition used in the present invention, a conventionally known storage container can be used. In addition, as a storage container, in order to prevent impurities from being mixed into the raw materials or the composition, it is also preferable to use a multi-layer bottle composed of six kinds of six-layer resin or a bottle having six resins in a seven-layer structure. As such a container, the container described in Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

＜ Kits ＞
The present invention discloses a kit comprising an underlayer film-forming composition for imprinting and a curable composition for imprinting including a polymerizable compound.
In the kit of the present invention, the Hansen solubility parameter of the release component (the compound represented by the formula (r1) or (r2) or the compound represented by the formula (r1-1)) and the quality of the sclerosing composition for imprinting are used. Mori solubility parameter and the ΔHSP value calculated from the following mathematical formula (H1) is preferably 5 or less, more preferably 7.0 or less, further preferably 5.0 or less, and more preferably 4.0 or less. The lower limit value may be 0, but it is actually 0.1 or more.
ΔHSP = (4.0 × ΔD ² + ΔP ² + ΔH ² ) ^0.5 …… (H1)
ΔD is the difference between the dispersion term component of the Hansen solubility parameter vector of the hardening composition for imprint and the dispersion term component of the Hansen solubility parameter vector of the detached component.
ΔP is the difference between the polar term component of the Hansen solubility parameter vector of the hardening composition for imprint and the polar term component of the Hansen solubility parameter vector of the detached component.
ΔH is the difference between the hydrogen bonding term component of the Hansen solubility parameter vector of the embossable hardening composition and the hydrogen bonding term component of the Hansen solubility parameter vector of the release component.

＜ Laminated body and its manufacturing method ＞
As a preferred embodiment of the kit of the present invention, a laminated body formed from the kit is mentioned. The laminated body of this embodiment preferably has an underlayer film formed of the above-mentioned underlayer film-forming composition for imprinting, and an imprint layer formed of the above-mentioned hardening composition for imprinting and located on the surface of the underlayer film. The manufacturing method is not particularly limited, but examples include a manufacturing method including the use of the kit and applying a hardening composition for imprinting on the surface of an underlayer film formed from the underlayer film-forming composition for imprinting. At this time, it is preferable that the curable composition for imprinting is applied to the surface of the above-mentioned underlayer film by an inkjet method (IJ method). Furthermore, a method for manufacturing a laminated body includes a process for applying the above-mentioned underlayer film-forming composition for imprinting on a substrate to a layered process, and further comprising applying the underlayer film-forming composition for imprinting applicable to the above-mentioned layer at 80 to 250 ° C. (150-250 ° C is preferred) (Processing temperature) The process of heating (baking) is better.

＜ Hardened material pattern and its manufacturing method ＞
The method for manufacturing a hardened pattern according to a preferred embodiment of the present invention uses the above kit to produce a hardened pattern. The method includes: an underlayer film forming process, applying an underlayer film forming composition for imprint on a substrate to form an underlayer film; In the manufacturing process, a hardening composition for imprinting is applied to the surface of the lower layer film; a mold contact process is performed to bring the hardening composition for imprinting into contact with a mold having a pattern for transferring a pattern shape; a light irradiation process is applied to the above The curable composition for imprint is irradiated with light to form a cured product; and a mold release process is performed to separate the cured product from the mold.
Hereinafter, a method for forming a cured product pattern (a method for manufacturing a cured product pattern) will be described with reference to FIG. 1. Obviously, the structure of the present invention is not limited to the illustration.

＜〈 Underlayer Film Formation Process 〉＞
In the lower-layer film formation process, as shown in (1) and (2) in FIG. 1, an lower-layer film 2 is formed on the substrate 1. The underlayer film is preferably formed on a substrate by applying an underlayer film-forming composition for imprinting to a layer.

A method for applying the underlayer film-forming composition for imprint to a substrate is not particularly limited, and a generally known and applicable method can be adopted. Specifically, examples of the applicable method include a dip coating method, a pneumatic coating method, a curtain coating method, a wire bar coat method, a gravure coating method, an extrusion coating method, and a spin coating method. A coating method, a slit scanning method, or an inkjet method is preferable, and a spin coating method is preferable.
Furthermore, after the imprinting underlayer film-forming composition is applied to a substrate on a substrate, the solvent is evaporated (dried) by heat to form an underlayer film as a thin film.

