WO2019172156A1 - Underlayer film forming composition for imprinting, curable composition for imprinting, and kit - Google Patents

Underlayer film forming composition for imprinting, curable composition for imprinting, and kit Download PDF

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Publication number
WO2019172156A1
WO2019172156A1 PCT/JP2019/008277 JP2019008277W WO2019172156A1 WO 2019172156 A1 WO2019172156 A1 WO 2019172156A1 JP 2019008277 W JP2019008277 W JP 2019008277W WO 2019172156 A1 WO2019172156 A1 WO 2019172156A1
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Prior art keywords
imprints
group
composition
ring
formula
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PCT/JP2019/008277
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French (fr)
Japanese (ja)
Inventor
直也 下重
雄一郎 後藤
旺弘 袴田
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富士フイルム株式会社
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Priority to JP2020505001A priority Critical patent/JP7017623B2/en
Publication of WO2019172156A1 publication Critical patent/WO2019172156A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34

Definitions

  • the present invention relates to the provision of an underprint film forming composition for imprinting, a curable composition for imprinting, and a kit.
  • the imprint method is to transfer a fine pattern by pressing a mold against a curable composition, curing the composition, and then peeling the mold. Attempts have been made to apply this method to the field of precision processing such as the manufacture of semiconductor integrated circuits.
  • the imprint method eliminates the need for expensive fine processing devices such as steppers and electron beams. Since the manufacturing cost is reduced, the process is simple, and high resolution and high throughput can be realized, research for mass production of devices is being actively conducted in various fields.
  • the imprint method there is a technique in which a photosensitive resin composition is used as a material applied for patterning and processing is performed by combining a light-transmitting mold.
  • a pattern is formed on the cured film of the photosensitive resin composition disposed on the substrate by irradiating light through a mold, and this is used as an insulating member or as a mask for further processing.
  • What uses ultraviolet (UV) as light to irradiate may be called especially the UV nanoimprint method.
  • the optical nanoimprinting method including the UV nanoimprinting method processing at room temperature is possible, unlike the thermal nanoimprinting method that requires heating using a thermosetting resin composition. Therefore, it can be widely applied as a technique for realizing high quality in the manufacture of semiconductor devices and the like that dissipate heat.
  • Patent Document 1 contains a resin having at least one group selected from a (meth) acryloyloxy group, an alkoxycarbonyl group, an oxiranyl group, and an oxetanyl group, a nonionic surfactant, and a solvent.
  • a resin composition for forming an underlayer film is disclosed. Accordingly, it is described that the variation in the residual film thickness after pressing the mold is small, and the variation in the line width distribution of the pattern after pressing is less likely to occur.
  • the formation of a fine pattern by imprinting is extremely efficient as compared with the technique by photolithography, and the manufacturing cost and productivity for manufacturing a semiconductor device can be greatly improved.
  • semiconductor technology advances further improvements in pattern miniaturization and manufacturing quality are required.
  • the lower film forming composition for imprinting in order to increase the adhesion between the substrate and the curable composition for imprinting, the lower film forming composition for imprinting is used, and the coating film of the lower film forming composition for imprinting is used.
  • it has been studied to apply a curable composition for imprints to a surface to form a film there is a demand for further improvement of the wettability of the film.
  • the present invention is superior in the wettability of the curable composition for imprints to the coating film of the underlayer film forming composition for imprints, and the adhesion between the underlayer film and the imprint layer formed from these compositions. It is an object of the present invention to provide an underprint film forming composition for imprinting, a curable composition for imprinting, and a kit using these.
  • the above problems can be solved by employing a polymer capable of generating a specific desorption component in the composition for forming an underlayer film for imprinting. It was. Specifically, the above problem has been solved by the following means ⁇ 1>, preferably ⁇ 2> to ⁇ 27>.
  • An underprint film-forming composition for imprints comprising a polymer and a solvent, wherein when the above-mentioned undercoat film-forming composition for imprints is formed into a film and baked at 80 ° C., from the polymer, the following formula (r1) Or a composition for forming an underlayer film for imprinting, wherein a compound represented by (r2) and having a molecular weight of 210 or more is eliminated;
  • R r1 , R r2 , R r4 , R r5 , and R r6 are each independently a hydrogen atom or a monovalent substituent, and at least one of R r1 and R r2 is a substituent, R r4 , At least one of R r5 and R r6 is a substituent, and R r3 is a divalent substituent.
  • composition for forming an underlayer film for imprints according to ⁇ 1>, wherein the compound represented by the formula (r1) or (r2) is represented by the formula (r1-1);
  • 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.
  • composition for forming an underlayer film for imprints according to ⁇ 1> or ⁇ 2>, wherein the polymer includes a group represented by any of the following formulas (R-1) to (R-4);
  • 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
  • X is a bonding position to the main chain of the polymer. Represents.
  • ⁇ 4> From the polymer containing a substituent represented by any one of the above formulas (R-1) to (R-4), the C—O bond in the formula is decomposed, and the above formula (r1) or (r2) The composition for forming an underlayer film for imprints according to ⁇ 3>, wherein a compound having a molecular weight of 210 or more is eliminated.
  • ⁇ 5> The composition for forming an underlayer film for imprints according to any one of ⁇ 1> to ⁇ 4>, wherein the polymer contains a polymerizable group.
  • ⁇ 6> The underlayer film-forming composition for imprints according to ⁇ 5>, wherein the polymerizable group includes a (meth) acryloyl group.
  • ⁇ 7> The composition for forming a lower layer film for imprints according to any one of ⁇ 1> to ⁇ 6>, wherein the polymer includes an aromatic ring.
  • ⁇ 8> The imprint according to any one of ⁇ 1> to ⁇ 7>, wherein the polymer includes at least one structural unit represented by any of the following formulas (1) to (6): An underlayer film forming composition;
  • R P4 represents a hydrogen atom or a methyl group;
  • R P1 represents a group capable of leaving the compound represented by the formula (r1) or (r2).
  • ⁇ 9> The underlayer film-forming composition for imprints according to any one of ⁇ 1> to ⁇ 8>, wherein the compound represented by the formula (r1) or (r2) includes an aromatic ring.
  • ⁇ 13> The underlayer film-forming composition for imprints according to any one of ⁇ 1> to ⁇ 12>, wherein the compound represented by the formula (r1) or (r2) has a molecular weight of 1000 or less.
  • ⁇ 14> The underlayer film-forming composition for imprints according to any one of ⁇ 1> to ⁇ 13>, further comprising an elimination reaction accelerator or a precursor thereof.
  • ⁇ 15> The composition for forming an underlayer film for imprints according to any one of ⁇ 1> to ⁇ 14>, further comprising a photopolymerization initiator.
  • ⁇ 16> Formation of an underprint film for imprinting according to any one of ⁇ 1> to ⁇ 15>, wherein the compound represented by the formula (r1) or (r2) has a surface tension of 35 to 55 mN / m Composition.
  • ⁇ 19> A kit comprising the imprint underlayer film forming composition according to any one of ⁇ 1> to ⁇ 17>, and an imprint curable composition comprising a polymerizable compound.
  • a ⁇ HSP value calculated by the following formula (H1) is 5
  • the kit according to ⁇ 19>, which is: ⁇ HSP (4.0 ⁇ ⁇ D 2 + ⁇ P 2 + ⁇ H 2 ) 0.5 (H1) ⁇ D is the difference between the dispersion term component of the Hansen solubility parameter vector of the curable composition for imprints and the dispersion term component of the Hansen solubility parameter vector of the compound represented by the formula (r1) or (r2), ⁇ P is the difference between the polar term component of the Hansen solubility parameter vector of the curable composition for imprints and the polar term component of the Hans
  • ⁇ 21> A lower layer film formed from the lower layer film forming composition according to any one of ⁇ 1> to ⁇ 17>.
  • ⁇ 22> A laminate formed from the kit according to ⁇ 19> or ⁇ 20>, The laminated body which has the lower layer film formed from the said lower layer film formation composition for imprints, and the imprint layer formed from the said curable composition for imprints, and located in the surface of the said lower layer film.
  • ⁇ 23> A method for producing a laminate using the kit according to ⁇ 19> or ⁇ 20>, wherein the surface of the lower layer film formed from the lower layer film forming composition for imprinting is cured for imprinting.
  • the manufacturing method of a laminated body including applying an adhesive composition.
  • the method further includes the step of applying the lower layer film-forming composition for imprinting on the substrate in a layered manner, and heating the lower layer film forming composition for imprinting applied to the layered state at 80 to 250 ° C.
  • ⁇ 26> A method for producing a cured product pattern using the kit according to ⁇ 19> or ⁇ 20>, wherein a lower layer film is formed on a substrate by applying the lower film forming composition for imprinting Contact the film forming step, the application step of applying the curable composition for imprints to the surface of the lower layer film, the curable composition for imprints, and the mold having a pattern for transferring the pattern shape.
  • Production method. ⁇ 27> A method for producing a circuit board, comprising a step of obtaining a cured product pattern by the production method according to ⁇ 26>.
  • the wettability of the curable composition for imprints with respect to the coating film of the lower layer film-forming composition for imprints, and the adhesion between the lower layer film and the imprint layer formed from these compositions are improved. Became possible.
  • imprint preferably refers to pattern transfer having a size of 1 nm to 10 mm, more preferably pattern transfer (nanoimprint) having a size of approximately 10 nm to 100 ⁇ m.
  • group (atomic group) in this specification the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • light includes not only light in a wavelength region such as ultraviolet, near ultraviolet, far ultraviolet, visible, infrared, and electromagnetic waves, but also radiation.
  • radiation include microwaves, electron beams, extreme ultraviolet rays (EUV), and X-rays.
  • Laser light such as a 248 nm excimer laser, a 193 nm excimer laser, and a 172 nm excimer laser can also be used.
  • the light may be monochromatic light (single wavelength light) that has passed through an optical filter, or may be light having a plurality of different wavelengths (composite light).
  • the temperature in the present invention is 23 ° C. unless otherwise specified.
  • the underlayer film-forming composition for imprints of the present invention contains a polymer and a solvent.
  • the following formula (r1) or (r2) is determined from the polymer. Is desorbed (hereinafter also referred to as a desorbing component).
  • the generation of a low molecular component causes a decrease in interfacial tension on the surface of the lower layer film, and accordingly, wettability is improved.
  • the curable component of the curable composition for imprints penetrates into the region where the low molecular component was present in the lower layer film, and the portion is cured, thereby lower layer film It is considered that the adhesion between the cured product and the cured product is improved.
  • ⁇ Underlayer film-forming composition for imprint> when the composition for forming a lower layer film for imprinting is formed into a film and baked at 80 ° C., a compound represented by the following formula (r1) or (r2) and having a molecular weight of 210 or more is desorbed from the polymer. To do.
  • the above compound is referred to as a desorbing component.
  • the desorbing component is a component that desorbs from the polymer when the underlayer film forming composition for imprinting is formed into a film and baked at 80 ° C., and is a compound having a predetermined structure and having a molecular weight of 210 or more. is there.
  • the desorption component in the first embodiment of the present invention is represented by the following formula (r1) or (r2).
  • the desorbing component is a compound represented by the formula (r1) or (r2)
  • the polymerization initiator in the curable composition for imprinting diffuses into the underlayer film forming composition for imprinting, and for imprinting.
  • the composition for forming a lower layer film for imprints is cured, and the adhesion between the curable composition for imprints and the lower layer film is more excellent.
  • R r1 , R r2 , R r4 , R r5 , and R r6 are each independently a hydrogen atom or a monovalent substituent, and at least one of R r1 and R r2 is a substituent, R r4 , At least one of R r5 and R r6 is a substituent, and R r3 is a divalent substituent.
  • the compound represented by the formula (r1) or (r2) is preferably represented by the following formula (r1-1).
  • 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 (preferably the following ring aCy or hCy).
  • an aromatic ring preferably the following ring aCy or hCy.
  • at least one of R r1 and R r2 of formula (r1), at least one of R r4 to R r6 of formula (r2), and at least one of R r1 and R r2 of formula (r1-1) are aromatic rings It is preferable to contain.
  • the aromatic ring is preferably the following ring aCy or hCy.
  • aromatic ring is an aromatic ring
  • aromatic ring examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, phenalene ring, fluorene ring, acenaphthylene ring, biphenyl ring, terphenyl ring, indene ring, indane ring, triphenylene Ring, tetraphenylene ring, pyrene ring, chrysene ring, perylene ring, tetrahydronaphthalene ring and the like.
  • the aromatic ring may have a structure in which a plurality of aromatic rings are connected with or without a connecting group L, and examples thereof include a biphenyl ring, a diphenylmethane ring, and a triphenylmethane ring.
  • examples of the structure in which a plurality of benzene rings are linked include those represented by the following formulas Ar1 to Ar5.
  • a straight line drawn outward from the center of the benzene ring indicates a bond. It is bonded to an arbitrary linking group through this single bond, or is bonded to L 1 , L 2 , P of the following formula (T1), or the main chain of the polymer through or without it. Means that.
  • a 1 is a divalent linking group, and examples of the linking group L are preferable.
  • An alkylene group which may be substituted with a fluorine atom (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and 1 to 3 carbon atoms being preferred) Further preferred are a carbonyl group, an oxygen atom, a sulfonyl group, a sulfinyl group, and —NR N —.
  • a 2 represents a nitrogen atom, a trivalent linking group containing a phosphorus atom, or a methine group.
  • the carbon number thereof is preferably 1 to 12, more preferably 1 to 6, and further preferably 1 to 5.
  • Specific examples thereof include thiophene ring, furan ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, oxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, isoindole.
  • the aromatic heterocyclic ring may have a structure in which a plurality of ring structures are connected through or without the connecting group L.
  • the aromatic heterocycle shown here is referred to as ring hCy.
  • the aromatic ring contained in the leaving component is preferably a benzene ring.
  • the aromatic ring may have a substituent T as long as the effects of the present invention are achieved.
  • substituents T they may be bonded to each other, or may be bonded to a ring in the formula through or without a linking group L to form a ring.
  • the alkyl group, alkenyl group, aryl group, arylalkyl group and the like may be further substituted with a halogen atom (a fluorine atom is preferred).
  • the leaving component preferably contains a polymerizable group.
  • the polymerizable group include groups containing an ethylenically unsaturated group, an epoxy group, a glycidyl group, an oxetane group, and the like.
  • the ethylenically unsaturated group include a group including a vinyl group, an allyl group, a vinylphenyl group, a (meth) acryloyl group, and a (meth) acryloyloxy group.
  • the polymerizable group exemplified here is referred to as a polymerizable group Ps.
  • the polymerizable group Ps preferably contains a (meth) acryloyl group or a (meth) acryloyloxy group.
  • 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) are polymerizable.
  • it contains a group.
  • the polymerizable group the polymerizable group Ps is preferable.
  • the elimination component preferably contains an ethylenic double bond. In particular, it is preferable that an ethylenic double bond is formed by elimination from the polymer. By such desorption, the effect of adhesion is exhibited.
  • R r1 , R r2 , R r4 , R r5 , R r6 is a substituent
  • examples of the substituent T described below are examples of the substituent.
  • an aryl group preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms
  • an arylalkyl group preferably 7 to 23 carbon atoms, 7 To 19 are more preferable, and 7 to 11 are more preferable
  • a group represented by the following formula (RL-1) is preferable.
  • at least R r2 or R r6 is a group represented by the following formula (RL-1).
  • L R1 and L R2 are each independently a single bond or a linking group
  • Ar R is a linking group containing an aromatic ring
  • P R is a group having a polymerizable group.
  • nr is an integer of 0 to 8
  • mr is an integer of 1 to 4.
  • L R1 is, 1 + mr -valent aromatic ring (examples of the aCy or hCy is preferred), alicyclic (e.g. below alicyclic fCy is preferred), a linear or branched radical of an alkane structure (having 1 to 40 carbon atoms are preferred 1 to 30 is more preferable, and 1 to 20 is more preferable), a linear or branched alkene structure group (preferably 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, and further preferably 2 to 20 carbon atoms), or A group having a linear or branched alkyne structure (preferably having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, still more preferably 2 to 20 carbon atoms) is preferable.
  • alicyclic e.g. below alicyclic fCy is preferred
  • a linear or branched radical of an alkane structure having 1 to 40 carbon atoms are preferred 1 to 30 is more preferable,
  • Examples of the linking group of L R2 are preferably the following linking group L or a linking group Lh containing the following hetero atom.
  • an alkylene group preferably having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms
  • an arylene group preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and 6 to 10 carbon atoms. Is more preferable
  • (oligo) alkyleneoxy group the number of carbon atoms of the alkylene group in one structural unit is preferably 1 to 12, more preferably 1 to 6, and further preferably 1 to 3; the number of repetitions is 1 to 50).
  • L R2 may be bonded to L R1 via a linking group L or not to form a ring.
  • Ar R is a linking group containing an aromatic ring. However, when nr is 0, Ar R is a substituent containing an aromatic ring.
  • the aromatic ring is preferably the above ring aCy or hCy.
  • examples of the linking group include the following linking groups L.
  • an alkylene group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms) 6 is more preferable), an alkenylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms), an alkynylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms) 2 to 3 are more preferable), (oligo) alkyleneoxy group (the number of carbon atoms of the alkylene group in one structural unit is preferably 1 to 12, more preferably 1 to 6, still more preferably 1 to 3; 1 to 50, preferably 1 to 40, more preferably 1 to 30), and an arylene group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms).
  • Ar R is not through or via a linking group L, L R1, L R2 or may be bonded to
  • P R is the volatilization having a polymerizable group, the polymerizable group, examples of the polymerizable group Ps are preferred.
  • P R is not through or via a linking group L, they may form a ring with L R1, L R2.
  • L R1, L R2, Ar R , P R may have a substituent T to the extent that the effects of the present invention.
  • the alkyl group, alkenyl group, aryl group, arylalkyl group and the like may be further substituted with a halogen atom (a fluorine atom is preferred).
  • Nr is an integer of 0 to 8, preferably 0 to 6, more preferably 0 to 4, and still more preferably 0 to 2.
  • mr is an integer of 1 to 4, preferably 1 or 2.
  • R r3 examples include CH 2 (second embodiment described below), CHR r8 , and C (R r9 ) 2 .