The thickness of the lower layer film 2 is preferably 2 nm or more, more preferably 3 nm or more, even more preferably 4 nm or more, and may be 5 nm or more, or 7 nm or more. The thickness of the lower layer film is preferably 40 nm or less, more preferably 30 nm or less, even more preferably 20 nm or less, 15 nm or less, and further 10 nm or less. By setting the film thickness to be greater than the above-mentioned lower limit value, the spreadability (wetability) of the curable composition for imprint on the underlayer film is improved, and a uniform residual film can be formed after imprinting. By setting the film thickness to be equal to or less than the above-mentioned upper limit value, there is a tendency that the residual film after embossing becomes thin, uneven film thickness is unlikely to occur, and the uniformity of the residual film is improved.

The material of the substrate is not particularly limited, and it can be referred to the description in paragraph 0103 of Japanese Patent Application Laid-Open No. 2010-109092 (the publication number corresponding to the US application is the specification of US Patent Application Publication No. 2011/0183127), which is incorporated herein. Manual. In the present invention, a silicon substrate, a glass substrate, a quartz substrate, a sapphire substrate, a silicon carbide (silicon carbide) substrate, a gallium nitride substrate, an aluminum substrate, an amorphous alumina substrate, a polycrystalline alumina substrate, and GaAsP, GaP , AlGaAs, InGaN, GaN, AlGaN, ZnSe, AlGa, InP or ZnO. Specific examples of the material of the glass substrate include aluminosilicate glass, aluminoborosilicate glass, and barium borosilicate glass. In the present invention, a silicon substrate is preferred.

＜＜ Applicable Process ＞＞
In the applicable process, for example, as shown in (3) of FIG. 1, the hardening composition 3 for imprint is applied to the surface of the lower layer film 2.
The method for applying the curable composition for imprinting is not particularly limited, and reference can be made to paragraph 0102 of Japanese Patent Application Laid-Open No. 2010-109092 (the publication number corresponding to US application is US Patent Application Publication No. 2011/0199592) This content is incorporated into this manual. The curable composition for imprint is preferably applied to the surface of the underlayer film by an inkjet method. Moreover, the hardening composition for imprints can be applied by multiple application. In the method of arranging droplets on the surface of the lower film by an inkjet method or the like, the amount of the droplets is preferably about 1 to 20 pL, and the droplets are preferably arranged on the surface of the lower film at intervals. The droplet interval is preferably an interval of 10 to 1000 μm. In the case of the inkjet method, the droplet interval is set as the arrangement interval of the nozzles for inkjet.
Further, the volume ratio of the lower layer film 2 to the film-like imprintable curable composition 3 applied to the lower layer film is preferably 1: 1 to 500, more preferably 1:10 to 300, and 1:50 to 200. Is even better.
In addition, a method for manufacturing a laminated body according to a preferred embodiment of the present invention is a method for manufacturing a kit using the present invention, the method comprising applying an imprint on a surface of an underlayer film formed from the above-mentioned underlayer film forming composition for imprinting. Process for hardening composition. Furthermore, a method for manufacturing a multilayer body according to a preferred embodiment of the present invention includes a process for applying the above-mentioned lower-layer film-forming composition for imprinting on a substrate to a layered process, and the process is performed at 80 to 250 ° C (150 ° C or higher and 250 ° C). The following is preferred.) The heating (baking) process suitable for the above-mentioned layered underlayer film-forming composition for imprinting is preferred. The heating time can be set from 30 seconds to 5 minutes.

＜〈 Mold contact process 〉＞
For example, as shown in (4) in FIG. 1, in the mold contact process, the hardening composition 3 for imprint is brought into contact with a mold 4 having a pattern for transferring a pattern shape. Through this process, a desired hardened pattern (embossed pattern) is obtained.
Specifically, in order to transfer a desired pattern to the film-like embossable curable composition, the surface of the film-like embossable curable composition 3 is covered with the mold 4.

The mold may be a light-transmitting mold or a non-light-transmitting mold. When using a light-transmitting mold, it is preferable to irradiate light to the curable composition 3 for imprint from the mold side. On the other hand, when using a non-light-transmitting mold, it is preferable to use a light-transmitting substrate as the substrate and irradiate light from the substrate side. In the present invention, it is more preferable to use a light-transmitting mold and irradiate light from the mold side.
The mold which can be used in the present invention is a mold having a pattern for transfer. The pattern possessed by the mold can be formed, for example, by photolithography, electron beam scanning, or the like with a desired processing accuracy. However, in the present invention, the method for producing a mold pattern is not particularly limited. The pattern formed by the method for manufacturing a cured product pattern according to the preferred embodiment of the present invention can also be used as a mold.
The material constituting the light-transmitting mold used in the present invention is not particularly limited, and examples thereof include light-transmitting resins such as glass, quartz, polymethyl methacrylate (PMMA), polycarbonate resin, transparent metal vapor-deposited films, and polymer materials. For soft films such as dimethylsilane, light-hardened films, metal films, and the like, quartz is preferred.
The non-light-transmitting mold 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. Specific 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, polycrystalline silicon, silicon oxide, and amorphous silicon. It is not particularly limited.