  • R r8 and R r9 are each independently a substituent T described later, and among them, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 3 carbon atoms), alkenyl group Groups (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms), alkynyl groups (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and further preferably 2 to 3 carbon atoms)
  • An aryl group preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms
  • an arylalkyl group preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and 7
  • the linking group Lh containing a hetero atom includes an oxygen atom, a sulfur atom, a carbonyl group, a thiocarbonyl group, a sulfonyl group, a sulfinyl group, —NR N —, an (oligo) alkyleneoxy group (of the alkylene group in one constituent unit).
  • the number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, more preferably 1 to 3; the number of repetitions is preferably 1 to 50, more preferably 1 to 40, still more preferably 1 to 30), or these Examples of the linking group include a combination.
  • 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, particularly preferably from 1 to 50, excluding hydrogen atoms.
  • the number of linking atoms of Lh is preferably 1 to 25, more preferably 1 to 20, still more preferably 1 to 15, and still more preferably 1 to 10.
  • the (oligo) alkyleneoxy group means an alkyleneoxy group or an oligoalkyleneoxy group.
  • the (oligo) alkyleneoxy group may be linear or cyclic, and may be linear or branched.
  • the linking group is a group capable of forming a salt such as when —NR N — or a carboxyl group is substituted, the group may form a salt.
  • substituent T examples include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms), and an arylalkyl group (preferably having 7 to 21 carbon atoms, more preferably 7 to 15 carbon atoms). 7 to 11 are more preferable), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms), an alkynyl group (preferably 2 to 12 carbon atoms are preferable and 2 to 6 carbon atoms are preferable).
  • an alkyl group preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms
  • an arylalkyl group preferably having 7 to 21 carbon atoms, more preferably 7 to 15 carbon atoms. 7 to 11 are more preferable
  • an alkenyl group preferably 2 to 24 carbon atoms, more preferably 2
  • hydroxyl group preferably having 0 to 24 carbon atoms, more preferably 0 to 12 and further preferably 0 to 6
  • thiol group carboxyl group, aryl group (carbon A number of 6 to 22, preferably 6 to 18, more preferably 6 to 10, and an alkoxyl group (preferably having a carbon number of 1 to 12, more preferably 1 to 6, To 3 are more preferable)
  • an aryloxy group preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms
  • an acyl group preferably having 2 to 12 carbon atoms and more preferably 2 to 6 carbon atoms).
  • acyloxy groups preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms
  • aryloyl groups preferably 7 to 23 carbon atoms, 7 to 19 carbon atoms. More preferably, 7 to 11 are more preferable
  • aryloyloxy group preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 11 carbon atoms
  • carbamoyl group preferably 1 to 12 carbon atoms are preferable).
  • a sulfamoyl group (having 0 to 12 carbon atoms is preferable, 0 to 6 is more preferable, and 0 to 3 is more preferable).
  • a sulfo group, an alkylsulfonyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), an arylsulfonyl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms).
  • a heterocyclic group preferably having a carbon number of 1 to 12, preferably 1 to 8, more preferably 2 to 5, and preferably including a 5-membered or 6-membered ring
  • RN represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, 2 to 3 are more preferable), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms).
  • an arylalkyl group preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 11 carbon atoms
  • a hydrogen atom preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 11 carbon atoms
  • the alkyl moiety, alkenyl moiety, and alkynyl moiety contained in each substituent may be linear or cyclic, and may be linear or branched.
  • the substituent T may further have a substituent T.
  • the alkyl group may be a halogenated alkyl group, or may be a (meth) acryloyloxyalkyl group, an aminoalkyl group, or a carboxyalkyl group.
  • the substituent is a group capable of forming a salt such as a carboxyl group or an amino group, the group may form a salt.
  • an alkylene group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms), an alkenylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms) 2 to 3 are more preferable), an alkynylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 and further preferably 2 to 3), an (oligo) alkyleneoxy group (of the alkylene group in one structural unit)
  • the number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3; the number of repetitions is preferably 1 to 50, more preferably 1 to 40, still more preferably 1 to 30, and the arylene group ( Preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), oxygen atom, sulfur atom, sulfonyl group, carbonyl group, thi
  • the alkylene group may have the substituent T.
  • the alkylene group may have a hydroxyl group.
  • the number of atoms contained in the linking group L is preferably 1 to 50, more preferably 1 to 40, and even more preferably 1 to 30, excluding hydrogen atoms.
  • the number of connected atoms means the number of atoms located in the shortest path among the atomic groups involved in the connection. For example, in the case of —CH 2 — (C ⁇ O) —O—, there are 6 atoms involved in the connection, and 4 atoms excluding hydrogen atoms. On the other hand, the shortest atom involved in the connection is —C—C—O—, which is three.
  • the number of connecting atoms is preferably 1 to 24, more preferably 1 to 12, and still more preferably 1 to 6.
  • the alkylene group, alkenylene group, alkynylene group, and (oligo) alkyleneoxy group may be linear or cyclic, and may be linear or branched.
  • the linking group is a group capable of forming a salt such as —NR N —, the group may form a salt.
  • the desorption component has a molecular weight of 210 or more.
  • the molecular weight of the desorbing component is preferably 210 or more, more preferably 250 or more, and even more preferably 300 or more.
  • the upper limit is practically 1000 or less.
  • the surface tension of the desorbing component is preferably 28 mN / m or more, more preferably 30 mN / m or more, further preferably 36 mN / m or more, and still more preferably 38 mN / m or more. 40 mN / m or more is even more preferable, and 42 mN / m or more is even more preferable.
  • the upper limit is preferably 80 mN / m or less, more preferably 60 mN / m or less, and still more preferably 50 mN / m or less.
  • the dispersion term component (component d) is preferably 14.0 to 20.0, more preferably 15.0 to 19.0, and more preferably 16.0 to 19.5. Even more preferred;
  • the polar term component (p component) is preferably from 2.0 to 9.0, more preferably from 3.0 to 6.0, and preferably from 3.5 to 5.0. Even more preferred;
  • the hydrogen bond term component (component h) is preferably 3.0 to 12.0, more preferably 4.7 to 7.0, and more preferably 5.0 to 6.5. Is more preferable.
  • the polymer used in the present invention (hereinafter, this polymer may be referred to as a specific polymer) is obtained when the underlayer film forming composition for imprinting containing this specific polymer is formed into a film and baked at 80 to 250 ° C.
  • a wide variety of polymers can be used that desorb the desorbing component from the polymer. More specifically, the specific polymer is preferably a polymer having a group serving as a leaving component in the side chain. In the present invention, preferably 30% by mass or more, more preferably 40% by mass or more of all structural units constituting the polymer are structural units capable of desorbing a desorbing component. The upper limit is not particularly defined, and may be 100% by mass.
  • the desorbing component 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 mass of the specific polymer.
  • the upper limit is not particularly defined, but is, for example, 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less.
  • the specific polymer preferably contains a substituent represented by any of the following formulas (R-1) to (R-4).
  • 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
  • X is a bonding position to the main chain of the polymer. Represents.
  • R 4 to R 6 , R 7 to R 9 , and R 10 to R 12 are not all hydrogen atoms.
  • a group containing a carbon atom bonded to an oxygen atom in formula (R-1), that is, a carbon atom substituted by R 1 to R 3 (hereinafter, the carbon atom at this position is referred to as an ⁇ carbon atom in each formula) is a second group.
  • a primary alkyl group or a tertiary alkyl group is preferred.
  • the group containing an ⁇ carbon atom is preferably a secondary alkyl group or a tertiary alkyl group.
  • the group containing the ⁇ carbon atom in the formulas (R-3) and (R-4) is preferably a primary alkyl group or a secondary alkyl group.
  • At least one of R 1 to R 3 is preferably a substituent, and at least two are preferably substituents.
  • At least one of R 4 to R 6 is preferably a substituent, and at least two are preferably substituents.
  • At least one of R 7 to R 9 is preferably a substituent, preferably two are hydrogen atoms and one is a substituent.
  • At least one of R 10 to R 12 is preferably a substituent, preferably two are hydrogen atoms and one is a substituent.
  • 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.
  • R 1 to R 12 may further have a substituent T as long as the effects of the present invention are exhibited.
  • the alkyl group, alkenyl group, aryl group, arylalkyl group and the like may be further substituted with a halogen atom (a fluorine atom is preferred).
  • the C—O bond in the formula is decomposed from the polymer containing a substituent represented by any one of the formulas (R-1) to (R-4), and the formula (r1) or (r2)
  • a compound represented by the formula (r1-1) and having a molecular weight of 210 or more is preferably eliminated.
  • the carbon atom substituted by R r1 and R r2 in formula (r1) (the carbon atom in the second position with the carbon atom contained in R r3 as the first position) is removed from the R in formula (R-1) before the elimination.
  • 1 to R 3 is preferably a carbon atom ( ⁇ carbon atom) to be substituted.
  • the carbon atom at the 2-position of the formula (r1) is preferably a carbon atom substituted by R 4 to R 6 of the formula (R-2) before elimination.
  • the tertiary carbon atom substituted by R r4 to R r6 is a carbon atom substituted by each of the ⁇ carbon atoms, that is, R 1 to R 3 in the formula (R-1) before elimination.
  • An atom or R 4 to R 6 in formula (R-2) is preferably a carbon atom to be substituted.
  • R 1 to R 3 is decomposed at the position of C—O, and a double bond is formed at the elimination position (alpha carbon atom position) on the elimination component side.
  • an alkyl group preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms
  • more preferably an ethyl group more preferably an ethyl group, and further preferably a methyl group.
  • R 4 to R 6 is preferably an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and even more preferably 1 to 3), It is more preferably an ethyl group, and further preferably a methyl group.
  • the specific polymer also preferably contains a polymerizable group, the polymerizable group is preferably a polymerizable group Ps, and more preferably contains a (meth) acryloyl group.
  • the polymerizable group may have a constituent unit having a group capable of leaving the leaving component, or may have another constituent unit. In the present invention, it is preferable that at least a constituent unit other than the constituent unit having a group capable of leaving the leaving component has a polymerizable group.
  • the proportion of the structural unit having a polymerizable group is preferably 10 to 100 mol%, more preferably 50 to 100 mol%, and more preferably 80 to 100 mol% of the total structural units. More preferably.
  • the specific polymer preferably includes an aromatic ring, and the aromatic ring is preferably a ring aCy or hCy.
  • the aromatic ring may be contained in a constituent unit having a group capable of leaving the leaving component, or may be contained in another constituent unit. In the present invention, it is preferable that at least the structural unit having a group capable of leaving the leaving component has an aromatic ring.
  • the proportion of the structural unit containing an aromatic ring is preferably 10 to 100 mol%, and more preferably 40 to 100 mol% of the total structural units.
  • the type of the specific polymer is not particularly limited.
  • the specific polymer further preferably includes at least one structural unit represented by any of the following formulas (1) to (6).
  • R P4 is a hydrogen atom or a methyl group.
  • R P1 represents a group capable of leaving the compound represented by the formula (r1) or (r2) or the compound represented by the formula (r1-1), and is preferably a group represented by the formula (R-1) to (R -4).
  • a linking group may be interposed between X in the formulas (R-1) to (R-4) and the main chain atom. Examples of the linking group include the linking group L. In this case, the linking group may be trivalent or more. In that case, the structural unit of the polymer has a plurality of groups represented by the formulas (R-1) to (R-4) through the linking group.
  • Examples of the trivalent or higher linking group include a group having an aromatic ring (aCy, hCy) structure, a group having an alkane structure (preferably having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and further preferably 1 to 20 carbon atoms), A group having 2 to 40 carbon atoms (preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms), and an alkyne structure group (2 to 40 carbon atoms are preferable, 2 to 30 carbon atoms are more preferable, and 2 to 20 carbon atoms are And a group according to a combination thereof, or a group according to a combination of these and a linking group Lh.
  • aCy, hCy an aromatic ring
  • alkane structure preferably having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and further preferably 1 to 20 carbon atoms
  • a group having 2 to 40 carbon atoms preferably 2 to 30 carbon atoms, more preferably 2
  • the group having an alkane structure, the group having an alkene structure, or the group having an alkyne structure may be linear or cyclic, and may be linear or branched.
  • this trivalent or higher valent linking group is referred to as a linking group Lm.
  • two or more substituents R P1 may be substituted on the same structural unit.
  • those in which two or more R P1 are substituted on the benzene ring are also exemplified as preferred embodiments of the present invention.
  • the polymer main chain and the substituent R P1 in the formulas (1) to (6) may have a substituent T as long as the effects of the present invention are exhibited.
  • the specific polymer is preferably a copolymer.
  • the copolymer component preferably contains at least one of structural units represented by any of the following formulas (1-1) to (1-6) (hereinafter sometimes referred to as other structural units).
  • each of the substituents R P2 is independently a substituent containing a polymerizable group
  • R P4 is a hydrogen atom or a methyl group.
  • the polymerizable group contained in R P2 is preferably the above Ps.
  • RP2 may have a linking group between the polymerizable group and the main chain, and in the case of a divalent linking group, examples of the linking group L are mentioned. An example of Lm is given.
  • R P2 When there are two or more R P2 in the formulas (1-1) to (1-6), that is, (R P2 ) n (n is a natural number of 1 or more), a plurality of R P2 are bonded to each other. A ring may be formed. Also, R P2 may form a ring attached to the backbone. Further, the formula (1-1) backbone and substituent T to the extent that the effect of the present invention is the substituent R P2 of to Formula (1-6) may be substituted.
  • RP2 is preferably the following formula (T2).
  • the formula weight of RP2 is preferably 80 or more and 1000 or less, more preferably 100 or more and 800 or less, and further preferably 150 or more and 600 or less.
  • L 4 is the above-described linking group L or Lm, among which an alkylene group, an arylene group, an (oligo) alkyleneoxy group, a carbonyl group, an oxygen atom, an alkane structure group, an alkene structure group, an aryl structure group, The linking group according to the combination is preferable.
  • n6 is an integer of 0-6.
  • P is a polymerizable group Ps.
  • n7 is an integer of 1 to 6, preferably 1 or 2.
  • the terminal L 4 may be a tetravalent or higher linking group and all P may be substituted, but two or more L 4 may be substituted with P. Good.
  • the specific polymer includes a structural unit represented by the formula (1), the other structural unit is preferably a structural unit represented by the formula (1-1).
  • the formulas (2) to (6) preferably include structural units represented by the formulas (1-2) to (1-6), respectively.
  • the specific polymer further includes a structural unit having no polymerizable group (sometimes referred to as “further structural unit”).
  • the other structural unit preferably has a skeleton of the formulas (1-1) to (1-6) defined in the other structural unit.
  • the substituent R P2 becomes a substituent R P3 having no polymerizable group.
  • two or more of R P2 in the other structural units (1-1), (1-2), (1-4), and (1-6) may be substituted with a ring structure group.
  • the substituent T may be substituted on the other structural unit within the range in which the effect of the present invention is exerted on the main chain portion and R P3 .
  • RP3 is preferably the following formula (T3).
  • the formula weight of RP3 is preferably 80 or more and 1000 or less, more preferably 100 or more and 800 or less, and further preferably 150 or more and 600 or less.
  • L 5 is the above linking group L or Lm, among which an alkylene group, an arylene group, an (oligo) alkyleneoxy group, a carbonyl group, an oxygen atom, an alkane structure group, an alkene structure group, an aryl structure group, The linking group according to the combination is preferable.
  • T 1 is the above-described substituent T, and examples thereof include an alkyl group, an aryl group, an alkoxy group, and an acyl group.
  • n9 is an integer of 1 to 6, preferably 1 or 2.
  • the terminal L 5 may be a tetravalent or higher linking group and all T 1 may be substituted, but two or more L 5 may be substituted with T 1. Good.
  • L 4 , L 5 , P and T 1 may have the substituent T as long as the effects of the present invention are exhibited.
  • an alkane structure group, an alkene structure group, an aryl structure group, or the like may be further substituted with a halogen atom (a fluorine atom is preferred).
  • the structural unit represented by any one of the formulas (1) to (6) may constitute all of the polymer (homopolymer having a structural ratio of 100 mol%), Furthermore, it may be a copolymer with other structural units.
  • a structural unit having a group capable of leaving a leaving component for example, a structural unit represented by formula (1) to formula (6)) / other structural unit (a structural unit having a polymerizable group) ) /
  • the composition ratio of other structural units is preferably 10 to 100/0 to 80/0 to 50, more preferably 30 to 100/0 to 70/0 to 30, and more preferably 50 to 100 / 0 to 50/0 to 10 is more preferable, and may be 50 to 90/10 to 50/0 to 10.
  • the specific polymer may contain only one kind of each of a structural unit having a group capable of leaving a leaving component, another structural unit (a structural unit having a polymerizable group), and another structural unit. And 2 or more types may be included.
  • the total is preferably the above ratio.
  • the constitutional unit is substantially free of other constitutional units other than the constitutional unit having a group capable of leaving the leaving component and the constitutional unit having a polymerizable group. “Substantially not contained” means, for example, 5% by mass or less of all structural units, preferably 3% by mass or less, and more preferably 1% by mass or less.
  • the weight average molecular weight of the specific polymer is preferably 4,000 or more, more preferably 5,000 or more, further preferably 7,000 or more, and even more preferably 10,000 or more.
  • As an upper limit 2,000,000 or less is preferable, 1,500,000 or less is more preferable, and 1,000,000 or less is more preferable.
  • the measuring method of a weight average molecular weight shall be based on the method shown in the following Example.
  • the content of the specific polymer in the composition for forming a lower layer film for imprinting is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1.0% by mass or more. It is more preferable that it is 1.5 mass% or more. As an upper limit, it is preferable that it is 10 mass% or less, It is more preferable that it is 7 mass% or less, It is further more preferable that it is 5 mass% or less, It is still more preferable that it is 4 mass% or less, 3 mass % Or less is even more preferable. By making this quantity more than the said lower limit, the effect by having mix
  • the content of the specific polymer with respect to the non-volatile component (meaning the solid content excluding the solvent in the composition) in the underlayer film-forming composition for imprints is preferably 90% by mass or more, It is more preferably 95% by mass or more, and further preferably 99% by mass or more.
  • the upper limit is 100% by mass.
  • the amount is not more than the above upper limit value, the effect of using the solvent is suitably exhibited, and it becomes easy to form a uniform film over a wide area.
  • One kind of specific polymer may be used, or two or more kinds thereof may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
  • the substituent R P1 which forms a leaving component can be introduced into the main chain by a conventional method.
  • a desorption reaction accelerator is a compound that, when coexisting with a specific polymer in the system, acts on a specific polymer by a predetermined trigger and promotes a reaction for desorbing a desorbing component from the specific polymer.
  • the elimination reaction accelerator is a compound having an acidic functional group or a basic functional group.
  • the elimination reaction accelerator is preferably present as a precursor in the composition. Examples of the precursor include a compound that reacts by applying external energy such as heat and light, and is converted into an elimination reaction accelerator compound. Specific examples include thermal acid generators, photoacid generators, thermal base generators, photobase generators, thermal acid generators and photoacid generators are preferred, and thermal acid generators are more preferred.
  • the pKa of the elimination accelerator is preferably 2 or less, more preferably 1 or less, and even more preferably 0 or less.
  • the lower limit is not particularly defined, but may be, for example, ⁇ 10 or more.
  • the pKa of the conjugate acid is preferably 5 or more, more preferably 7 or more, and still more preferably 8 or more.
  • the upper limit value is not particularly defined, but may be 15 or less, for example.
  • specific examples of the elimination reaction accelerator or its precursor include acid proliferators described in paragraphs 0012, 0017, and 0026 to 0037 of JP 2014-047329 A, and light described in paragraphs 0038 to 0040.
  • Acid generator thermal acid generator described in paragraph 0041, photobase proliferating agent described in paragraphs 0029 to 0066 of JP2012-237776, photobase generator described in paragraphs 0073 to 0087, paragraphs 0087 to 0090
  • a thermal base generator described in paragraphs 0012 to 0015 and 0023 to 0029 of Japanese Patent No. 5687442; a photoacid generator described in paragraphs 0033 to 0075 of WO 2009/123122;
  • the base generators described in paragraphs 0038 to 0069 of Kai 2011-236416 can be used, and among these, Of which are incorporated herein.
  • the content of the elimination 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 2.0% by mass or more. More preferably it is. As an upper limit, it is practical that it is 10.0 mass% or less, and may be 5.0 mass% or less. Only one type of elimination reaction accelerator or its precursor may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
  • the undercoat film-forming composition for imprinting may contain an alkylene glycol compound.
  • the alkylene glycol compound preferably has 3 to 1000 alkylene glycol structural units, more preferably 4 to 500, still more preferably 5 to 100, and more preferably 5 to It is more preferable to have 50 pieces.
  • the weight average molecular weight (Mw) of the alkylene glycol compound is preferably 150 to 10,000, more preferably 200 to 5,000, still more preferably 300 to 3,000, and even more preferably 300 to 1,000.
  • the alkylene glycol compounds are polyethylene glycol, polypropylene glycol, mono- or dimethyl ether, mono- or dioctyl ether, mono- or dinonyl ether, mono- or didecyl ether, monostearate, monooleate, monoadipate, monosuccinate.
  • the acid ester include polyethylene glycol and polypropylene glycol.
  • 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 defined, but is, for example, 48.0 mN / m or less.
  • the alkylene glycol compound When the alkylene glycol compound is contained, it is 40% by mass or less of the nonvolatile component, preferably 30% by mass or less, more preferably 20% by mass or less, and preferably 1 to 15% by mass. Further preferred.
  • One type of alkylene glycol compound may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
  • a polymerization initiator may be included.
  • the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator, and a photopolymerization initiator is preferred from the viewpoint of improving the crosslinking reactivity with the curable composition for imprints.
  • a radical polymerization initiator and a cationic polymerization initiator are preferable, and a radical polymerization initiator is more preferable.
  • a plurality of photopolymerization initiators may be used in combination.
  • halogenated hydrocarbon derivatives eg, compounds containing a triazine skeleton, compounds containing an oxadiazole skeleton, compounds containing a trihalomethyl group
  • acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives, etc.
  • oxime compounds are preferred. With respect to these details, reference can be made to the descriptions in paragraphs 0165 to 0182 of JP-A-2016-027357, the contents of which are incorporated herein.
  • acylphosphine compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
  • Commercially available products such as IRGACURE-819, IRGACURE1173, and IRGACURE-TPO (trade names: all manufactured by BASF) can be used.
  • the content of the photopolymerization initiator used in the above-described imprint lower layer film-forming composition is, for example, 0.01 to 15% by mass, preferably 0.1 to 12% by mass in the nonvolatile component. %, More preferably 0.2 to 7% by mass.
  • the total amount becomes the said range.
  • a polymerization inhibitor may be included.
  • the polymerization inhibitor (B) according to the present embodiment is a compound having the ability to trap radicals generated in the curable main agent (A) before they undergo a growth reaction. Thereby, a polymerization inhibitor (B) acts so that superposition
  • the polymerization inhibitor (B) can be any of hydroquinones, catechols, phenothiazines, and phenoxazines.
  • Specific examples of the polymerization inhibitor (B) include 4-methoxyphenol, 4-methoxy-1-naphthol, 4-tert-butylcatechol, 2,6-di-tert-butylphenol, 2,6-di-tert- Mention may be made of phenolic compounds such as butyl-p-cresol, 2-tert-butyl-4,6-dimethylphenol, 2,4,6-tri-tert-butylphenol, hydroquinone and tert-butylhydroquinone.
  • polymerization inhibitor (B) examples 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 N, such as 2,2,6,6-tetramethylpiperidine-N-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl.
  • -Oxyl compounds can also be mentioned. The compounds listed here are merely examples, and the polymerization inhibitor (B) may be other compounds.
  • the content of the polymerization inhibitor is preferably 0.0001% by mass or more and 10.0% by mass or less of the solid component, more preferably 0.001% by mass or more and 1.0% by mass or less. More preferably, it is 005 mass% or more and 0.1 mass% or less. Only one type of polymerization inhibitor may be used, or two or more types may be used. When using 2 or more types, it is preferable that those total amounts become the said range.
  • non-volatile component mix blended with the underlayer film forming composition for imprints
  • thermal polymerization initiator and the like each component described in JP2013-036027A, JP2014-090133A, JP2013-189537A can be used.
  • the description in the above publication can be referred to.
  • it can also be set as the structure which does not contain surfactant substantially in the underlayer film forming composition for imprints. “Substantially not contained” means 0.1% by mass or less of the nonvolatile component in the composition for forming a lower layer film for imprinting.
  • the underlayer film forming composition for imprints contains a solvent.
  • the solvent preferably contains, for example, a compound having a boiling point of 250 ° C. or lower (solvent for the lower layer film) at a rate of 70.0% by mass or more at 23 ° C.
  • the nonvolatile component finally forms the lower layer film.
  • the lower film forming composition for imprinting preferably contains 80.0% by mass or more of the solvent for the lower layer film, more preferably 90.0% by mass or more, and more preferably 93.0% by mass or more. Preferably, it is 94.0 mass% or more, and 95.0 mass% or more, 98.0 mass% or more, and 99.0 mass% or more may be sufficient.
  • the solvent only 1 type may be contained in the underlayer film forming composition for imprint, and 2 or more types may be contained. When 2 or more types are included, the total amount is preferably within the above range.
  • the boiling point of the solvent for the lower layer film is preferably 230 ° C. or less, more preferably 200 ° C. or less, further preferably 180 ° C. or less, further preferably 160 ° C. or less, and 130 ° C. or less. Is more preferable.
  • the lower limit is 23 ° C., but practically 60 ° C. or higher.
  • the solvent for the lower layer film is preferably an organic solvent.
  • the solvent is preferably a solvent containing any one or more of an ester group, a carbonyl group, a hydroxyl group and an ether group. Among these, it is preferable to use an aprotic polar solvent.
  • alkoxy alcohol propylene glycol monoalkyl ether carboxylate, propylene glycol monoalkyl ether, lactic acid ester, acetic acid ester, alkoxypropionic acid ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate are selected.
  • alkoxy alcohol examples include methoxyethanol, ethoxyethanol, methoxypropanol (eg 1-methoxy-2-propanol), ethoxypropanol (eg 1-ethoxy-2-propanol), propoxypropanol (eg 1-propoxy-2- Propanol), methoxybutanol (eg 1-methoxy-2-butanol, 1-methoxy-3-butanol), ethoxybutanol (eg 1-ethoxy-2-butanol, 1-ethoxy-3-butanol), methylpentanol (For example, 4-methyl-2-pentanol).
  • methoxypropanol eg 1-methoxy-2-propanol
  • ethoxypropanol eg 1-ethoxy-2-propanol
  • propoxypropanol eg 1-propoxy-2- Propanol
  • methoxybutanol eg 1-methoxy-2-butanol, 1-
  • the propylene glycol monoalkyl ether carboxylate is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate. It is particularly preferred.
  • propylene glycol monoalkyl ether propylene glycol monomethyl ether or propylene glycol monoethyl ether is preferable.
  • lactic acid ester ethyl lactate, butyl lactate or propyl lactate is preferable.
  • 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.
  • alkoxypropionate methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferable.
  • chain ketones include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, Acetonyl acetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone or methyl amyl ketone are preferred.
  • cyclic ketone methylcyclohexanone, isophorone or cyclohexanone is preferable.
  • lactone ⁇ -butyrolactone is preferable.
  • alkylene carbonate propylene carbonate is preferable.
  • an ester solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, more preferably 7 to 10) and a hetero atom number of 2 or less.
  • ester solvent having 7 or more carbon atoms and 2 or less hetero atoms include amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, butyl propionate, Examples thereof include isobutyl isobutyrate, heptyl propionate, and butyl butanoate, and it is particularly preferable to use isoamyl acetate.
  • a solvent having a flash point (hereinafter also referred to as fp) of 30 ° C. or higher.
  • fp a solvent having a flash point
  • examples of such components include propylene glycol monomethyl ether (fp: 47 ° C.), ethyl lactate (fp: 53 ° C.), ethyl 3-ethoxypropionate (fp: 49 ° C.), methyl amyl ketone (fp: 42 ° C.), Cyclohexanone (fp: 30 ° C.), pentyl acetate (fp: 45 ° C.), methyl 2-hydroxyisobutyrate (fp: 45 ° C.), ⁇ -butyrolactone (fp: 101 ° C.) or propylene carbonate (fp: 132 ° C.) is preferred.
  • propylene glycol monoethyl ether, ethyl lactate, pentyl acetate or cyclohexanone is more preferred, and propylene glycol monoethyl ether or ethyl lactate is particularly preferred.
  • solvents for the lower layer film water, 1-methoxy-2-propanol, propylene glycol monomethyl ether acetate (PGMEA), ethoxyethyl propionate, cyclohexanone, 2-heptanone, ⁇ -butyrolactone, butyl acetate, propylene At least one selected from the group consisting of glycol monomethyl ether (PGME), ethyl lactate and 4-methyl-2-pentanol, selected from the group consisting of 1-methoxy-2-propanol, PGMEA and butyl acetate At least one is more preferable.
  • a conventionally known storage container can be used as the storage container for the composition for forming an underlayer film for imprint.
  • the inner wall of the container is a multi-layer bottle composed of 6 types and 6 layers of resin, and 6 types of resins are made into a 7 layer structure. It is also preferred to use bottles that have been used. Examples of such a container include a container described in JP-A-2015-123351.
  • the curable composition for imprints preferably contains a polymerizable compound, and preferably contains a polymerizable compound having an aromatic ring.
  • the polymerizable compound may be a monofunctional polymerizable compound or a polyfunctional polymerizable compound. Moreover, it is preferable that both a monofunctional polymerizable compound and a polyfunctional polymerizable compound are included.
  • the molecular weight of the monofunctional polymerizable compound used in the curable composition for imprints is preferably 50 or more, more preferably 100 or more, and still more preferably 150 or more.
  • the molecular weight is preferably 1,000 or less, more preferably 800 or less, further preferably 300 or less, and even more preferably 270 or less. There exists a tendency which can suppress volatility by making molecular weight more than the said lower limit. By setting the molecular weight to the above upper limit or less, the viscosity tends to be reduced.
  • the boiling point of the monofunctional polymerizable compound used in the curable composition for imprints is preferably 85 ° C. or higher, more preferably 110 ° C.
  • the boiling point is not particularly defined, but for example, the boiling point can be 350 ° C. or lower.
  • the type of polymerizable group possessed by the monofunctional polymerizable compound used in the curable composition for imprints is not particularly defined, and examples thereof include ethylenically unsaturated groups and epoxy groups, with ethylenically unsaturated groups being preferred.
  • ethylenically unsaturated group a (meth) acryloyl group is preferable, and an acryloyl group is more preferable.
  • the type of atoms constituting the monofunctional polymerizable compound used in the curable composition for imprints is not particularly defined, but should be composed only of atoms selected from carbon atoms, oxygen atoms, hydrogen atoms and halogen atoms. Is preferable, and it is more preferably composed of only an atom selected from a carbon atom, an oxygen atom and a hydrogen atom.
  • a preferred first embodiment of the monofunctional polymerizable compound used in the curable composition for imprints is a compound having a linear or branched hydrocarbon chain having 4 or more carbon atoms.
  • the hydrocarbon chain in the present invention represents an alkyl chain, an alkenyl chain, or an alkynyl chain, preferably an alkyl chain or alkenyl chain, and more preferably an alkyl chain.
  • the alkyl chain represents an alkyl group and an alkylene group.
  • an alkenyl chain represents an alkenyl group and an alkenylene group
  • an alkynyl chain represents an alkynyl group and an alkynylene group.
  • a linear or branched alkyl group or an alkenyl group is more preferable, a linear or branched alkyl group is more preferable, and a linear alkyl group is more preferable.
  • the linear or branched hydrocarbon chain (preferably an alkyl group) has 4 or more carbon atoms, preferably 6 or more carbon atoms, more preferably 8 or more carbon atoms, still more preferably 10 or more carbon atoms, and more carbon atoms. 12 or more is more preferable.
  • the upper limit value of the carbon number is not particularly defined, but can be, for example, 25 or less.
  • the linear or branched hydrocarbon chain may contain an ether group (—O—), but preferably does not contain an ether group from the viewpoint of improving releasability.
  • a monofunctional polymerizable compound having a hydrocarbon chain By using such a monofunctional polymerizable compound having a hydrocarbon chain, the elastic modulus of the cured product (pattern) is reduced and the releasability is improved with a relatively small addition amount. Further, when a monofunctional polymerizable compound having a linear or branched alkyl group is used, the interfacial energy between the mold and the cured product (pattern) can be reduced, and the releasability can be further improved.
  • Linear alkyl group having 8 or more carbon atoms The linear alkyl group having 8 or more carbon atoms is more preferably one having 10 or more carbon atoms, further preferably 11 or more carbon atoms, and still more preferably 12 or more carbon atoms. Moreover, 20 or less carbon atoms are preferable, 18 or less carbon atoms are more preferable, 16 or less carbon atoms are more preferable, and 14 or less carbon atoms are still more preferable.
  • the branched alkyl group having 10 or more carbon atoms is preferably one having 10 to 20 carbon atoms, more preferably 10 to 16 carbon atoms, still more preferably 10 to 14 carbon atoms, More preferably, the number of carbon atoms is 10 to 12.
  • a linear or branched alkyl group having 1 or more carbon atoms is more preferably a linear alkyl group. preferable.
  • 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 alicyclic ring, aromatic ring or aromatic heterocyclic ring may be a monocyclic ring or a condensed ring, but is preferably a monocyclic ring.
  • the number of rings is preferably 2 or 3.
  • the ring is preferably a 3- to 8-membered ring, more preferably a 5-membered ring or a 6-membered ring, and even more preferably a 6-membered ring.
  • Specific examples of the ring include an example of the ring Cz described later.
  • the monofunctional polymerizable compound used in the curable composition for imprints is preferably a compound in which a linear or branched hydrocarbon chain having 4 or more carbon atoms and a polymerizable group are bonded directly or via a linking group.
  • a compound in which any one of the above groups (1) to (3) and a polymerizable group are directly bonded is more preferable.
  • Examples of the linking group include —O—, —C ( ⁇ O) —, —CH 2 —, or a combination thereof.
  • the monofunctional polymerizable compound used in the present invention includes (1) a linear alkyl (meth) acrylate in which a linear alkyl group having 8 or more carbon atoms and a (meth) acryloyloxy group are directly bonded. preferable.
  • the monofunctional polymerizable compound is preferably a compound represented by the following formula (I-1).
  • R 12 is an alkyl group (preferably having a carbon number of 1 to 36, preferably 1 to 30, more preferably 1 to 24), or an alicyclic ring (preferably having 3 to 24 carbon atoms, more preferably 3 to 12 carbon atoms). 6 is more preferred), an aromatic ring (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms) and an aromatic heterocyclic ring (preferably having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms). More preferably, it represents a group of at least one selected from 2-5, or a combination thereof.
  • R 11 represents a hydrogen atom or a methyl group.
  • L 11 represents a single bond or the linking group L, and is preferably an alkylene group or an alkenylene group.
  • R 12 and L 11 may combine with or without a linking group L to form a ring.
  • R 12 and L 11 may have the substituent T.
  • a plurality of substituents T may be bonded to form a ring, may be bonded to R 12 , or may be bonded to L 11 to form a ring. When there are a plurality of substituents T, they may be the same or different.
  • the preferred range of the alicyclic ring, aromatic ring or aromatic heterocyclic ring for R 12 is the same as ring Cz described later.
  • Examples of the monofunctional polymerizable compound of the first embodiment include the following first group and second group. However, it goes without saying that the present invention is not limited to these examples.
  • the first group is more preferable than the second group.
  • a preferred second embodiment of the monofunctional polymerizable compound used in the curable composition for imprints is a compound having a cyclic structure.
  • the cyclic structure is preferably a 3- to 8-membered monocyclic ring or condensed ring.
  • the number of rings constituting the fused ring is preferably 2 or 3.
  • the cyclic structure is more preferably a 5-membered ring or a 6-membered ring, and even more preferably a 6-membered ring.
  • a single ring is more preferable.
  • the number of cyclic structures in one molecule of the polymerizable compound may be one or two or more, but one or two is preferable, and one is more preferable. In the case of a condensed ring, the condensed ring is considered as one cyclic structure.
  • Examples of the monofunctional polymerizable compound according to the second embodiment include the following compounds. However, it goes without saying that the present invention is not limited to these examples. Of the compounds described in the first embodiment, compounds having a cyclic structure are also exemplified as preferred compounds of this embodiment.
  • a monofunctional polymerizable compound other than the above monofunctional polymerizable compound may be used as long as it does not depart from the spirit of the present invention, and monofunctional polymerizable compounds described in JP-A-2014-170949 can be used. Examples of the polymerizable compound are included in the present specification.