In the manufacturing method of the said hardened | cured material pattern, when imprint lithography is performed using the hardenable composition for imprinting, it is preferable to set the mold pressure to 10 atmospheres or less. When the mold pressure is set to 10 atmospheres or less, there is a tendency that the mold or the substrate is not easily deformed and the pattern accuracy is improved. Further, it is also preferable from the viewpoint that the device can be downsized due to low pressure. The mold pressure is reduced from the residual film of the curable composition for imprint which touches the convex part of the mold, and the range capable of ensuring the uniformity of the mold transfer is preferably selected.
It is also preferable to contact the hardening composition for imprint and the mold in an atmosphere containing helium or a condensable gas, or an atmosphere containing both helium and a condensable gas.

＜＜ Light irradiation process ＞＞
In the light irradiation process, the hardening composition for imprint is irradiated with light to form a hardened material. The irradiation amount of light irradiation in the light irradiation process may be sufficiently larger than the minimum irradiation amount required for curing. The amount of irradiation required for curing is appropriately determined by investigating the consumption of unsaturated bonds in the curable composition for imprint and the like.
The type of light to be irradiated is not particularly limited, and ultraviolet light is exemplified.
Moreover, in the imprint lithography applied to the present invention, the substrate temperature during light irradiation is usually set to room temperature, but in order to improve reactivity, light irradiation may be performed while heating. When the vacuum state is used as the preparation stage for light irradiation, it is effective in preventing the inclusion of bubbles, suppressing the decrease in the reactivity caused by the incorporation of oxygen, and improving the adhesion between the mold and the hardening composition for imprinting. Light irradiation was performed in a vacuum state. Moreover, in the said hardened | cured material pattern manufacturing method, the preferable vacuum degree at the time of light irradiation is the range of ^10-1 Pa to normal pressure.
When exposed, the exposure illuminance is set to 1 ~ 500mW / cm ² and is preferred, to 10 ~ 400mW / cm ² more preferably in the range of. The exposure time is not particularly limited, but is preferably 0.01 to 10 seconds, and more preferably 0.5 to 1 second. The exposure amount is preferably in the range of 5 to 1000 mJ / cm ² , and more preferably in the range of 10 to 500 mJ / cm ² .
In the above-mentioned method for manufacturing a cured product pattern, after curing the film-shaped imprintable curable composition (pattern-forming layer) by light, the process may further include a process of heating and curing the cured pattern, if necessary. The temperature for heating and hardening the curable composition for imprinting after light irradiation is preferably 150 to 280 ° C, and more preferably 200 to 250 ° C. The time for applying heat is preferably 5 to 60 minutes, and more preferably 15 to 45 minutes.

＜＜ Release Process ＞＞
In the demolding process, the hardened material is separated from the mold ((5) in FIG. 1). The obtained hardened material pattern can be used in various applications as described later.
That is, in the present invention, there is disclosed a laminated body further having a hardened pattern formed of a hardenable composition for imprint on the surface of the underlayer film. Moreover, although the film thickness of the pattern formation layer containing the hardening composition for imprints used by this invention differs depending on the use used, it is about 0.01 micrometer-30 micrometers.
In addition, as described later, etching and the like can be performed.