  • the content of the monofunctional polymerizable compound used in the curable composition for imprints with respect to the total polymerizable compound is preferably 6% by mass or more, more preferably 8% by mass or more, and even more preferably 10% by mass or more. 12 mass% or more is more preferable.
  • the content is more preferably 60% by mass or less, and may be 55% by mass or less.
  • only one monofunctional polymerizable compound may be contained, or two or more kinds may be contained. When 2 or more types are included, the total amount is preferably within the above range.
  • the polyfunctional polymerizable compound used in the curable composition for imprints is not particularly defined, but preferably contains at least one of an alicyclic ring, an aromatic ring and an aromatic heterocyclic ring. More preferably, it contains at least one heterocyclic ring.
  • 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 imprints is preferably 1,000 or less, more preferably 800 or less, further preferably 500 or less, and further preferably 350 or less. .
  • the upper limit of the molecular weight is not particularly defined, but can be, for example, 200 or more.
  • the number of polymerizable groups contained in the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints is 2 or more, preferably 2 to 7, more preferably 2 to 4, more preferably 2 or 3. 2 is more preferable.
  • the type of polymerizable group possessed by the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints is not particularly defined, but examples thereof include ethylenically unsaturated groups and epoxy groups. preferable.
  • ethylenically unsaturated group a (meth) acryloyl group is more preferable, and an acryloyl group is more preferable.
  • Two or more polymerizable groups may be contained in one molecule, or two or more polymerizable groups of the same type may be contained.
  • the type of atoms constituting the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints is not particularly defined, but is composed only of atoms selected from carbon atoms, oxygen atoms, hydrogen atoms and halogen atoms. It is preferable that it is composed only of atoms selected from a carbon atom, an oxygen atom and a hydrogen atom.
  • the ring contained in the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints may be monocyclic or condensed, but is preferably monocyclic.
  • the number of rings is preferably 2 or 3.
  • the ring is preferably a 3- to 8-membered ring, more preferably a 5-membered ring or a 6-membered ring, and even more preferably a 6-membered ring.
  • the ring may be an alicyclic ring, an aromatic ring or an aromatic heterocyclic ring, but is preferably an aromatic ring or an aromatic heterocyclic ring, more preferably an aromatic ring.
  • Specific examples of the ring include an example of the ring Cz.
  • the number of rings in the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints may be one or two or more, but preferably one or two, more preferably one. . In the case of a condensed ring, one condensed ring is considered.
  • the structure of the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints is (polymerizable group)-(single bond or divalent linking group)-(divalent group having a ring)-(single bond). Or a divalent linking group)-(polymerizable group).
  • the linking group is preferably an alkylene group, more preferably an alkylene group having 1 to 3 carbon atoms.
  • the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints is preferably represented by the following formula (I-2).
  • Q is an alicyclic ring (preferably having 3 to 24 carbon atoms, more preferably 3 to 12 carbon atoms, still more preferably 3 to 6 carbon atoms) or an aromatic ring (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 10 represents a 1 + q-valent group having at least one selected from 10 and more preferably an aromatic heterocyclic ring (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and further preferably 2 to 5 carbon atoms).
  • R 21 and R 22 each independently represents a hydrogen atom or a methyl group.
  • L 21 and L 22 each independently represent a single bond or the above linking group L.
  • Q and L 21 or L 22 may combine with or without a linking group L to form a ring.
  • Q, L 21 and L 22 may have the substituent T.
  • a plurality of substituents T may be bonded to form a ring, may be bonded to Q, or may be bonded to L 21 or L 22 to form a ring.
  • When there are a plurality of substituents T they may be the same or different.
  • the preferable range of the alicyclic ring, aromatic ring or aromatic heterocyclic ring in Q includes ring Cz described later.
  • q is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1.
  • Q has 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 connected. You may do it.
  • Examples of the structure in which the aromatic rings are linked include the structures of the above formulas Ar1 to Ar5.
  • Examples of the polyfunctional polymerizable compound used in the curable composition for imprints include the following first group and second group. However, it goes without saying that the present invention is not limited to these examples.
  • the first group is more preferable.
  • the curable composition for imprints may contain a polyfunctional polymerizable compound other than the ring-containing polyfunctional polymerizable compound.
  • a polyfunctional polymerizable compound other than the ring-containing polyfunctional polymerizable compound.
  • compounds represented by the following formula (I-3) are preferable.
  • L 30 is a group having a linear or branched alkane structure (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and further preferably 1 to 3), or a group having a linear or branched alkene structure (having 2 carbon atoms).
  • To 12 are preferable, 2 to 6 are more preferable, and 2 to 3 are more preferable.
  • a linear or branched alkyne structure group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6, more preferably 2 to 3).
  • R 25 and R 26 each independently represents a hydrogen atom or a methyl group.
  • L 25 and L 26 each independently represent a single bond or the above linking group L.
  • L 30 and L 25 or L 26 may combine with or without a linking group L to form a ring.
  • L 25 , L 26 and L 30 may have the substituent T.
  • a plurality of substituents T may be bonded to form a ring, or may be bonded to another linking group to form a ring. When there are a plurality of substituents T, they may be the same or different.
  • r is an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1.
  • a hetero linking group (O, S, NR N ) may be interposed in L 30 .
  • the number of intervening hetero linking group is preferably a rate of one having 1 to 6 carbon atoms, L 30.
  • Examples of other polyfunctional polymerizable compounds used in the curable composition for imprints include polyfunctional polymerizable compounds having no ring among the polymerizable compounds described in JP-A No. 2014-170949. Is included herein. More specifically, for example, the following compounds are exemplified.
  • the ring Cz examples include the following aromatic rings, aromatic heterocyclic rings and alicyclic rings.
  • the aromatic ring contained in the compound containing an aromatic ring is preferably one having 6 to 22 carbon atoms, more preferably 6 to 18 and even more preferably 6 to 10.
  • Specific examples of the aromatic ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, phenalene ring, fluorene ring, acenaphthylene ring, biphenylene ring, indene ring, indane ring, triphenylene ring, pyrene ring, chrysene ring, perylene ring.
  • the aromatic ring may have a structure in which a plurality of aromatic rings are connected, and examples thereof include a biphenyl ring and a bisphenyl ring.
  • the aromatic heterocyclic ring preferably has 1 to 12 carbon atoms, more preferably 1 to 6 and even more preferably 1 to 5.
  • thiophene ring examples include thiophene ring, furan ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, oxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, isoindole ring, indole.
  • the alicyclic ring preferably has 3 to 22 carbon atoms, more preferably 4 to 18 and even more preferably 6 to 10.
  • cyclopropane ring examples include cyclopropane ring, cyclobutane ring, cyclobutene ring, cyclopentane ring, cyclohexane ring, cyclohexene ring, cycloheptane ring, cyclooctane ring, dicyclopentadiene ring, tetrahydrodicyclopentadiene ring, octahydronaphthalene ring, Examples include a decahydronaphthalene ring, a hexahydroindane ring, a bornane ring, a norbornane ring, a norbornene ring, an isobornane ring, a tricyclodecane ring, a tetracyclododecane ring, and an adamantane ring.
  • the polyfunctional polymerizable compound is preferably contained in an amount of 30% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, based on the total polymerizable compound in the curable composition for imprints. 55 mass% or more is still more preferable, 60 mass% or more may be sufficient, and 70 mass% or more may be sufficient. Moreover, it is preferable that an upper limit is less than 95 mass%, it is further more preferable that it is 90 mass% or less, and it can also be 85 mass% or less.
  • the curable composition for imprints may contain only one type of polyfunctional polymerizable compound or two or more types. When 2 or more types are included, the total amount is preferably within the above range.
  • 85% by mass or more of the composition is preferably a polymerizable compound, more preferably 90% by mass or more is a polymerizable compound, and 93% by mass or more. More preferably, it is a polymerizable compound.
  • the dispersion term component (component d) is preferably 14.0 to 20.0, more preferably 15.0 to 19.0, and more preferably 16.0 to 18.5. Even more preferred;
  • the polar term component (p component) is preferably 3.5 to 8.0, more preferably 3.8 to 6.0, and 4.0 to 5.0. Even more preferred;
  • the hydrogen bond term component (component h) is preferably 4.0 to 8.0, more preferably 4.7 to 7.0, and 5.2 to 6.5. Is more preferable.
  • the dispersion term component, polar term component, and hydrogen bond term component of the HSP vector of the curable composition for imprints are set by the methods described in the examples described later.
  • the curable composition for imprints may contain additives other than the polymerizable compound.
  • additives include a polymerization initiator, a surfactant, a sensitizer, a release agent, an antioxidant, a polymerization inhibitor and the like.
  • Specific examples of the curable composition for imprints that can be used in the present invention include the compositions described in JP2013-036027A, JP2014-090133A, and JP2013-189537A. The contents of which are incorporated herein. The description of the above publication can be referred to for the preparation of the curable composition for imprints and the method for forming the film (pattern forming layer), and the contents thereof are incorporated in the present specification.
  • the viscosity of the curable composition for imprints 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, It may be 9.0 mPa ⁇ s or less. Although it does not specifically limit as a lower limit of the said viscosity, For example, it can be 4.0 mPa * s or more, Furthermore, it can be 5.0 mPa * s or more.
  • the surface tension ( ⁇ Resist) of the curable composition for imprints is preferably 29.0 mN / m or more, more preferably 30.0 mN / m or more, and further preferably 31.0 mN / m or more. preferable.
  • the upper limit of the surface tension is not particularly limited, but it is preferably 42.0 mN / m or less from the viewpoint of imparting the relationship with the lower layer film and inkjet suitability. More preferably, it may be 38.0 mN / m or less.
  • the Onishi parameter of the curable composition for imprints is preferably 5.0 or less, more preferably 4.0 or less, and still more preferably 3.7 or less.
  • the lower limit value of the Onishi parameter of the curable composition for imprints is not particularly defined, but may be, for example, 1.0 or more, or 2.0 or more.
  • the Onishi parameter can be obtained by substituting the numbers of carbon atoms, hydrogen atoms, and oxygen atoms of all constituent components into the following formulas for the polymerizable compound of the curable composition for imprints.
  • Onishi parameter sum of the number of carbon, hydrogen and oxygen atoms / (number of carbon atoms-number of oxygen atoms)
  • the Hansen Solubility Parameter (HSP) vector of the polymerizable compound contained in the curable composition for imprints (I)
  • the dispersion term component (component d) is preferably 14.0 to 20.0, more preferably 15.0 to 19.0, and more preferably 16.0 to 18.5. Even more preferred;
  • the polar term component (p component) is preferably 3.5 to 8.0, more preferably 3.8 to 6.0, and 4.0 to 5.0. Even more preferred;
  • the hydrogen bond term component (component h) is preferably 4.0 to 8.0, more preferably 4.7 to 7.0, and 5.2 to 6.5. Is more preferable.
  • the dispersion term component, polar term component, and hydrogen bond term component of the HSP vector are each set by the method described in the examples described later.
  • the content of the solvent in the curable composition for imprints is preferably 5% by mass or less of the curable composition for imprints, more preferably 3% by mass or less, and 1% by mass. More preferably, it is as follows.
  • the curable composition for imprints is a polymer (preferably a polymer having a weight average molecular weight of more than 1,000, more preferably a weight average molecular weight of more than 2,000, and still more preferably a weight average molecular weight of 10,000 or more. ) May not be substantially contained. “Containing substantially no polymer” means, for example, that the polymer content is 0.01% by mass or less of the curable composition for imprints, preferably 0.005% by mass or less, and not contained at all. Is more preferable.
  • the container for the curable composition for imprints used in the present invention a conventionally known container can be used.
  • the inner wall of the container is a multi-layer bottle composed of 6 types and 6 layers of resin, and 6 types of resins are made into a 7 layer structure. It is also preferred to use bottles that have been used. Examples of such a container include a container described in JP-A-2015-123351.
  • the present invention discloses a kit comprising a composition for forming an underlayer film for imprinting and a curable composition for imprinting containing a polymerizable compound.
  • the kit of the present invention comprises a Hansen solubility parameter of a desorbing component (a compound represented by formula (r1) or (r2) or a compound represented by formula (r1-1)) and Hansen of a curable composition for imprints.
  • the ⁇ HSP value calculated by the following mathematical formula (H1) based on the solubility parameter is preferably 5 or less, more preferably 7.0 or less, further preferably 5.0 or less, and 4.0. More preferably, it is as follows. The lower limit may be 0, but is practically 0.1 or more.
  • ⁇ HSP (4.0 ⁇ ⁇ D 2 + ⁇ P 2 + ⁇ H 2 ) 0.5 (H1)
  • ⁇ D is the difference between the dispersion term component of the Hansen solubility parameter vector of the curable composition for imprints and the dispersion term component of the Hansen solubility parameter vector of the elimination component.
  • ⁇ P is the difference between the polar term component of the Hansen solubility parameter vector of the curable composition for imprints and the polar term component of the Hansen solubility parameter vector of the elimination component.
  • ⁇ H is the difference between the hydrogen bond term component of the Hansen solubility parameter vector of the imprint curable composition and the hydrogen bond term component of the Hansen solubility parameter vector of the desorption component.
  • a preferred embodiment of the kit of the present invention includes a laminate formed from the kit.
  • the laminate of the present embodiment comprises an underlayer film formed from the above-described imprint underlayer film-forming composition, and an imprint layer formed from the above-mentioned curable composition for imprints and located on the surface of the underlayer film. It is preferable to have.
  • the manufacturing method is not particularly limited, a manufacturing method including applying the curable composition for imprints to the surface of the lower layer film formed from the lower layer film forming composition for imprints using the kit described above. Can be mentioned.
  • the curable composition for imprints is preferably applied to the surface of the lower layer film by an inkjet method (IJ method).
  • the method for producing a laminate includes a step of applying the above-described imprint lower layer film-forming composition in a layer form on a substrate. Preferably includes heating (baking) at 150 to 250 ° C. (process temperature).
  • a method for producing a cured product pattern according to a preferred embodiment of the present invention is a method for producing a cured product pattern using the above-described kit, wherein a lower layer film-forming composition for imprinting is applied to a lower layer on a substrate.
  • An underlayer film forming step of forming a film An application step of applying the curable composition for imprints to the surface of the underlayer film, the curable composition for imprints, and a pattern for transferring the pattern shape
  • a method for forming a cured product pattern (a method for producing a cured product pattern) will be described with reference to FIG. It goes without saying that the configuration of the present invention is not limited by the drawings.
  • Lower layer formation process the lower layer film 2 is formed on the substrate 1 as shown in FIGS. 1 (1) and (2).
  • the lower layer film is preferably formed by applying the lower film forming composition for imprinting in a layer form on the substrate.
  • the application method of the composition for forming an underlayer film for imprinting on the substrate is not particularly defined, and generally known application methods can be employed. Specifically, as an application method, for example, dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spin coating method, slit scanning method, or ink jet method And a spin coating method is preferable. Moreover, after applying the lower film
  • the thickness of the lower layer film 2 is preferably 2 nm or more, more preferably 3 nm or more, further preferably 4 nm or more, and may be 5 nm or more, or 7 nm or more. Further, the thickness of the lower layer film is preferably 40 nm or less, more preferably 30 nm or less, further preferably 20 nm or less, may be 15 nm or less, and further 10 nm or less. Also good.
  • the expandability (wetting property) on the lower layer film of the curable composition for imprinting is improved, and a uniform residual film after imprinting can be formed.
  • the remaining film after imprinting becomes thin, film thickness unevenness hardly occurs, and the remaining film uniformity tends to be improved.
  • a silicon substrate is not particularly defined, and the description in paragraph 0103 of JP 2010-109092 A (the publication number of the corresponding US application is US Patent Application Publication No. 2011/0183127) can be referred to. Is incorporated herein by reference.
  • the curable composition 3 for imprinting is applied to the surface of the lower layer film 2.
  • the method for applying the curable composition for imprints is not particularly defined, and paragraph 0102 of JP 2010-109092 A (the publication number of the corresponding US application is US Patent Application Publication No. 2011/0199592). The contents of which are incorporated herein by reference.
  • the curable composition for imprints is preferably applied to the surface of the lower layer film by an inkjet method. Moreover, you may apply
  • the amount of the droplets is preferably about 1 to 20 pL, and it is preferable to dispose the droplets on the surface of the lower layer film with an interval between the droplets.
  • the interval between the droplets is preferably 10 to 1000 ⁇ m.
  • the liquid drop interval is the arrangement interval of the ink jet nozzles.
  • the volume ratio of the lower film 2 and the film-like curable composition for imprint 3 applied on the lower film is preferably 1: 1 to 500, more preferably 1:10 to 300. A ratio of 1:50 to 200 is more preferable.
  • the manufacturing method of the laminated body which concerns on preferable embodiment of this invention is a method of manufacturing using the kit of this invention, Comprising: On the surface of the lower layer film formed from the said lower layer film formation composition for imprints, Applying a curable composition for imprints.
  • the manufacturing method of the laminated body which concerns on preferable embodiment of this invention includes the process of applying the said underlayer film formation composition for imprints on a board
  • Mold contact process For example, as shown in FIG. 1 (4), the curable composition for imprints 3 is brought into contact with the mold 4 having a pattern for transferring the pattern shape. Through such a process, a desired cured product pattern (imprint pattern) is obtained. Specifically, in order to transfer a desired pattern to the film-shaped curable composition for imprints, the mold 4 is pressed against the surface of the film-shaped curable composition for imprints 3.
  • the mold may be a light transmissive mold or a light non-transmissive mold.
  • a light-transmitting mold it is preferable to irradiate the curable composition 3 for imprinting with light from the mold side.
  • a light-impermeable mold it is preferable to use a light-transmitting substrate as the substrate and irradiate light from the substrate side.
  • a light transmissive mold and irradiate light from the mold side is more preferable to use.
  • the mold that can be used in the present invention is a mold having a pattern to be transferred.
  • the mold pattern manufacturing method in particular is not restrict
  • cured material pattern manufacturing method which concerns on preferable embodiment of this invention can also be used as a mold.
  • the material constituting the light-transmitting mold used in the present invention is not particularly limited, but includes a light-transmitting resin such as glass, quartz, polymethyl methacrylate (PMMA), and polycarbonate resin, a transparent metal vapor-deposited film, and polydimethylsiloxane. Examples thereof include a flexible film, a photocured film, and a metal film, and quartz is preferable.