＜ The hardened pattern and its application ＞
As described above, the hardened pattern formed by the method for manufacturing a hardened pattern can be used as a permanent film used in a liquid crystal display device (LCD), etc., or as an etching resist (mask for lithography) for semiconductor device manufacturing. ).
In particular, the present invention discloses a method for manufacturing a circuit board, which includes a process of obtaining a hardened pattern by a method for manufacturing a hardened pattern according to a preferred embodiment of the present invention. Furthermore, the method for manufacturing a circuit board according to a preferred embodiment of the present invention may include a process and formation of etching or ion implantation on the substrate using the hardened pattern obtained by the above-mentioned hardened pattern manufacturing method as a mask. Process of electronic components. The circuit board-based semiconductor element is preferably. Furthermore, a method for manufacturing an electronic device is disclosed in the present invention. The method includes a process for obtaining a circuit board by the method for manufacturing a circuit board and a process for connecting the circuit board to a control mechanism that controls the circuit board.
In addition, a grid pattern is formed on the glass substrate of the liquid crystal display device by using the pattern formed by the above-mentioned hardened pattern manufacturing method, thereby making it possible to inexpensively manufacture a large screen size (eg, 55 inches, greater than 60 inches with less reflection or absorption). Inch) polarizer. For example, a polarizing plate described in Japanese Patent Application Laid-Open No. 2015-132825 or International Publication No. 2011/132649 can be manufactured. Furthermore, 1 inch is 25.4 mm.
As shown in (6) in FIG. 1 and (7) in FIG. 1, the hardened pattern formed by the present invention is also useful as an etching resist (mask for lithography). When a hardened pattern is used as an etching resist, first, a silicon substrate (silicon wafer, etc.), for example, a thin film of SiO ₂ or the like is used as a substrate, and a nano pattern is formed on the substrate by the above-mentioned hardened pattern manufacturing method, for example. Or micron-level fine hardened pattern. In the present invention, it is particularly effective to form a nano-scale fine pattern, and it is also possible to form a pattern having a size of 50 nm or less, especially 30 nm or less. The lower limit value of the size of the hardened | cured material pattern formed by the said hardened | cured material pattern manufacturing method is not specifically limited, For example, it can be 1 nm or more.
As a preferred embodiment, a process for obtaining a hardened pattern on a substrate by a method for manufacturing a hardened pattern and a process for embossing a mold using the obtained hardened pattern to etch the substrate can also be mentioned. Production method.
In wet etching, etching is performed using hydrogen fluoride or the like, and in dry etching, etching gas such as CF ₄ is used to form a desired hardened pattern on the substrate. The hardened material pattern is particularly excellent in etching resistance against dry etching. That is, the pattern formed by the above-mentioned hardened pattern manufacturing method is preferably used as a mask for lithography.

FIG. 2 is a plan view schematically showing a state of wetting and spreading of the hardening composition for imprinting when the hardening composition for imprinting is applied to the surface of the underlayer film by an inkjet method. When the hardening composition for imprinting is applied by the inkjet (IJ) method, for example, as shown in FIG. 2, the liquid droplets of the hardening composition 22 for imprinting are dripped at regular intervals on the surface of the lower film 21 (FIG. 2). (A) in 2). When the mold is contacted here, the above-mentioned droplets spread on the lower layer film 21 and become film-like hardening compositions 22a, 22b, and 22c for imprinting ((b) in FIG. 2 and (c) in FIG. 2 ((D) in Figure 2). However, the hardening composition for imprinting does not spread uniformly. For example, if the wetting expansion stops in (c) in FIG. 2, the state of forming the hardening composition 22b for imprinting on the lower film 21 is not present. Fully expanded film. That is, there may be a case where the film thickness is thin or there is no region 23. In this manner, a portion of the mold which is not sufficiently filled with the hardening composition for imprint is generated in the pattern of the mold, and a portion without a pattern is generated in the imprint layer. For example, when the pattern of the imprinted layer with a defect or an insufficient thickness in a part is used as a mask as described above, the area from the thin film thickness to the area without the film 23 and the other The uneven etching occurs in the region 22b, making it difficult to uniformly etch and transfer a desired pattern shape throughout the entire imprinted region.
In contrast, according to the present invention, the surface tension between the underlayer film and the hardening composition for imprint formation is improved, and the wettability is improved. Therefore, the curable composition 22c for imprinting is expanded more reliably to each corner of the state of (d) in FIG. 2. As a result, the curable composition for imprint can be reliably and sufficiently filled in the mold throughout the entirety, and a good patterning without unevenness in thickness can be achieved in the formed imprint layer. In addition, high-speed embossing can be performed by improving the filling property, which leads to improvement in throughput.
In addition, in the above description, an example in which the hardening composition for imprint is applied to the underlayer film by the inkjet method is described to explain the action mechanism of the preferred embodiment of the present invention, but the present invention is not limited thereto. And explain. For example, in screen coating or spin coating, good wettability and excellent filling properties are also related to advantages in processing and product quality, and the effects of the invention can be appropriately exerted.

Specifically, the pattern formed by the present invention can be preferably used for the production of a guide pattern or the like, which is used to form a self-organized fine pattern (directed self-assembly, DSA (directed self-assembly)) ), 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, filters, microlens arrays, thin film transistors, organic transistors, color filters, anti-reflection films, polarizers, polarizers, optical films, pillars, and other flat panel display components Nano-devices, immunoassay wafers, DNA separation wafers, microreactors, photonic liquid crystals, block copolymers.
[Example]

The following examples further illustrate the present invention. The materials, usage amounts, proportions, processing contents, processing sequence, and the like shown in the following examples can be appropriately changed as long as they do not depart 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>
To a three-necked flask with N ₂ flowing, methanol (MeOH) (300 g), 5-Bromoisophthalic Acid (5-bromoisophthalic acid) (manufactured by Tokyo Chemical Industry Co., Ltd., 10 g), and concentrated sulfuric acid (1 mL) were added, and The mixture was heated to 90 ° C and aged for 4 hours. Then, it concentrated under reduced pressure. The concentrate, ethyl acetate (500 g), and a 3% aqueous sodium hydrogen carbonate solution (300 g) were added to the separatory funnel and stirred. The organic layer was concentrated to synthesize the target compound (intermediate G-1A).