  • the non-light-transmitting mold material used when a light-transmitting substrate is used is not particularly limited as long as it has a predetermined strength.
  • Specific examples include ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, and substrates such as SiC, silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon. There are no particular restrictions.
  • the mold pressure is preferably selected from a range in which the residual film of the curable composition for imprint hitting the mold convexity is reduced while ensuring the uniformity of mold transfer.
  • the curable composition for imprints is irradiated with light to form a cured product.
  • the irradiation amount of light irradiation in the light irradiation step may be sufficiently larger than the minimum irradiation amount necessary for curing.
  • the amount of irradiation necessary for curing is appropriately determined by examining the consumption of unsaturated bonds of the curable composition for imprints.
  • an ultraviolet light is illustrated.
  • the substrate temperature at the time of light irradiation is usually room temperature, but light irradiation may be performed while heating in order to increase the reactivity.
  • a pre-stage of light irradiation if it is in a vacuum state, it is effective in preventing bubble mixing, suppressing the decrease in reactivity due to oxygen mixing, and improving the adhesion between the mold and the curable composition for imprinting. It may be irradiated with light.
  • a preferable degree of vacuum at the time of light irradiation is in the range of 10 ⁇ 1 Pa to normal pressure.
  • the exposure illuminance is preferably in the range of 1 to 500 mW / cm 2 , and more preferably in the range of 10 to 400 mW / cm 2 .
  • the exposure time is not particularly limited, but is preferably 0.01 to 10 seconds, and more preferably 0.5 to 1 second.
  • Exposure amount is preferably in a range of 5 ⁇ 1000mJ / cm 2, and more preferably in the range of 10 ⁇ 500mJ / cm 2.
  • the film-shaped curable composition for imprints is cured by light irradiation, and then is further cured by applying heat to the cured pattern as necessary. A process may be included.
  • the temperature for heat-curing the curable composition for imprints after light irradiation is preferably 150 to 280 ° C, more preferably 200 to 250 ° C.
  • the time for applying heat is preferably 5 to 60 minutes, more preferably 15 to 45 minutes.
  • the cured product and the mold are separated (FIG. 1 (5)).
  • the obtained cured product pattern can be used for various applications as described later. That is, in this invention, the laminated body which has further the hardened
  • the cured product pattern formed by the method for producing a cured product pattern is used as a permanent film used for a liquid crystal display (LCD) or the like, or as an etching resist (lithography mask) for manufacturing a semiconductor element.
  • the present invention discloses a circuit board manufacturing method including a step of obtaining a cured product pattern by a cured product pattern manufacturing method according to a preferred embodiment of the present invention.
  • the step of performing etching or ion implantation on the substrate using the cured product pattern obtained by the method for manufacturing a cured product pattern as a mask, and the formation of the electronic member are formed. You may have a process.
  • the circuit board is preferably a semiconductor element.
  • the present invention discloses a method for manufacturing an electronic device, which includes a step of obtaining a circuit board by the method for manufacturing a circuit board, and a step of connecting the circuit board and a control mechanism for controlling the circuit board.
  • a grid pattern is formed on the glass substrate of the liquid crystal display device using the pattern formed by the above-described cured product pattern manufacturing method, and polarized light having a large screen size (for example, 55 inches or more than 60 inches) with little reflection and absorption. It is possible to manufacture the plate at a low cost. For example, a polarizing plate described in JP-A-2015-132825 and International Publication No. 2011-132649 can be produced. One inch is 25.4 mm.
  • the cured product pattern formed in the present invention is also useful as an etching resist (lithographic mask) as shown in FIGS.
  • the cured product pattern As an etching resist, first, for example, a silicon substrate (such as a silicon wafer) on which a thin film such as SiO 2 is formed as a substrate, and the cured product pattern manufacturing method on the substrate, for example, A fine cured material pattern of nano or micron order is formed.
  • a nano-order fine pattern can be formed, and a pattern having a size of 50 nm or less, particularly 30 nm or less can be formed.
  • the lower limit of the size of the cured product pattern formed by the cured product pattern manufacturing method is not particularly defined, but can be, for example, 1 nm or more.
  • a method for producing an imprint mold comprising: a step of obtaining a cured product pattern by a method of producing a cured product pattern on a substrate; and a step of etching the substrate using the obtained cured product pattern.
  • a desired cured product pattern can be formed on the substrate by etching using an etching gas such as hydrogen fluoride in the case of wet etching or CF 4 in the case of dry etching.
  • the cured product pattern has particularly good etching resistance against dry etching. That is, the pattern formed by the cured product pattern manufacturing method is preferably used as a lithography mask.
  • FIG. 2 is a plan view schematically showing a wet spread state of the curable composition for imprints when the curable composition for imprints is applied to the surface of the lower layer film by an inkjet method.
  • IJ inkjet
  • droplets of the curable composition for imprints 22 are dropped on the surface of the lower layer film 21 at equal intervals.
  • FIG. 2A When the mold is brought into contact therewith, the droplets spread on the lower layer film 21 and become film-shaped curable compositions for imprints 22a, 22b, 22c (FIGS. 2B, 2C, 2C). (D)).
  • the state of the curable composition for imprints 22b is completely on the lower layer film 21.
  • a film that does not spread is formed. That is, a region 23 having a thin film thickness or no film may be generated. If it becomes like this, the part in which the curable composition for imprints is not fully filled will arise in the pattern of a mold, and the part without a pattern will be made in an imprint layer. For example, when etching is performed using a pattern of an imprint layer having a defect or an insufficiently thick portion in such a part as a mask, a thin region or a region 23 without a film and another region 22b.
  • the lower layer film forming composition for imprints of the present invention the interfacial tension between the lower layer film formed thereby and the curable composition for imprints is improved, and the wettability is improved. Therefore, the curable composition for imprint 22c is more reliably spread to every corner of the state of FIG. As a result, the curable composition for imprints can be filled in the mold accurately and sufficiently, and good patterning with uniform thickness can be achieved in the formed imprint layer. In addition, the improvement of filling property enables high-speed imprinting, which can lead to an improvement in throughput.
  • the pattern formed in the present invention includes a recording medium such as a magnetic disk, a light receiving element such as a solid-state image sensor, a light emitting element such as an LED (light emitting diode) or an organic EL (organic electroluminescence), a liquid crystal display.
  • a recording medium such as a magnetic disk
  • a light receiving element such as a solid-state image sensor
  • a light emitting element such as an LED (light emitting diode) or an organic EL (organic electroluminescence)
  • a liquid crystal display such as a magnetic disk
  • a light receiving element such as a solid-state image sensor
  • a light emitting element such as an LED (light emitting diode) or an organic EL (organic electroluminescence)
  • a liquid crystal display such as a liquid crystal display.
  • Optical devices such as devices (LCD), optical components such as diffraction gratings, relief holograms, optical waveguides, optical filters, microlens arrays, thin film transistors, organic transistors, color filters, antireflection films, polarizing plates, polarizing elements, optical films, Flat panel display members such as pillars, nanobiodevices, immunoassay chips, deoxyribonucleic acid (DNA) separation chips, microreactors, photonic liquid crystals, micropattern formation using self-assembly of block copolymers (directed self-assembly, DSA) It can be preferably used in the preparation of the guide pattern, etc. for.
  • LCD liquid crystals
  • DSA directed self-assembly
  • Tetrahydrofuran (THF) (300 g) and G-1A (10 g) are added to a three-necked flask with N 2 flow, cooled to 0 ° C., and LiAlH 4 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., 3 g) is gradually added. In addition, aging was performed for 2 hours. Thereafter, water (3 g), a 15% aqueous sodium hydroxide solution (3 g) and water (9 g) were added and aged for 1 hour. Then, the target compound (intermediate G-1B) was synthesized by filtering and concentrating the filtrate.
  • G-1D (10 g) and cyclohexane (100 g) were added to a three-necked flask with N 2 flow, cooled to 0 ° C., and a 20% butyl lithium cyclohexane solution (Tokyo Chemical Industry Co., Ltd., 12 mL) was added dropwise. Aged for time. Thereafter, methacrylic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd., 3 g) was added dropwise and aging was performed for 1 hour. Thereafter, THF (100 g) and 1M HCl aqueous solution were added, and aging was performed for 5 hours.
  • PGMEA (30 g) was added to a three-necked flask with N 2 flow and heated to 60 ° C.
  • 2-Hydroxyethyl Methacrylate (Tokyo Chemical Industry Co., Ltd., 13 g, 100 mmol)
  • G-1E 26 g, 100.0 mmol
  • photo radical polymerization initiator (Fuji Film Wako Pure Chemical Industries, Ltd., V-65, 1) 0.0 g, 4.0 mmol) was dissolved in PGMEA (70 g), and the resulting mixture was added dropwise over 2 hours at a temperature where the internal temperature of the flask did not exceed 65 ° C., followed by aging at 90 ° C. for 4 hours. It was.
  • PGMEA 45.38 g
  • intermediate G-1F (19.7 g, 100.0 mmol)
  • triethylamine manufactured by Tokyo Chemical Industry Co., Ltd., 15 g, 150.0 mmol
  • PGMEA 45.38 g
  • Acryloy Chylide 14 g, 150.0 mmol
  • composition for forming lower layer film Each component is blended as shown in Tables 1 to 4 below, and two-stage filtration is performed with a polytetrafluoroethylene (PTFE) filter having a pore size of 0.1 ⁇ m and a UPE filter (ultra high molecular weight polyethylene) having a pore size of 0.003 ⁇ m.
  • PTFE polytetrafluoroethylene
  • UPE ultra high molecular weight polyethylene
  • a composition for forming a lower layer film for imprinting was spin-coated on a silicon wafer (diameter 8 inches). Then, it heated using the hotplate on baking conditions of 80 degreeC and the air atmosphere for 3 minutes, and formed the lower layer film
  • the obtained lower layer film was immersed in tetrahydrofuran (THF) for 30 minutes, and the obtained THF solution was analyzed using LC / MS.
  • THF tetrahydrofuran
  • curable composition for imprint Each compound shown in Table 5 was mixed, and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical (manufactured by Tokyo Chemical Industry) as a polymerization inhibitor was further polymerized among the compounds shown in the table.
  • the curable composition for imprints was obtained by adding 200 mass ppm (0.02 mass%) to the total amount of the functional compound. This was two-stage filtered through a polytetrafluoroethylene (PTFE) filter having a pore size of 0.1 ⁇ m and a UPE (ultra high molecular weight polyethylene) filter having a pore size of 0.003 ⁇ m.
  • PTFE polytetrafluoroethylene
  • ⁇ Surface tension> The surface tension was measured at 23 ° C. using a surface tension meter SURFACETENSOMETER CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd. using a glass plate. The unit is indicated by mN / m. Two samples were prepared for each level, measured three times each, and a total of six arithmetic average values were adopted as evaluation values.
  • ⁇ HSP Hansen solubility parameter
  • ⁇ HSP (4.0 ⁇ ⁇ D 2 + ⁇ P 2 + ⁇ H 2 ) 0.5 (H1)
  • the Hansen solubility parameter when there are a plurality of compounds in each calculation target component (for example, when there are two or more desorption components), the value of the most abundant component (mass basis) among the corresponding compounds is adopted. In addition, when there are two or more kinds of the most abundant components, the average value is determined according to the mixing ratio.
  • Tables 1 to 4 show the distance ( ⁇ HSP) of the Hansen solubility parameter between the desorbing component and the curable composition calculated by the formula (H1).
  • the weight average molecular weight (Mw) of the polymer was defined as a polystyrene equivalent value according to gel permeation chromatography (GPC measurement).
  • the apparatus used was HLC-8220 (manufactured by Tosoh Corporation), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation) were used as columns.
  • THF tetrahydrofuran
  • a UV ray (ultraviolet) wavelength 254 nm detector was used.
  • a composition for forming a lower layer film for imprinting was spin-coated on a silicon wafer (diameter 8 inches). Then, it heated using the hotplate on baking conditions of 150 degreeC and the air atmosphere for 3 minutes, and formed the lower layer film
  • the curable composition for imprints adjusted to a temperature of 23 ° C. was ejected with a droplet amount of 1 pL per nozzle using an inkjet printer DMP-2831 manufactured by Fujifilm Dimatics, Inc.
  • a quartz mold (rectangular line / space pattern (1/1), line width 40 nm, groove depth 100 nm, line edge roughness 3.5 nm) is placed thereon so as to be in contact with the curable composition layer for imprinting, and a quartz wafer From the side, exposure was performed at 300 mJ / cm 2 using a high-pressure mercury lamp. After the exposure, the quartz wafer was separated and the peeling force at that time was measured. This peeling force corresponds to the adhesion force F (unit: N).
  • the peeling force was measured according to the method for measuring the peeling force described in Comparative Examples described in paragraph numbers 0102 to 0107 of JP 2011-209777 A. That is, it was performed according to the peeling steps 1 to 6 and 16 to 18 in FIG. A: F ⁇ 45N B: 45N> F ⁇ 30N C: 30N> F ⁇ 20N D: 20N> F
  • a composition for forming a lower layer film for imprinting was spin-coated on a silicon wafer (diameter 8 inches). Thereafter, heating was performed using a hot plate at 150 ° C. for 3 minutes under baking conditions in an air atmosphere to form a lower layer film on the adhesion layer. The thickness of the obtained lower layer film was about 10 nm.
  • the curable composition for imprints adjusted to a temperature of 23 ° C. was ejected with a droplet amount of 1 pL per nozzle using an inkjet printer DMP-2831 manufactured by Fujifilm Dimatics, Inc.
  • T-1, T-4, T-5, T-6 and T-7 are photoacid generators.
  • T-2 is a thermal base generator.
  • T-3 is a thermal acid generator.
  • the underlayer film forming composition for imprints of the present invention contains a polymer that desorbs a specific desorbing component, and when used in combination with the curable composition for imprints. It was found that excellent wettability and good adhesion were exhibited (Examples 1 to 21). On the other hand, it was found that if the desorbing component does not desorb, or even if the desorbing component desorbs, it does not take a specific chemical structure and is inferior in wettability or wettability (Comparative Examples 1 to 3).
  • a quartz mold having a pattern with a width of 500 nm was brought into contact with the film of the curable composition for imprints produced in each example. Thereafter, the film was cured by irradiating ultraviolet rays from the mold side. Subsequently, the mold was pulled apart to obtain a cured product pattern to which the mold pattern was transferred. As a result, it was confirmed that a good pattern could be formed in any cured product.

Abstract

An underlayer film forming composition for imprinting, which contains a polymer and a solvent, and which is configured such that if this underlayer film forming composition is formed into a film and baked at 80°C, a specific compound that has a molecular weight of 210 or more is separated from the polymer. The present invention also relates to: a curable composition for imprinting, which is relevant to this underlayer film forming composition for imprinting; and a kit which uses this underlayer film forming composition for imprinting or this curable composition for imprinting.

Description

インプリント用下層膜形成組成物、インプリント用硬化性組成物、キットImprint underlayer film forming composition, imprint curable composition, kit
　本発明は、インプリント用下層膜形成組成物、インプリント用硬化性組成物、キットの提供に関する。 The present invention relates to the provision of an underprint film forming composition for imprinting, a curable composition for imprinting, and a kit.
　インプリント法は、モールドを硬化性の組成物に押しつけ、組成物を硬化させた後、モールドを剥離することで微細なパターンを転写するものである。この方法を、半導体集積回路の製造などの精密加工分野に応用する試みが進められている。インプリント法により、ステッパーや電子ビームなどの高価な微細加工装置が不要となる。製造原価を下げ、プロセスが簡便で、高解像度、高スループットが実現できるため、様々な分野でデバイスの量産化に向けた研究が精力的に行われている。 The imprint method is to transfer a fine pattern by pressing a mold against a curable composition, curing the composition, and then peeling the mold. Attempts have been made to apply this method to the field of precision processing such as the manufacture of semiconductor integrated circuits. The imprint method eliminates the need for expensive fine processing devices such as steppers and electron beams. Since the manufacturing cost is reduced, the process is simple, and high resolution and high throughput can be realized, research for mass production of devices is being actively conducted in various fields.
　インプリント法において、パターニングに適用する材料として感光性樹脂組成物を用い、光透過性のモールドを組み合わせて加工する技術がある。この製造方法では、モールドを介して光を照射することで基板に配設した感光性樹脂組成物の硬化膜にパターンを形成し、それを絶縁部材としたり、さらに加工するためのマスクにしたりする。照射する光として紫外線（ＵＶ：Ultraviolet）を用いるものを、特にＵＶナノインプリント法と呼ぶことがある。このＵＶナノインプリント法をはじめとした光ナノインプリント法では、熱硬化性樹脂組成物を用い加熱を必要とする熱ナノインプリント法と異なり、室温での加工が可能となる。そのため、熱をきらう半導体デバイスなどの製造において高品質を実現する技術として広く対応することができる。 In the imprint method, there is a technique in which a photosensitive resin composition is used as a material applied for patterning and processing is performed by combining a light-transmitting mold. In this manufacturing method, a pattern is formed on the cured film of the photosensitive resin composition disposed on the substrate by irradiating light through a mold, and this is used as an insulating member or as a mask for further processing. . What uses ultraviolet (UV) as light to irradiate may be called especially the UV nanoimprint method. In the optical nanoimprinting method including the UV nanoimprinting method, processing at room temperature is possible, unlike the thermal nanoimprinting method that requires heating using a thermosetting resin composition. Therefore, it can be widely applied as a technique for realizing high quality in the manufacture of semiconductor devices and the like that dissipate heat.
　感光性樹脂組成物を用いた光ナノインプリント法において、下層膜を利用する技術が提案されている（特許文献１参照）。例えば、特許文献１では、（メタ）アクリロイルオキシ基とアルコキシカルボニル基とオキシラニル基およびオキセタニル基から選択される少なくとも１種の基とを有する樹脂と、ノニオン性界面活性剤と、溶剤とを含有する下層膜形成用樹脂組成物が開示されている。これにより、モールド押圧後の残膜厚みのばらつきが小さく、加圧後のパターンの線幅分布にばらつきが生じにくくなると記載されている。 In the optical nanoimprint method using a photosensitive resin composition, a technique using a lower layer film has been proposed (see Patent Document 1). For example, Patent Document 1 contains a resin having at least one group selected from a (meth) acryloyloxy group, an alkoxycarbonyl group, an oxiranyl group, and an oxetanyl group, a nonionic surfactant, and a solvent. A resin composition for forming an underlayer film is disclosed. Accordingly, it is described that the variation in the residual film thickness after pressing the mold is small, and the variation in the line width distribution of the pattern after pressing is less likely to occur.