To a three-necked flask with N ₂ flowing, tetrahydrofuran (THF) (300 g) and G-1A (10 g) were cooled to 0 ° C, and LiAlH ₄ (manufactured by FUJIFILM Wako Pure Chemical Corporation, 3 g) was added little by little; It was aged for 2 hours. Thereafter, water (3 g), a 15% aqueous sodium hydroxide solution (3 g), and water (9 g) were added, and the mixture was aged for 1 hour. Thereafter, the target compound (intermediate G-1B) was synthesized by filtering and concentrating the filtrate.

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

Mg (1 g), G-1C (10 g), and THF (100 g) were added to a three-necked flask flowing N _{2, and} the mixture was cooled to 0 ° C. and aged for 1 hour. Thereafter, acetone (2 g) was added little by little, and the mixture was aged for 2 hours. Then, it concentrated under reduced pressure. The concentrate, ethyl acetate (500 g), and a 3% aqueous sodium hydrogen carbonate solution (300 g) were added to the separatory funnel and stirred. The target compound (intermediate G-1D) was synthesized by concentrating the organic layer and purifying it by a silica gel layer method.

To a three-necked flask with N ₂ flowing, G-1D (10 g) and cyclohexane (100 g) were added, cooled to 0 ° C, and a 20% butyllithium cyclohexane solution (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. , 12 mL) and aged for 1 hour. After that, methacrylic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd., 3 g) was added dropwise, and the mixture was aged for 1 hour. Thereafter, THF (100 g) and a 1 M aqueous HCl solution were added, and the mixture was aged for 5 hours. Thereafter, ethyl acetate (1000 g) and a 3% aqueous sodium hydrogen carbonate solution (300 g) were added and stirred. The target compound (intermediate G-1E) was synthesized by concentrating the organic layer and purifying it by a silica gel layer method.

PGMEA (30 g) was added to a three-necked flask with N ₂ flowing and warmed to 60 ° C. Dissolve 2-Hydroxyethyl Methacrylate (made by Tokyo Chemical Industry Co., Ltd., 13g, 100mmol), G-1E (26g, 100.0mmol), photo radical in PGMEA (70g) A polymerization initiator (FUJIFILM Wako Pure Chemical Corporation, V-65, 1.0 g, 4.0 mmol), and the obtained mixture was added dropwise over a period of 2 hours at a temperature not exceeding 65 ° C inside the flask, and at 90 ° C. The aging was performed at 4 ° C for 4 hours. After that, it was cooled to 25 ° C. Diisopropyl ether (435.5 g) and hexane (186.6 g) were added to another three-necked flask, and the mixture was cooled to 0 ° C and stirred. The reaction liquid in the flask was added dropwise to the mixed liquid in another three-necked flask over a period of 30 minutes at a temperature not exceeding 5 ° C., and stirred for 1 hour. Then, it was left to stand 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 added to a three-necked flask with N ₂ flowing, and cooled. To 0 ° C. PGMEA (45.38 g) and Acryloyl Choride (propylene gallium chloride) (14 g, 150.0 mmol) were mixed and added dropwise over a period of 2 hours at a temperature not exceeding 10 ° C inside the flask, and then performed at 20 ° C for 4 hours Mature. After that, it was cooled to 0 ° C. Diisopropyl ether (435.5 g) and hexane (186.6 g) were added to another three-necked flask, and the mixture was cooled to 0 ° C and stirred. The reaction liquid in the flask was added dropwise to the mixed liquid in another three-necked flask over a period of 30 minutes at a temperature not exceeding 5 ° C., and stirred for 1 hour. Then, it was left to stand for 1 hour, and filtered under reduced pressure. The obtained powder was washed with water and dried under reduced pressure to synthesize the target compound G-1.
Other polymers were synthesized following the above synthesis example.

<Preparation of the Underlayer Film-forming Composition>
The components are blended as shown in Tables 1 to 4 below. Two stages of filtration are 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. The underlayer film-forming composition for imprint in Examples and Comparative Examples. In Tables 1 to 4, the serial numbers of the curable compositions for imprinting used in combination are marked together.