国際公開第２０１６／０２７８４３号International Publication No. 2016/027843
　上述のように、フォトリソグラフィによる技術に比し、インプリントによる微細パターンの形成はきわめて効率がよく、半導体デバイスの製造に係る製造原価および生産性を大幅に改善することができる。そして、半導体技術の進歩に伴い、パターンの微細化や製造品質においてさらなる改善が求められている。例えば、インプリントによる製造過程においては、基板とインプリント用硬化性組成物の密着性を高めるため、インプリント用下層膜形成組成物を用い、上記インプリント用下層膜形成組成物の塗膜の表面に、インプリント用硬化性組成物を適用して膜を形成することが検討されているが、その膜の濡れ性について、さらなる向上の要求がある。また、当然にこれらの組成物から形成される下層膜とインプリント層の密着性も求められる。
　そこで、本発明は、インプリント用下層膜形成組成物の塗膜に対するインプリント用硬化性組成物の濡れ性により優れ、かつ、これらの組成物から形成される下層膜とインプリント層の密着性に優れた、インプリント用下層膜形成組成物、インプリント用硬化性組成物、およびこれらを用いたキットの提供を目的とする。 As described above, the formation of a fine pattern by imprinting is extremely efficient as compared with the technique by photolithography, and the manufacturing cost and productivity for manufacturing a semiconductor device can be greatly improved. As semiconductor technology advances, further improvements in pattern miniaturization and manufacturing quality are required. For example, in the manufacturing process by imprinting, in order to increase the adhesion between the substrate and the curable composition for imprinting, the lower film forming composition for imprinting is used, and the coating film of the lower film forming composition for imprinting is used. Although it has been studied to apply a curable composition for imprints to a surface to form a film, there is a demand for further improvement of the wettability of the film. Naturally, the adhesion between the underlayer film formed from these compositions and the imprint layer is also required.
Therefore, the present invention is superior in the wettability of the curable composition for imprints to the coating film of the underlayer film forming composition for imprints, and the adhesion between the underlayer film and the imprint layer formed from these compositions. It is an object of the present invention to provide an underprint film forming composition for imprinting, a curable composition for imprinting, and a kit using these.
　上記課題のもと、本発明者らが検討を行った結果、インプリント用下層膜形成組成物において特定の脱離成分を生じうるポリマーを採用することにより、上記課題を解決しうることを見出した。具体的には、下記手段＜１＞により、好ましくは＜２＞～＜２７＞により、上記課題は解決された。
＜１＞　ポリマーと溶剤とを含むインプリント用下層膜形成組成物であって、上記インプリント用下層膜形成組成物を膜状にし、８０℃でベークした場合、上記ポリマーから下記式（ｒ１）または（ｒ２）で表され、かつ、分子量が２１０以上である化合物が脱離する、インプリント用下層膜形成組成物；
Figure JPOXMLDOC01-appb-C000005
 　式中、Ｒｒ１、Ｒｒ２、Ｒｒ４、Ｒｒ５、およびＲｒ６はそれぞれ独立に水素原子または１価の置換基であり、Ｒｒ１およびＲｒ２の少なくとも一方は置換基であり、Ｒｒ４、Ｒｒ５、およびＲｒ６の少なくとも１つは置換基であり、Ｒｒ３は２価の置換基である。
＜２＞　上記式（ｒ１）または（ｒ２）で表される化合物が式（ｒ１－１）で表される、＜１＞に記載のインプリント用下層膜形成組成物；
Figure JPOXMLDOC01-appb-C000006
 　式中、Ｒｒ１およびＲｒ２はそれぞれ独立に水素原子または１価の置換基であり、Ｒｒ１およびＲｒ２の少なくとも一方は置換基である。
＜３＞　上記ポリマーが下記式（Ｒ－１）～（Ｒ－４）のいずれかで表される基を含む、＜１＞また＜２＞に記載のインプリント用下層膜形成組成物；
Figure JPOXMLDOC01-appb-C000007
 　式中、Ｒ１～Ｒ３はそれぞれ独立に１価の置換基であり、Ｒ４～Ｒ１２はそれぞれ独立に水素原子または１価の置換基であり、Ｘはポリマーの主鎖への結合位置を表す。
＜４＞　上記式（Ｒ－１）～（Ｒ－４）のいずれかで表される置換基を含むポリマーから、式中のＣ－Ｏ結合が分解して、上記式（ｒ１）または（ｒ２）で表され、かつ、分子量２１０以上の化合物が脱離する、＜３＞に記載のインプリント用下層膜形成組成物。
＜５＞　上記ポリマーが重合性基を含む、＜１＞～＜４＞のいずれか１つに記載のインプリント用下層膜形成組成物。
＜６＞　上記重合性基が（メタ）アクリロイル基を含む、＜５＞に記載のインプリント用下層膜形成組成物。
＜７＞　上記ポリマーが芳香環を含む、＜１＞～＜６＞のいずれか１つに記載のインプリント用下層膜形成組成物。
＜８＞　上記ポリマーが下記式（１）～式（６）のいずれかで表される構成単位の少なくとも１種を含む、＜１＞～＜７＞のいずれか１つに記載のインプリント用下層膜形成組成物；
Figure JPOXMLDOC01-appb-C000008
 　式中、ＲＰ４は水素原子またはメチル基である；ＲＰ１は、式（ｒ１）または（ｒ２）で表される化合物を脱離可能な基を表す。
＜９＞　上記式（ｒ１）または（ｒ２）で表される化合物が芳香環を含む、＜１＞～＜８＞のいずれか１つに記載のインプリント用下層膜形成組成物。
＜１０＞　上記式（ｒ１）または（ｒ２）で表される化合物が重合性基を含む、＜１＞～＜９＞のいずれか１つに記載のインプリント用下層膜形成組成物。
＜１１＞　上記重合性基が（メタ）アクリロイル基を含む、＜１０＞に記載のインプリント用下層膜形成組成物。
＜１２＞　上記式（ｒ１）のＲｒ１およびＲｒ２の少なくとも１つ、および、式（ｒ２）のＲｒ４～Ｒｒ６の少なくとも１つの少なくとも１つが重合性基を含む、＜１＞～＜１１＞のいずれか１つに記載のインプリント用下層膜形成組成物。
＜１３＞　上記式（ｒ１）または（ｒ２）で表される化合物の分子量が１０００以下である、＜１＞～＜１２＞のいずれか１つに記載のインプリント用下層膜形成組成物。
＜１４＞　さらに、脱離反応促進剤またはその前駆体を含む、＜１＞～＜１３＞のいずれか１つに記載のインプリント用下層膜形成組成物。
＜１５＞　さらに、光重合開始剤を含む、＜１＞～＜１４＞のいずれか１つに記載のインプリント用下層膜形成組成物。
＜１６＞　上記式（ｒ１）または（ｒ２）で表される化合物の表面張力が３５～５５ｍＮ／ｍである、＜１＞～＜１５＞のいずれか１つに記載のインプリント用下層膜形成組成物。
＜１７＞　溶剤を９５．０質量％以上の割合で含む、＜１＞～＜１６＞のいずれか１つに記載のインプリント用下層膜形成組成物。
＜１８＞　＜１＞～＜１７＞のいずれか１つに記載のインプリント用下層膜形成組成物と組み合わせて用いる、重合性化合物を含むインプリント用硬化性組成物。
＜１９＞　＜１＞～＜１７＞のいずれか１つに記載のインプリント用下層膜形成組成物と、重合性化合物を含むインプリント用硬化性組成物とを含むキット。
＜２０＞　上記式（ｒ１）または（ｒ２）で表される化合物のハンセン溶解度パラメータと上記インプリント用硬化性組成物のハンセン溶解度パラメータとに基づき下記数式（Ｈ１）で算出されるΔＨＳＰ値が５以下である、＜１９＞に記載のキット；
　　ΔＨＳＰ＝（４．０×ΔＤ２＋ΔＰ２＋ΔＨ２）０．５　　　　（Ｈ１）
　上記ΔＤは、インプリント用硬化性組成物のハンセン溶解度パラメータベクトルの分散項成分と、式（ｒ１）または（ｒ２）で表される化合物のハンセン溶解度パラメータベクトルの分散項成分の差であり、上記ΔＰは、インプリント用硬化性組成物のハンセン溶解度パラメータベクトルの極性項成分と、式（ｒ１）または（ｒ２）で表される化合物のハンセン溶解度パラメータベクトルの極性項成分の差であり、上記ΔＨは、インプリント用硬化性組成物のハンセン溶解度パラメータベクトルの水素結合項成分と、式（ｒ１）または（ｒ２）で表される化合物のハンセン溶解度パラメータベクトルの水素結合項成分の差である。
＜２１＞　＜１＞～＜１７＞のいずれか１つに記載の下層膜形成組成物から形成された下層膜。
＜２２＞　＜１９＞または＜２０＞に記載のキットから形成される積層体であって、
　上記インプリント用下層膜形成組成物から形成された下層膜と、上記インプリント用硬化性組成物から形成され、上記下層膜の表面に位置するインプリント層とを有する、積層体。
＜２３＞　＜１９＞または＜２０＞に記載のキットを用いて積層体を製造する方法であって、上記インプリント用下層膜形成組成物から形成された下層膜の表面に、インプリント用硬化性組成物を適用することを含む、積層体の製造方法。
＜２４＞　上記インプリント用硬化性組成物は、インクジェット法により、上記下層膜の表面に適用する、＜２３＞に記載の積層体の製造方法。
＜２５＞　さらに、上記インプリント用下層膜形成組成物を基板上に層状に適用する工程を含み、上記層状に適用したインプリント用下層膜形成組成物を８０～２５０℃で、加熱することを含む、＜２３＞または＜２４＞に記載の積層体の製造方法。
＜２６＞　＜１９＞または＜２０＞に記載のキットを用いて硬化物パターンを製造する方法であって、基板上に、インプリント用下層膜形成組成物を適用して下層膜を形成する下層膜形成工程と、上記下層膜の表面に、インプリント用硬化性組成物を適用する適用工程と、上記インプリント用硬化性組成物と、パターン形状を転写するためのパターンを有するモールドとを接触させるモールド接触工程と、上記インプリント用硬化性組成物に光を照射して硬化物を形成する光照射工程と、上記硬化物と上記モールドとを引き離す離型工程と、を有する硬化物パターンの製造方法。
＜２７＞　＜２６＞に記載の製造方法により硬化物パターンを得る工程を含む、回路基板の製造方法。 As a result of investigations by the present inventors based on the above problems, it has been found that the above problems can be solved by employing a polymer capable of generating a specific desorption component in the composition for forming an underlayer film for imprinting. It was. Specifically, the above problem has been solved by the following means <1>, preferably <2> to <27>.
<1> An underprint film-forming composition for imprints comprising a polymer and a solvent, wherein when the above-mentioned undercoat film-forming composition for imprints is formed into a film and baked at 80 ° C., from the polymer, the following formula (r1) Or a composition for forming an underlayer film for imprinting, wherein a compound represented by (r2) and having a molecular weight of 210 or more is eliminated;
Figure JPOXMLDOC01-appb-C000005
 In the formula, R r1 , R r2 , R r4 , R r5 , and R r6 are each independently a hydrogen atom or a monovalent substituent, and at least one of R r1 and R r2 is a substituent, R r4 , At least one of R r5 and R r6 is a substituent, and R r3 is a divalent substituent.
<2> The composition for forming an underlayer film for imprints according to <1>, wherein the compound represented by the formula (r1) or (r2) is represented by the formula (r1-1);
Figure JPOXMLDOC01-appb-C000006
 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 composition for forming an underlayer film for imprints according to <1> or <2>, wherein the polymer includes a group represented by any of the following formulas (R-1) to (R-4);
Figure JPOXMLDOC01-appb-C000007
 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 is a bonding position to the main chain of the polymer. Represents.
<4> From the polymer containing a substituent represented by any one of the above formulas (R-1) to (R-4), the C—O bond in the formula is decomposed, and the above formula (r1) or (r2) The composition for forming an underlayer film for imprints according to <3>, wherein a compound having a molecular weight of 210 or more is eliminated.
<5> The composition for forming an underlayer film for imprints according to any one of <1> to <4>, wherein the polymer contains a polymerizable group.
<6> The underlayer film-forming composition for imprints according to <5>, wherein the polymerizable group includes a (meth) acryloyl group.
<7> The composition for forming a lower layer film for imprints according to any one of <1> to <6>, wherein the polymer includes an aromatic ring.
<8> The imprint according to any one of <1> to <7>, wherein the polymer includes at least one structural unit represented by any of the following formulas (1) to (6): An underlayer film forming composition;
Figure JPOXMLDOC01-appb-C000008
 In the formula, R P4 represents a hydrogen atom or a methyl group; R P1 represents a group capable of leaving the compound represented by the formula (r1) or (r2).
<9> The underlayer film-forming composition for imprints according to any one of <1> to <8>, wherein the compound represented by the formula (r1) or (r2) includes an aromatic ring.
<10> The underlayer film forming composition for imprints according to any one of <1> to <9>, wherein the compound represented by the formula (r1) or (r2) includes a polymerizable group.
<11> The underlayer film forming composition for imprints according to <10>, wherein the polymerizable group includes a (meth) acryloyl group.
<12> At least one of R r1 and R r2 in the formula (r1) and at least one of R r4 to R r6 in the formula (r2) include a polymerizable group, <1> to <11 The underlayer film forming composition for imprints as described in any one of>.
<13> The underlayer film-forming composition for imprints according to any one of <1> to <12>, wherein the compound represented by the formula (r1) or (r2) has a molecular weight of 1000 or less.
<14> The underlayer film-forming composition for imprints according to any one of <1> to <13>, further comprising an elimination reaction accelerator or a precursor thereof.
<15> The composition for forming an underlayer film for imprints according to any one of <1> to <14>, further comprising a photopolymerization initiator.
<16> Formation of an underprint film for imprinting according to any one of <1> to <15>, wherein the compound represented by the formula (r1) or (r2) has a surface tension of 35 to 55 mN / m Composition.
<17> The composition for forming an underlayer film for imprints according to any one of <1> to <16>, comprising a solvent in a proportion of 95.0 mass% or more.
<18> A curable composition for imprints containing a polymerizable compound, which is used in combination with the composition for forming an underprint film for imprints according to any one of <1> to <17>.
<19> A kit comprising the imprint underlayer film forming composition according to any one of <1> to <17>, and an imprint curable composition comprising a polymerizable compound.
<20> Based on the Hansen solubility parameter of the compound represented by the above formula (r1) or (r2) and the Hansen solubility parameter of the curable composition for imprints, a ΔHSP value calculated by the following formula (H1) is 5 The kit according to <19>, which is:
ΔHSP = (4.0 × ΔD 2 + ΔP 2 + ΔH 2 ) 0.5 (H1)
ΔD is the difference between the dispersion term component of the Hansen solubility parameter vector of the curable composition for imprints and the dispersion term component of the Hansen solubility parameter vector of the compound represented by the formula (r1) or (r2), ΔP is the difference between the polar term component of the Hansen solubility parameter vector of the curable composition for imprints and the polar term component of the Hansen solubility parameter vector of the compound represented by the formula (r1) or (r2). Is the difference between the hydrogen bond term component of the Hansen solubility parameter vector of the curable composition for imprints and the hydrogen bond term component of the Hansen solubility parameter vector of the compound represented by the formula (r1) or (r2).
<21> A lower layer film formed from the lower layer film forming composition according to any one of <1> to <17>.
<22> A laminate formed from the kit according to <19> or <20>,
The laminated body which has the lower layer film formed from the said lower layer film formation composition for imprints, and the imprint layer formed from the said curable composition for imprints, and located in the surface of the said lower layer film.
<23> A method for producing a laminate using the kit according to <19> or <20>, wherein the surface of the lower layer film formed from the lower layer film forming composition for imprinting is cured for imprinting. The manufacturing method of a laminated body including applying an adhesive composition.
<24> The method for producing a laminate according to <23>, wherein the curable composition for imprints is applied to a surface of the lower layer film by an inkjet method.
<25> Further, the method further includes the step of applying the lower layer film-forming composition for imprinting on the substrate in a layered manner, and heating the lower layer film forming composition for imprinting applied to the layered state at 80 to 250 ° C. The manufacturing method of the laminated body as described in <23> or <24> containing.
<26> A method for producing a cured product pattern using the kit according to <19> or <20>, wherein a lower layer film is formed on a substrate by applying the lower film forming composition for imprinting Contact the film forming step, the application step of applying the curable composition for imprints to the surface of the lower layer film, the curable composition for imprints, and the mold having a pattern for transferring the pattern shape. A mold contact step, a light irradiation step of irradiating the curable composition for imprints with light to form a cured product, and a releasing step of separating the cured product from the mold. Production method.
<27> A method for producing a circuit board, comprising a step of obtaining a cured product pattern by the production method according to <26>.
　本発明により、インプリント用下層膜形成組成物の塗膜に対するインプリント用硬化性組成物の濡れ性、および、これらの組成物から形成される下層膜とインプリント層の密着性を向上させることが可能になった。また、その技術を適用したインプリント用下層膜形成組成物、インプリント用硬化性組成物、およびこれらを用いたキットを提供することが可能になった。 According to the present invention, the wettability of the curable composition for imprints with respect to the coating film of the lower layer film-forming composition for imprints, and the adhesion between the lower layer film and the imprint layer formed from these compositions are improved. Became possible. In addition, it has become possible to provide an underprint film forming composition for imprinting, a curable composition for imprinting, and a kit using these, to which the technology is applied.
硬化物パターンの形成、および、得られた硬化物パターンをエッチングによる基板の加工に用いる場合の製造プロセスの一例を示す工程説明図である。It is process explanatory drawing which shows an example of the manufacturing process in the case of using formation of a hardened | cured material pattern and the process of the board | substrate by an etching obtained by the obtained hardened | cured material pattern. 濡れ性の低い下層膜の表面にインプリント用硬化性組成物をインクジェット法により塗布した場合の、インプリント用硬化性組成物の濡れ広がりの状態を模式的に示す平面図である。It is a top view which shows typically the state of the wet spreading of the curable composition for imprints when the curable composition for imprints is apply | coated to the surface of the lower layer film | membrane with low wettability by the inkjet method.
　以下において、本発明の内容について詳細に説明する。尚、本明細書において「～」とはその前後に記載される数値を下限値および上限値として含む意味で使用される。
　本明細書において、「（メタ）アクリレート」は、アクリレートおよびメタクリレートを表す。 Hereinafter, the contents of the present invention will be described in detail. In this specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In this specification, “(meth) acrylate” represents acrylate and methacrylate.
　本明細書において、「インプリント」は、好ましくは、１ｎｍ～１０ｍｍのサイズのパターン転写をいい、より好ましくは、およそ１０ｎｍ～１００μｍのサイズのパターン転写（ナノインプリント）をいう。
　本明細書における基（原子団）の表記において、置換および無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含するものである。
　本明細書において、「光」には、紫外、近紫外、遠紫外、可視、赤外等の領域の波長の光や、電磁波だけでなく、放射線も含まれる。放射線には、例えばマイクロ波、電子線、極端紫外線（ＥＵＶ）、Ｘ線が含まれる。また２４８ｎｍエキシマレーザー、１９３ｎｍエキシマレーザー、１７２ｎｍエキシマレーザーなどのレーザー光も用いることができる。これらの光は、光学フィルタを通したモノクロ光（単一波長光）を用いてもよいし、複数の波長の異なる光(複合光)でもよい。
　本発明における温度は、特に述べない限り、２３℃とする。
　本発明における沸点とは、１気圧(１ａｔｍ＝１０１３．２５ｈＰａ）における沸点をいう。 In the present specification, “imprint” preferably refers to pattern transfer having a size of 1 nm to 10 mm, more preferably pattern transfer (nanoimprint) having a size of approximately 10 nm to 100 μm.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, “light” includes not only light in a wavelength region such as ultraviolet, near ultraviolet, far ultraviolet, visible, infrared, and electromagnetic waves, but also radiation. Examples of radiation include microwaves, electron beams, extreme ultraviolet rays (EUV), and X-rays. Laser light such as a 248 nm excimer laser, a 193 nm excimer laser, and a 172 nm excimer laser can also be used. The light may be monochromatic light (single wavelength light) that has passed through an optical filter, or may be light having a plurality of different wavelengths (composite light).
The temperature in the present invention is 23 ° C. unless otherwise specified.
The boiling point in the present invention refers to the boiling point at 1 atmosphere (1 atm = 1013.25 hPa).
　本発明のインプリント用下層膜形成組成物は、ポリマーと溶剤とを含み、インプリント用下層膜形成組成物を膜状にし８０℃でベークした場合、ポリマーから下記式（ｒ１）または（ｒ２）で表される化合物（以下、脱離成分ということがある）が脱離することを特徴とする。これにより、インプリントにおけるインプリント用下層膜形成組成物の塗膜に対するインプリント用硬化性組成物の濡れ性が向上し、かつ、これらの組成物から形成される下層膜およびインプリント層の密着性が向上する。この理由は以下のように推定される。すなわち、低分子成分の生成は下層膜の表面における界面張力の低下をもたらし、それに伴って濡れ性が向上すると考えられる。また、下層膜中に拡散パスが発生することにより下層膜において低分子成分が存在していた領域にインプリント用硬化性組成物の硬化性成分が浸入し、その部分が硬化することで下層膜と硬化物との間と密着性が向上すると考えられる。 The underlayer film-forming composition for imprints of the present invention contains a polymer and a solvent. When the underlayer film-forming composition for imprints is formed into a film and baked at 80 ° C., the following formula (r1) or (r2) is determined from the polymer. Is desorbed (hereinafter also referred to as a desorbing component). Thereby, the wettability of the curable composition for imprints with respect to the coating film of the underlayer film forming composition for imprints in imprinting is improved, and adhesion between the lower layer film and the imprint layer formed from these compositions is improved. Improves. The reason for this is estimated as follows. That is, it is considered that the generation of a low molecular component causes a decrease in interfacial tension on the surface of the lower layer film, and accordingly, wettability is improved. In addition, when a diffusion path occurs in the lower layer film, the curable component of the curable composition for imprints penetrates into the region where the low molecular component was present in the lower layer film, and the portion is cured, thereby lower layer film It is considered that the adhesion between the cured product and the cured product is improved.
＜インプリント用下層膜形成組成物＞
　本発明では、インプリント用下層膜形成組成物を膜状にし８０℃でベークした場合、上記ポリマーから下記式（ｒ１）または（ｒ２）で表され、かつ、分子量が２１０以上の化合物が脱離する。以下、本明細書では、上記化合物を脱離成分という。 <Underlayer film-forming composition for imprint>
In the present invention, when the composition for forming a lower layer film for imprinting is formed into a film and baked at 80 ° C., a compound represented by the following formula (r1) or (r2) and having a molecular weight of 210 or more is desorbed from the polymer. To do. Hereinafter, in the present specification, the above compound is referred to as a desorbing component.
＜＜脱離成分＞＞
　脱離成分は、インプリント用下層膜形成組成物を膜状にし８０℃でベークした場合、ポリマーから脱離する成分であって、所定の構造を有し、かつ、分子量が２１０以上の化合物である。 << Desorption component >>
The desorbing component is a component that desorbs from the polymer when the underlayer film forming composition for imprinting is formed into a film and baked at 80 ° C., and is a compound having a predetermined structure and having a molecular weight of 210 or more. is there.
　本発明の第１実施形態における脱離成分は下記式（ｒ１）または（ｒ２）で表される。脱離成分が式（ｒ１）または（ｒ２）で表される化合物であると、インプリント用硬化性組成物中の重合開始剤がインプリント用下層膜形成組成物にも拡散し、インプリント用硬化性組成物の硬化と同時にインプリント用下層膜形成組成物も硬化し、インプリント用硬化性組成物と下層膜との密着性がより優れる。
Figure JPOXMLDOC01-appb-C000009
 　式中、Ｒｒ１、Ｒｒ２、Ｒｒ４、Ｒｒ５、およびＲｒ６はそれぞれ独立に水素原子または１価の置換基であり、Ｒｒ１およびＲｒ２の少なくとも一方は置換基であり、Ｒｒ４、Ｒｒ５、およびＲｒ６の少なくとも１つは置換基であり、Ｒｒ３は２価の置換基である。 The desorption component in the first embodiment of the present invention is represented by the following formula (r1) or (r2). When the desorbing component is a compound represented by the formula (r1) or (r2), the polymerization initiator in the curable composition for imprinting diffuses into the underlayer film forming composition for imprinting, and for imprinting. Simultaneously with the curing of the curable composition, the composition for forming a lower layer film for imprints is cured, and the adhesion between the curable composition for imprints and the lower layer film is more excellent.
Figure JPOXMLDOC01-appb-C000009
 In the formula, R r1 , R r2 , R r4 , R r5 , and R r6 are each independently a hydrogen atom or a monovalent substituent, and at least one of R r1 and R r2 is a substituent, R r4 , At least one of R r5 and R r6 is a substituent, and R r3 is a divalent substituent.
　式（ｒ１）または（ｒ２）で表される化合物は下記式（ｒ１－１）で表されることが好ましい。
Figure JPOXMLDOC01-appb-C000010
 　式中、Ｒｒ１およびＲｒ２はそれぞれ独立に水素原子または１価の置換基であり、Ｒｒ１およびＲｒ２の少なくとも一方は置換基である。 The compound represented by the formula (r1) or (r2) is preferably represented by the following formula (r1-1).
Figure JPOXMLDOC01-appb-C000010
 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.
　脱離成分（式（ｒ１）または（ｒ２）で表される化合物あるいは式（ｒ１－１）で表される化合物）は芳香環（好ましくは、下記環ａＣｙまたはｈＣｙ）を含むことが好ましい。
　特に、式（ｒ１）のＲｒ１およびＲｒ２の少なくとも１つ、式（ｒ２）のＲｒ４～Ｒｒ６の少なくとも１つ、式（ｒ１－１）のＲｒ１およびＲｒ２の少なくとも１つが芳香環を含むことが好ましい。芳香環としては、下記の環ａＣｙまたはｈＣｙであることが好ましい。 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 (preferably the following ring aCy or hCy).
In particular, at least one of R r1 and R r2 of formula (r1), at least one of R r4 to R r6 of formula (r2), and at least one of R r1 and R r2 of formula (r1-1) are aromatic rings It is preferable to contain. The aromatic ring is preferably the following ring aCy or hCy.
　芳香環が芳香族環であるときの具体例としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、フェナレン環、フルオレン環、アセナフチレン環、ビフェニル環、テルフェニル環、インデン環、インダン環、トリフェニレン環、テトラフェニレン環、ピレン環、クリセン環、ペリレン環、テトラヒドロナフタレン環などが挙げられる。芳香族環は連結基Ｌを介してまたは介さずに複数が連結した構造を取っていてもよく、例えば、ビフェニル環、ジフェニルメタン環、トリフェニルメタン環が挙げられる。あるいは、一部上記で例示したものも含め、複数のベンゼン環が連結した構造としては下記式Ａｒ１～Ａｒ５のものが挙げられる。式中ベンゼン環の中心付近から外へ向けて引いた直線は結合手を示している。この単結合を介して、任意の連結基に結合しているか、これを介してもしくは介さずに、下記式（Ｔ１）のＬ１、Ｌ２、Ｐ、またはポリマーの主鎖に結合していることを意味する。Ａ１は２価の連結基であり、連結基Ｌの例が好ましく、フッ素原子で置換されていてもよいアルキレン基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい）、カルボニル基、酸素原子、スルホニル基、スルフィニル基、－ＮＲＮ－がより好ましい。Ａ２は窒素原子、リン原子を含む３価の連結基、またはメチン基を意味する。式Ａｒ１～Ａｒ５において結合手は任意に２個また３個あることを示しているが、必要な連結数に応じて必要な部分で結合すればよいことを意味する。例えば、１つのベンゼン環から２つの結合手が延びることも本発明の好ましい態様として挙げることができる。また、３つの環をもつＡｒ２が２価の連結基であることも本発明の好ましい態様として挙げることができる。
Figure JPOXMLDOC01-appb-C000011
 　上記化学式のものを含め、ここで例示した芳香族環の例を環ａＣｙと呼ぶ。 Specific examples when the aromatic ring is an aromatic ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, phenalene ring, fluorene ring, acenaphthylene ring, biphenyl ring, terphenyl ring, indene ring, indane ring, triphenylene Ring, tetraphenylene ring, pyrene ring, chrysene ring, perylene ring, tetrahydronaphthalene ring and the like. The aromatic ring may have a structure in which a plurality of aromatic rings are connected with or without a connecting group L, and examples thereof include a biphenyl ring, a diphenylmethane ring, and a triphenylmethane ring. Alternatively, examples of the structure in which a plurality of benzene rings are linked, including those exemplified above, include those represented by the following formulas Ar1 to Ar5. In the formula, a straight line drawn outward from the center of the benzene ring indicates a bond. It is bonded to an arbitrary linking group through this single bond, or is bonded to L 1 , L 2 , P of the following formula (T1), or the main chain of the polymer through or without it. Means that. A 1 is a divalent linking group, and examples of the linking group L are preferable. An alkylene group which may be substituted with a fluorine atom (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and 1 to 3 carbon atoms being preferred) Further preferred are a carbonyl group, an oxygen atom, a sulfonyl group, a sulfinyl group, and —NR N —. A 2 represents a nitrogen atom, a trivalent linking group containing a phosphorus atom, or a methine group. In the formulas Ar1 to Ar5, it is shown that there are two or three bonds, but it means that the bonds may be bonded at a necessary portion according to the required number of linkages. For example, it can be mentioned as a preferred embodiment of the present invention that two bonds extend from one benzene ring. Moreover, it can also be mentioned as a preferable aspect of the present invention that Ar2 having three rings is a divalent linking group.
Figure JPOXMLDOC01-appb-C000011
 Examples of the aromatic ring exemplified here including those of the above chemical formula are referred to as ring aCy.
　芳香環が芳香族複素環であるときは、その炭素数は１～１２が好ましく、１～６がより好ましく、１～５がさらに好ましい。その具体例としては、チオフェン環、フラン環、ピロール環、イミダゾール環、ピラゾール環、トリアゾール環、テトラゾール環、チアゾール環、オキサゾール環、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環、トリアジン環、イソインドール環、インドール環、インダゾール環、プリン環、キノリジン環、イソキノリン環、キノリン環、フタラジン環、ナフチリジン環、キノキサリン環、キナゾリン環、シンノリン環、カルバゾール環、アクリジン環、フェナジン環、フェノチアジン環、フェノキサジン環などが挙げられる。
　芳香族複素環は複数の環構造が連結基Ｌを介してまたは介さずに連結した構造であってもよい。
　ここで示した芳香族複素環を環ｈＣｙと称する。 When the aromatic ring is an aromatic heterocyclic ring, the carbon number thereof is preferably 1 to 12, more preferably 1 to 6, and further preferably 1 to 5. Specific examples thereof include thiophene ring, furan ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, oxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, isoindole. Ring, indole ring, indazole ring, purine ring, quinolidine ring, isoquinoline ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, carbazole ring, acridine ring, phenazine ring, phenothiazine ring, phenoxazine ring Etc.
The aromatic heterocyclic ring may have a structure in which a plurality of ring structures are connected through or without the connecting group L.
The aromatic heterocycle shown here is referred to as ring hCy.
　脱離成分に含まれる芳香環としては、なかでも、ベンゼン環が好ましい。
　芳香環は、本発明の効果を奏する範囲で、置換基Ｔを有していてもよい。置換基Ｔは複数あるとき互いに結合して、あるいは連結基Ｌを介してまたは介さずに式中の環と結合して環を形成していてもよい。例えば、アルキル基、アルケニル基、アリール基、アリールアルキル基等はさらにハロゲン原子（フッ素原子が好ましい）で置換されていてもよい。 Among them, the aromatic ring contained in the leaving component is preferably a benzene ring.
The aromatic ring may have a substituent T as long as the effects of the present invention are achieved. When there are a plurality of substituents T, they may be bonded to each other, or may be bonded to a ring in the formula through or without a linking group L to form a ring. For example, the alkyl group, alkenyl group, aryl group, arylalkyl group and the like may be further substituted with a halogen atom (a fluorine atom is preferred).
　また、脱離成分は重合性基を含むことが好ましい。重合性基としては例えば、エチレン性不飽和基、エポキシ基、グリシジル基、オキセタン基などを含む基が挙げることができる。エチレン性不飽和基としては、ビニル基、アリル基、ビニルフェニル基、（メタ）アクリロイル基、（メタ）アクリロイルオキシ基を含む基が挙げられる。ここで例示した重合性基を重合性基Ｐｓと呼ぶ。本発明においては、中でも、重合性基Ｐｓは（メタ）アクリロイル基または（メタ）アクリロイルオキシ基を含むことが好ましい。
　特に、式（ｒ１）のＲｒ１およびＲｒ２の少なくとも１つ、式（ｒ２）のＲｒ４～Ｒｒ６の少なくとも１つ、式（ｒ１－１）のＲｒ１およびＲｒ２の少なくとも１つが重合性基を含むことが好ましい。重合性基としては、上記の重合性基Ｐｓが好ましい。
　さらに、脱離成分は、エチレン性二重結合を含むことが好ましい。特に、ポリマーから脱離することによって、エチレン性二重結合が形成されることが好ましい。このような脱離をすることにより、密着力という効果が発揮される。 The leaving component preferably contains a polymerizable group. Examples of the polymerizable group include groups containing an ethylenically unsaturated group, an epoxy group, a glycidyl group, an oxetane group, and the like. Examples of the ethylenically unsaturated group include a group including a vinyl group, an allyl group, a vinylphenyl group, a (meth) acryloyl group, and a (meth) acryloyloxy group. The polymerizable group exemplified here is referred to as a polymerizable group Ps. In the present invention, among them, the polymerizable group Ps preferably contains a (meth) acryloyl group or a (meth) acryloyloxy group.
In particular, at least one of R r1 and R r2 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) are polymerizable. Preferably it contains a group. As the polymerizable group, the polymerizable group Ps is preferable.
Further, the elimination component preferably contains an ethylenic double bond. In particular, it is preferable that an ethylenic double bond is formed by elimination from the polymer. By such desorption, the effect of adhesion is exhibited.
　式（ｒ１）または（ｒ２）あるいは式（ｒ１－１）において、Ｒｒ１、Ｒｒ２、Ｒｒ４、Ｒｒ５、Ｒｒ６が置換基であるとき、その置換基として後述の置換基Ｔの例が挙げられ、なかでも、それぞれ独立にアルキル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい）、アルケニル基（炭素数２～１２が好ましく、２～６がより好ましく、２～３がさらに好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）、アリールアルキル基（炭素数７～２３が好ましく、７～１９がより好ましく、７～１１がさらに好ましい）、または下記の式（ＲＬ－１）で表される基であることが好ましい。さらに式（ｒ１）および（ｒ２）においては、少なくともＲｒ２またはＲｒ６が下記式（ＲＬ－１）で表される基であることが特に好ましい。 In the formula (r1) or (r2) or the formula (r1-1), when R r1 , R r2 , R r4 , R r5 , R r6 is a substituent, examples of the substituent T described below are examples of the substituent. Among them, each independently an alkyl group (preferably having a carbon number of 1 to 12, preferably 1 to 6, more preferably 1 to 3, and an alkenyl group (preferably having a carbon number of 2 to 12, preferably 2 to 6). More preferably, 2 to 3 are more preferable, an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, 7 To 19 are more preferable, and 7 to 11 are more preferable), or a group represented by the following formula (RL-1) is preferable. Further, in the formulas (r1) and (r2), it is particularly preferable that at least R r2 or R r6 is a group represented by the following formula (RL-1).
Figure JPOXMLDOC01-appb-C000012
 　ＬＲ１およびＬＲ２はそれぞれ独立に単結合または連結基であり、ＡｒＲは芳香環を含む連結基であり、ＰＲは重合性基を有する基である。ｎｒは０～８の整数であり、ｍｒは１～４の整数である。
Figure JPOXMLDOC01-appb-C000012
 L R1 and L R2 are each independently a single bond or a linking group, Ar R is a linking group containing an aromatic ring, P R is a group having a polymerizable group. nr is an integer of 0 to 8, and mr is an integer of 1 to 4.