<How to check the detached components when baking at 80 ° C>
A silicon wafer (8 inches in diameter) is spin-coated with an underlayer film-forming composition for imprinting. After that, under a baking condition of 80 ° C. for 3 minutes in 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. The obtained lower film was immersed in tetrahydrofuran (THF) for 30 minutes, and the obtained THF solution was analyzed by LC / MS.
In this manner, it was confirmed whether a compound represented by the formula (r1) or (r2) or the formula (r1-1) and having a molecular weight of 210 or more was detected.
A compound surrounded by a dotted line below a polymer to be described later is a compound having been detached. Regarding the polymers H-1 to H-3, no detachment of the compound having a molecular weight of 210 or more was confirmed. Regarding the polymer H-3, no separation of the compound represented by the formula (r1) or (r2) or the compound represented by the formula (r1-1) was confirmed.

<Preparation of hardening composition for imprinting>
Each compound shown in Table 5 was mixed, and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy radical (manufactured by Tokyo Chemical Industry Co., Ltd.) was further used as a polymerization inhibitor. It added so that it might become 200 mass ppm (0.02 mass%) with respect to the total amount of the polymerizable compound among the compounds shown in the table, and it prepared, and obtained the curable composition for imprints. For this purpose, a two-stage filtration was performed using a polytetrafluoroethylene (PTFE) filter with a pore size of 0.1 μm and a UPE (ultra high molecular weight polyethylene) filter with a pore size of 0.003 μm.

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

＜ Calculation of Hansen solubility parameter distance （ΔHSP） ＞
Hanson solubility parameters were calculated using HSP calculation software HSPiP.
The structural formula of each compound was input to the above software in the form of SMILES, whereby each component (d component, p component, h component) of the Hansen solubility parameter was calculated. Regarding the calculated Hansen solubility parameter, the distance between the Hansen solubility parameters (ΔHSP: ΔD, ΔP, ΔH) between the components is calculated as needed.
ΔHSP = (4.0 × ΔD ² + ΔP ² + ΔH ² ) ^0.5 …… (H1)
When there are a plurality of compounds in each calculation target component (for example, when there are two or more detached components, etc.), the value of the largest component (mass basis) in the compound is used as the Hansen solubility parameter. When the maximum amount component is two or more types, it is set to (average value based on the mixing ratio).
Tables 1 to 4 show the distance (ΔHSP) between the detached component and the Hansen solubility parameter of the hardening composition calculated from the formula (H1).

＜ Method of measuring molecular weight ＞
The weight average molecular weight (Mw) of a polymer is defined as a polystyrene conversion value according to gel permeation chromatography (GPC measurement). HLC-8220 (manufactured by TOSOH CORPORATION) was used for the apparatus, and protective column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) were used as the column. As the eluent, THF (tetrahydrofuran) was used. The detection uses a UV (ultraviolet) wavelength 254nm detector.

＜ Adhesiveness ＞
A silicon wafer (8 inches in diameter) was spin-coated with an underlayer film-forming composition for imprinting. Thereafter, under a baking condition of 150 ° C. for 3 minutes in 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, an inkjet printer DMP-2831 manufactured by FUJIFILM Dimatix was used to eject a hardening composition for imprint adjusted to a temperature of 23 ° C. at a drop volume of 1 pL per nozzle, and the liquid was applied to the lower film. Coating was performed so that a square array with an interval of about 100 μm was dropped.
A quartz mold (a rectangular line / spacer pattern (1/1), a line width of 40 nm, a groove depth of 100 nm, and a line edge roughness of 3.5 nm) was mounted so as to contact the hardenable composition layer for imprinting. A high-pressure mercury lamp was used on the wafer side and exposed at 300 mJ / cm ² . After the exposure, the quartz wafer was separated, and the peel force at this time was measured.
This peeling force corresponds to the adhesion force F (unit: N). The peeling force was measured according to the measuring method of the peeling force of the comparative example described in paragraphs 0102 to 0107 of Japanese Patent Application Laid-Open No. 2011-206977. That is, the peeling steps 1 to 6 and 16 to 18 of FIG. 5 in the aforementioned publication are performed.
A: F≥45N
B: 45N ＞ F≥30N
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. After that, under a baking condition of 150 ° C. for 3 minutes in an air atmosphere, the lower layer film was formed on the adhesion layer by heating with a hot plate. The thickness of the obtained underlayer film was about 10 nm.
On the surface of the lower film, an inkjet printer DMP-2831 manufactured by FUJIFILM Dimatix was used to eject a hardening composition for imprint adjusted to a temperature of 23 ° C. at a drop volume of 1 pL per nozzle, and the liquid was applied to the lower film. Coating was performed so as to form a square array with an interval of about 100 μm.
After coating, the shape of the droplet was photographed 3 seconds later, and the diameter of the droplet was measured. Two samples were used for each level, and three measurements were taken. The arithmetic average of 6 times in total was adopted as the evaluation value. The results are shown in Tables 1 to 4.
A: The average diameter of IJ droplets is> 500 μm
B: 400 μm <IJ average diameter of droplets ≤ 500 μm
C: 320μm <IJ average diameter of droplets ≤400μm
D: average diameter of IJ droplets ≤320μm

[Table 1]


[Table 2]


[table 3]


[Table 4]

polymer
[Chemical Formula 21]

The dotted line indicates the detached component (the same applies hereinafter).
Molecular Weight refers to molecular weight.
[Chemical Formula 22]

[Chemical Formula 23]

[Chemical Formula 24]

[Chemical Formula 25]

[Chemical Formula 26]

[Chemical Formula 27]

[Chemical Formula 28]

[Chemical Formula 29]

Release reaction promoter or its precursor
T-1, T-4, T-5, T-6 and T-7 are photoacid generators. T-2 is a hot alkali generator. T-3 is a thermal acid generator.
[Chemical Formula 30]

Photopolymerization initiator
[Chemical Formula 31]

[table 5]

It is clear from the above results that the underlayer film-forming composition for imprints of the present invention contains a polymer that releases a specific release component and, when used in combination with a hardenable composition for imprints, exhibits excellent wettability and good adhesion. (Examples 1 to 21). On the other hand, it was found that those who did not detach the detached component or could not take a specific chemical structure even if the detached component detached, the wettability or adhesion was poor (Comparative Examples 1 to 3).

The film of the curable composition for imprint produced in each Example was brought into contact with a quartz mold having a pattern having 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 to which the pattern of the mold is transferred. As a result, it was confirmed that a good pattern can be formed in any hardened material.

1‧‧‧ substrate

2‧‧‧ lower film

3‧‧‧curable composition for imprinting

4‧‧‧ mold

21‧‧‧ under film

22‧‧‧ Curable composition for embossing

22a, 22b, 22c ‧‧‧ film-like hardening composition for embossing

23‧‧‧ Area without film

FIG. 1 is a manufacturing process explanatory drawing showing an example of the formation of a cured product pattern and an example of manufacturing steps when the obtained cured product pattern is used for processing by an etching substrate.

FIG. 2 is a plan view schematically showing the wet spreading state of the hardening composition for imprinting when the hardening composition for imprinting is applied to the surface of an underlayer film having low wettability by an inkjet method.

Claims (27)

An underlayer film-forming composition for imprinting includes a polymer and a solvent. In the composition, when the underlayer film-forming composition for imprinting is made into a film shape and baked at 80 ° C., the following formula (r1 ) Or a compound represented by formula (r2) and having a molecular weight of 210 or more is detached 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, and R ^r4 , R ^r5 and At least one of R ^r6 is a substituent, and R ^r3 is a divalent substituent. The underlayer film-forming composition for imprinting according to item 1 of the scope of patent application, wherein the compound represented by the formula (r1) or (r2) is represented by the formula (r1-1), In the formula, R ^r1 and R ^r2 are each independently a hydrogen atom or a monovalent substituent, and at least one of R ^r1 and R ^r2 is a substituent. The underlayer film-forming composition for imprinting according to item 1 or item 2 of the patent application scope, wherein the polymer contains one represented by any one of the following formulae (R-1) to (R-4) Group, 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 position to be bonded to the polymer's main chain. The underlayer film-forming composition for imprinting according to item 3 of the patent application scope, wherein The CO bond in the formula is decomposed from a polymer containing a substituent represented by any one of the formulae (R-1) to (R-4), so that the molecular weight is represented by the formula (r1) or (r2) Compounds above 210 are released from the polymer. The underlayer film-forming composition for imprinting as described in item 1 or 2 of the patent application scope, wherein The polymer contains a polymerizable group. The underlayer film-forming composition for imprinting according to item 5 of the scope of patent application, wherein This polymerizable group contains an acrylfluorenyl group or a methacrylfluorenyl group. The underlayer film-forming composition for imprinting as described in item 1 or 2 of the patent application scope, wherein The polymer contains an aromatic ring. The underlayer film-forming composition for imprinting according to item 1 or item 2 of the scope of patent application, wherein the polymer includes a component in a structural unit represented by any one of the following formulae (1) to (6). At least 1 In the formula, R ^P4 is a hydrogen atom or a methyl group, and R ^P1 represents a group capable of removing a compound represented by the formula (r1) or the formula (r2). The underlayer film-forming composition for imprinting as described in item 1 or 2 of the patent application scope, wherein The compound represented by this formula (r1) or (r2) contains an aromatic ring. The underlayer film-forming composition for imprinting as described in item 1 or 2 of the patent application scope, wherein The compound represented by this formula (r1) or (r2) contains a polymerizable group. The underlayer film-forming composition for imprinting according to item 10 of the patent application scope, wherein This polymerizable group contains an acrylfluorenyl group or a methacrylfluorenyl group. The underlayer film-forming composition for imprinting according to item 1 or item 2 of the scope of patent application, wherein at least one of R ^r1 and R ^r2 of the formula (r1) and R ^r4 to R of the formula (r2) At least one of ^r6 contains a polymerizable group. The underlayer film-forming composition for imprinting as described in item 1 or 2 of the patent application scope, wherein The molecular weight of the compound represented by the formula (r1) or (r2) is 1,000 or less. The underlayer film-forming composition for imprinting according to item 1 or item 2 of the patent application scope, further comprising a release reaction accelerator or a precursor thereof. The underlayer film-forming composition for imprinting according to item 1 or item 2 of the patent application scope, further comprising a photopolymerization initiator. The underlayer film-forming composition for imprinting as described in item 1 or 2 of the patent application scope, wherein The surface tension of the compound represented by this formula (r1) or (r2) is 35 mN / m to 55 mN / m. The underlayer film-forming composition for imprinting as described in item 1 or 2 of the patent application scope, wherein The solvent is contained in a proportion of 95.0% by mass or more. An embossable curable composition comprising a polymerizable compound and used in combination with the embossing underlayer film-forming composition according to any one of claims 1 to 17 of the scope of patent application. A kit comprising the underlayer film-forming composition for imprinting according to any one of claims 1 to 17 of the scope of patent application, and a hardening composition for imprinting containing a polymerizable compound. The kit according to item 19 of the scope of patent application, wherein the Hansen solubility parameter of the compound represented by the formula (r1) or the formula (r2) and the Hansen solubility parameter of the hardening composition for imprinting are determined by The ΔHSP value calculated by the following mathematical formula (H1) is 5 or less, ΔHSP = (4.0 × ΔD ² + ΔP ² + ΔH ² ) ^0.5 …… (H1) The above ΔD is the Hansen solubility parameter of the hardening composition for imprinting. The difference between the dispersion term component of the vector and the dispersion term component of the Hanson solubility parameter vector of the compound represented by formula (r1) or formula (r2), where ΔP is the polarity of the Hanson solubility parameter vector of the hardening composition for imprinting The difference between the term component and the polar term component of the Hansen solubility parameter vector of the compound represented by formula (r1) or formula (r2), where ΔH is the hydrogen bond term component of the Hansen solubility parameter vector of the hardening composition for imprinting Difference from the hydrogen bond term component of the Hansen solubility parameter vector of the compound represented by formula (r1) or formula (r2). An underlayer film formed of the underlayer film-forming composition according to any one of claims 1 to 17 of the scope of patent application. A laminated body formed by the kit described in the 19th or 20th in the scope of patent application, The laminated body includes: an underlayer film formed of the underlayer film forming composition for imprinting; and an imprint layer formed of the hardening composition for imprinting and located on a surface of the underlayer film. A manufacturing method of a laminated body, which uses the kit described in claim 19 or 20 of the patent application scope to manufacture the laminated body, the manufacturing method includes applying on the surface of the lower layer film formed from the lower layer film forming composition for imprinting Process for hardening composition for imprinting. The method for manufacturing a laminated body according to item 23 of the scope of patent application, wherein The curable composition for imprint is applied to the surface of the underlayer film by an inkjet method. According to the method for manufacturing a laminated body as described in the scope of application for the patent No. 23 or No. 24, the manufacturing method further includes a process for applying the lower-layer film-forming composition for imprinting to a layer on a substrate, and includes the process at 80 ° C. Heating at ~ 250 ° C is suitable for the process of forming the layered underlayer film-forming composition for imprinting. A method for manufacturing a hardened pattern, which uses the kit described in the 19th or 20th of the scope of application for a patent to manufacture a hardened pattern. The method has an underlayer film forming process and applies an underlayer film forming composition for imprinting on a substrate. An underlayer film is applied; a process is applied, and a hardening composition for imprinting is applied on the surface of the lower layer film; a mold contact process makes the hardening composition for imprinting contact with a mold having a pattern for transferring a pattern shape A light irradiation process to irradiate the hardening composition for imprint with light to form a hardened object; and a demolding process to separate the hardened object from the mold. A method for manufacturing a circuit board includes a process of obtaining a hardened pattern by the manufacturing method described in item 26 of the scope of patent application.