　ＬＲ１は、１＋ｍｒ価の芳香環（上記ａＣｙまたはｈＣｙの例が好ましい）、脂環（下記脂環ｆＣｙの例が好ましい）、直鎖もしくは分岐のアルカン構造の基（炭素数１～４０が好ましく、１～３０がより好ましく、１～２０がさらに好ましい）、直鎖もしくは分岐のアルケン構造の基（炭素数２～４０が好ましく、２～３０がより好ましく、２～２０がさらに好ましい）、または直鎖もしくは分岐のアルキン構造の基（炭素数２～４０が好ましく、２～３０がより好ましく、２～２０がさらに好ましい）であることが好ましい。 L R1 is, 1 + mr -valent aromatic ring (examples of the aCy or hCy is preferred), alicyclic (e.g. below alicyclic fCy is preferred), a linear or branched radical of an alkane structure (having 1 to 40 carbon atoms are preferred 1 to 30 is more preferable, and 1 to 20 is more preferable), a linear or branched alkene structure group (preferably 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, and further preferably 2 to 20 carbon atoms), or A group having a linear or branched alkyne structure (preferably having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, still more preferably 2 to 20 carbon atoms) is preferable.
　ＬＲ２の連結基は下記連結基Ｌまたは下記ヘテロ原子を含む連結基Ｌｈの例が好ましい。なかでも、アルキレン基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい）、アリーレン基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）、（オリゴ）アルキレンオキシ基（１つの構成単位中のアルキレン基の炭素数は１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい；繰り返し数は１～５０が好ましく、１～４０がより好ましく、１～３０がさらに好ましい）、カルボニル基、酸素原子、またはこれらを組み合わせた基が好ましい。
　ＬＲ２は連結基Ｌを介してまたは介さずにＬＲ１と結合して環を形成していてもよい。 Examples of the linking group of L R2 are preferably the following linking group L or a linking group Lh containing the following hetero atom. Of these, an alkylene group (preferably having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), an arylene group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and 6 to 10 carbon atoms). Is more preferable), (oligo) alkyleneoxy group (the number of carbon atoms of the alkylene group in one structural unit is preferably 1 to 12, more preferably 1 to 6, and further preferably 1 to 3; the number of repetitions is 1 to 50). Preferably 1 to 40, more preferably 1 to 30), and a carbonyl group, an oxygen atom, or a combination thereof.
L R2 may be bonded to L R1 via a linking group L or not to form a ring.
　ＡｒＲは芳香環を含む連結基である。ただしｎｒが０のときは、ＡｒＲは芳香環を含む置換基である。芳香環としては上記の環ａＣｙまたはｈＣｙが好ましい。ＡｒＲが芳香環以外の置換基含むとき、その連結基としては下記連結基Ｌの例が挙げられ、なかでも、アルキレン基（炭素数１～２４が好ましく、１～１２がより好ましく、１～６がさらに好ましい）、アルケニレン基（炭素数２～１２が好ましく、２～６がより好ましく、２～３がさらに好ましい）、アルキニレン基（炭素数２～１２が好ましく、２～６がより好ましく、２～３がさらに好ましい）、（オリゴ）アルキレンオキシ基（１つの構成単位中のアルキレン基の炭素数は１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい；繰り返し数は１～５０が好ましく、１～４０がより好ましく、１～３０がさらに好ましい）、アリーレン基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）、またはその組合せに係る連結基が挙げられる。ＡｒＲは連結基Ｌを介してまたは介さずに、ＬＲ１、ＬＲ２、またはＰＲと結合して環を形成していてもよい。 Ar R is a linking group containing an aromatic ring. However, when nr is 0, Ar R is a substituent containing an aromatic ring. The aromatic ring is preferably the above ring aCy or hCy. When Ar R contains a substituent other than an aromatic ring, examples of the linking group include the following linking groups L. Among them, an alkylene group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms) 6 is more preferable), an alkenylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms), an alkynylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms) 2 to 3 are more preferable), (oligo) alkyleneoxy group (the number of carbon atoms of the alkylene group in one structural unit is preferably 1 to 12, more preferably 1 to 6, still more preferably 1 to 3; 1 to 50, preferably 1 to 40, more preferably 1 to 30), and an arylene group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms). And a linking group according to a combination thereof. Ar R is not through or via a linking group L, L R1, L R2 or may be bonded to the P R to form a ring.
　ＰＲは重合性基を有する揮であり、重合性基は、上記重合性基Ｐｓの例が好ましい。ＰＲは連結基Ｌを介してまたは介さずに、ＬＲ１、ＬＲ２と結合して環を形成していてもよい。 P R is the volatilization having a polymerizable group, the polymerizable group, examples of the polymerizable group Ps are preferred. P R is not through or via a linking group L, they may form a ring with L R1, L R2.
　ＬＲ１、ＬＲ２、ＡｒＲ、ＰＲは本発明の効果を奏する範囲で置換基Ｔを有していてもよい。例えば、アルキル基、アルケニル基、アリール基、アリールアルキル基等はさらにハロゲン原子（フッ素原子が好ましい）で置換されていてもよい。 L R1, L R2, Ar R , P R may have a substituent T to the extent that the effects of the present invention. For example, the alkyl group, alkenyl group, aryl group, arylalkyl group and the like may be further substituted with a halogen atom (a fluorine atom is preferred).
　ｎｒは０～８の整数であり、０～６が好ましく、０～４がより好ましく、０～２がさらに好ましい。ｍｒは１～４の整数であり、１～２が好ましい。 Nr is an integer of 0 to 8, preferably 0 to 6, more preferably 0 to 4, and still more preferably 0 to 2. mr is an integer of 1 to 4, preferably 1 or 2.
　Ｒｒ３の２価の置換基としては、ＣＨ２（下記第２実施形態）、ＣＨＲｒ８、またはＣ（Ｒｒ９）２が挙げられる。ここで、Ｒｒ８およびＲｒ９はそれぞれ独立して後述する置換基Ｔであり、なかでもアルキル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい）、アルケニル基（炭素数２～１２が好ましく、２～６がより好ましく、２～３がさらに好ましい）、アルキニル基（炭素数２～１２が好ましく、２～６がより好ましく、２～３がさらに好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）、アリールアルキル基（炭素数７～２３が好ましく、７～１９がより好ましく、７～１１がさらに好ましい）が好ましい。Ｃ（Ｒｒ９）２の２つのＲｒ９は互いに同じでも異なっていてもよい。 Examples of the divalent substituent for R r3 include CH 2 (second embodiment described below), CHR r8 , and C (R r9 ) 2 . Here, R r8 and R r9 are each independently a substituent T described later, and among them, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 3 carbon atoms), alkenyl group Groups (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms), alkynyl groups (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and further preferably 2 to 3 carbon atoms) An aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and 7 to 11 carbon atoms being Further preferred). C (R r9) 2 two R r9 of 2 may be the same as or different from each other.
　ヘテロ原子を含む連結基Ｌｈとしては、酸素原子、硫黄原子、カルボニル基、チオカルボニル基、スルホニル基、スルフィニル基、－ＮＲＮ－、（オリゴ）アルキレンオキシ基（１つの構成単位中のアルキレン基の炭素数は１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい；繰り返し数は１～５０が好ましく、１～４０がより好ましく、１～３０がさらに好ましい）、またはこれらの組み合わせからなる連結基が挙げられる。ヘテロ原子を含む連結基Ｌｈを構成する原子の数は水素原子を除いて１～１００が好ましく、１～７０がより好ましく、１～５０が特に好ましい。Ｌｈの連結原子数は１～２５が好ましく、１～２０がより好ましく、１～１５がさらに好ましく、１～１０が一層好ましい。なお、（オリゴ）アルキレンオキシ基とは、アルキレンオキシ基でも、オリゴアルキレンオキシ基でもよい意味である。上記（オリゴ）アルキレンオキシ基は、鎖状でも環状でもよく、直鎖でも分岐でもよい。連結基が－ＮＲＮ－やカルボキシル基が置換している場合などの塩を形成しうる基の場合、その基が塩を形成していてもよい。 The linking group Lh containing a hetero atom includes an oxygen atom, a sulfur atom, a carbonyl group, a thiocarbonyl group, a sulfonyl group, a sulfinyl group, —NR N —, an (oligo) alkyleneoxy group (of the alkylene group in one constituent unit). The number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, more preferably 1 to 3; the number of repetitions is preferably 1 to 50, more preferably 1 to 40, still more preferably 1 to 30), or these Examples of the linking group include a combination. 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, particularly preferably from 1 to 50, excluding hydrogen atoms. The number of linking atoms of Lh is preferably 1 to 25, more preferably 1 to 20, still more preferably 1 to 15, and still more preferably 1 to 10. The (oligo) alkyleneoxy group means an alkyleneoxy group or an oligoalkyleneoxy group. The (oligo) alkyleneoxy group may be linear or cyclic, and may be linear or branched. In the case where the linking group is a group capable of forming a salt such as when —NR N — or a carboxyl group is substituted, the group may form a salt.
　置換基Ｔとしては、アルキル基（炭素数１～２４が好ましく、１～１２がより好ましく、１～６がさらに好ましい）、アリールアルキル基（炭素数７～２１が好ましく、７～１５がより好ましく、７～１１がさらに好ましい）、アルケニル基（炭素数２～２４が好ましく、２～１２がより好ましく、２～６がさらに好ましい）、アルキニル基（炭素数２～１２が好ましく、２～６がより好ましく、２～３がさらに好ましい）、ヒドロキシル基、アミノ基（炭素数０～２４が好ましく、０～１２がより好ましく、０～６がさらに好ましい）、チオール基、カルボキシル基、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）、アルコキシル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい）、アリールオキシ基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）、アシル基（炭素数２～１２が好ましく、２～６がより好ましく、２～３がさらに好ましい）、アシルオキシ基（炭素数２～１２が好ましく、２～６がより好ましく、２～３がさらに好ましい）、アリーロイル基（炭素数７～２３が好ましく、７～１９がより好ましく、７～１１がさらに好ましい）、アリーロイルオキシ基（炭素数７～２３が好ましく、７～１９がより好ましく、７～１１がさらに好ましい）、カルバモイル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい）、スルファモイル基（炭素数０～１２が好ましく、０～６がより好ましく、０～３がさらに好ましい）、スルホ基、アルキルスルホニル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい）、アリールスルホニル基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）、ヘテロ環基（炭素数１～１２が好ましく、１～８がより好ましく、２～５がさらに好ましい、５員環または６員環を含むことが好ましい）、（メタ）アクリロイル基、（メタ）アクリロイルオキシ基、ハロゲン原子（例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子）、オキソ基（＝Ｏ）、イミノ基（＝ＮＲＮ）、アルキリデン基（＝Ｃ（ＲＮ）２）などが挙げられる。ＲＮは水素原子、アルキル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい）、アルケニル基（炭素数２～１２が好ましく、２～６がより好ましく、２～３がさらに好ましい）、アルケニル基（炭素数２～１２が好ましく、２～６がより好ましく、２～３がさらに好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）、またはアリールアルキル基（炭素数７～２３が好ましく、７～１９がより好ましく、７～１１がさらに好ましい）であり、水素原子、メチル基、エチル基、またはプロピル基が好ましい。各置換基に含まれるアルキル部位、アルケニル部位、およびアルキニル部位は鎖状でも環状でもよく、直鎖でも分岐でもよい。上記置換基Ｔが置換基を取りうる基である場合にはさらに置換基Ｔを有してもよい。例えば、アルキル基は、ハロゲン化アルキル基となってもよいし、(メタ)アクリロイルオキシアルキル基、アミノアルキル基やカルボキシアルキル基になっていてもよい。置換基がカルボキシル基やアミノ基などの塩を形成しうる基の場合、その基が塩を形成していてもよい。 Examples of the substituent T include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms), and an arylalkyl group (preferably having 7 to 21 carbon atoms, more preferably 7 to 15 carbon atoms). 7 to 11 are more preferable), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms), an alkynyl group (preferably 2 to 12 carbon atoms are preferable and 2 to 6 carbon atoms are preferable). More preferably 2 to 3), hydroxyl group, amino group (preferably having 0 to 24 carbon atoms, more preferably 0 to 12 and further preferably 0 to 6), thiol group, carboxyl group, aryl group (carbon A number of 6 to 22, preferably 6 to 18, more preferably 6 to 10, and an alkoxyl group (preferably having a carbon number of 1 to 12, more preferably 1 to 6, To 3 are more preferable), an aryloxy group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms and more preferably 2 to 6 carbon atoms). Preferably 2 to 3), acyloxy groups (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms), aryloyl groups (preferably 7 to 23 carbon atoms, 7 to 19 carbon atoms). More preferably, 7 to 11 are more preferable), aryloyloxy group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 11 carbon atoms), carbamoyl group (preferably 1 to 12 carbon atoms are preferable). 1 to 6 are more preferable, and 1 to 3 are more preferable.) A sulfamoyl group (having 0 to 12 carbon atoms is preferable, 0 to 6 is more preferable, and 0 to 3 is more preferable). ), A sulfo group, an alkylsulfonyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), an arylsulfonyl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms). 6 to 10 are more preferable), a heterocyclic group (preferably having a carbon number of 1 to 12, preferably 1 to 8, more preferably 2 to 5, and preferably including a 5-membered or 6-membered ring), ( (Meth) acryloyl group, (meth) acryloyloxy group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), oxo group (= O), imino group (= NR N ), alkylidene group (= C (R N ) 2 ) and the like. RN represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, 2 to 3 are more preferable), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms). Preferably 6 to 10), or an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 11 carbon atoms), a hydrogen atom, a methyl group, an ethyl group, or A propyl group is preferred. The alkyl moiety, alkenyl moiety, and alkynyl moiety contained in each substituent may be linear or cyclic, and may be linear or branched. When the substituent T is a group that can take a substituent, the substituent T may further have a substituent T. For example, the alkyl group may be a halogenated alkyl group, or may be a (meth) acryloyloxyalkyl group, an aminoalkyl group, or a carboxyalkyl group. When the substituent is a group capable of forming a salt such as a carboxyl group or an amino group, the group may form a salt.
　連結基Ｌとしては、アルキレン基（炭素数１～２４が好ましく、１～１２がより好ましく、１～６がさらに好ましい）、アルケニレン基（炭素数２～１２が好ましく、２～６がより好ましく、２～３がさらに好ましい）、アルキニレン基（炭素数２～１２が好ましく、２～６がより好ましく、２～３がさらに好ましい）、（オリゴ）アルキレンオキシ基（１つの構成単位中のアルキレン基の炭素数は１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい；繰り返し数は１～５０が好ましく、１～４０がより好ましく、１～３０がさらに好ましい）、アリーレン基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）、酸素原子、硫黄原子、スルホニル基、カルボニル基、チオカルボニル基、－ＮＲＮ－、およびそれらの組み合わせにかかる連結基が挙げられる。アルキレン基は上記置換基Ｔを有していてもよい。例えば、アルキレン基がヒドロキシル基を有していてもよい。連結基Ｌに含まれる原子数は水素原子を除いて１～５０が好ましく、１～４０がより好ましく、１～３０がさらに好ましい。連結原子数は連結に関与する原子団のうち最短の道程に位置する原子数を意味する。例えば、－ＣＨ２－（Ｃ＝Ｏ）－Ｏ－だと、連結に関与する原子は６個であり、水素原子を除いても４個である。一方連結に関与する最短の原子は－Ｃ－Ｃ－Ｏ－であり、３個となる。この連結原子数として、１～２４が好ましく、１～１２がより好ましく、１～６がさらに好ましい。なお、上記アルキレン基、アルケニレン基、アルキニレン基、(オリゴ)アルキレンオキシ基は、鎖状でも環状でもよく、直鎖でも分岐でもよい。連結基が－ＮＲＮ－などの塩を形成しうる基の場合、その基が塩を形成していてもよい。 As the linking group L, an alkylene group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms), an alkenylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms) 2 to 3 are more preferable), an alkynylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 and further preferably 2 to 3), an (oligo) alkyleneoxy group (of the alkylene group in one structural unit) The number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3; the number of repetitions is preferably 1 to 50, more preferably 1 to 40, still more preferably 1 to 30, and the arylene group ( Preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), oxygen atom, sulfur atom, sulfonyl group, carbonyl group, thiocarbonyl group, NR N -, and the linking group according to a combination thereof. The alkylene group may have the substituent T. For example, the alkylene group may have a hydroxyl group. The number of atoms contained in the linking group L is preferably 1 to 50, more preferably 1 to 40, and even more preferably 1 to 30, excluding hydrogen atoms. The number of connected atoms means the number of atoms located in the shortest path among the atomic groups involved in the connection. For example, in the case of —CH 2 — (C═O) —O—, there are 6 atoms involved in the connection, and 4 atoms excluding hydrogen atoms. On the other hand, the shortest atom involved in the connection is —C—C—O—, which is three. The number of connecting atoms is preferably 1 to 24, more preferably 1 to 12, and still more preferably 1 to 6. The alkylene group, alkenylene group, alkynylene group, and (oligo) alkyleneoxy group may be linear or cyclic, and may be linear or branched. When the linking group is a group capable of forming a salt such as —NR N —, the group may form a salt.
　脱離成分は分子量が２１０以上である。分子量がこの下限値以上であることで、ベーク中の揮発が抑制され好ましい。脱離成分の分子量は、２１０以上であることが好ましく、２５０以上であることがより好ましく、３００以上であることがさらに好ましい。上限としては、１０００以下であることが実際的である。 The desorption component has a molecular weight of 210 or more. When the molecular weight is equal to or higher than the lower limit, volatilization during baking is suppressed, which is preferable. The molecular weight of the desorbing component is preferably 210 or more, more preferably 250 or more, and even more preferably 300 or more. The upper limit is practically 1000 or less.
　脱離成分の表面張力は、２８ｍＮ／ｍ以上であることが好ましく、３０ｍＮ／ｍ以上であることがより好ましく、３６ｍＮ／ｍ以上であることがさらに好ましく、３８ｍＮ／ｍ以上であることが一層好ましく、４０ｍＮ／ｍ以上であることがより一層好ましく、４２ｍＮ／ｍ以上であることがさらに一層好ましい。上限としては、８０ｍＮ／ｍ以下であることが好ましく、６０ｍＮ／以下であることがより好ましく、５０ｍＮ／ｍ以下であることがさらに好ましい。 The surface tension of the desorbing component is preferably 28 mN / m or more, more preferably 30 mN / m or more, further preferably 36 mN / m or more, and still more preferably 38 mN / m or more. 40 mN / m or more is even more preferable, and 42 mN / m or more is even more preferable. The upper limit is preferably 80 mN / m or less, more preferably 60 mN / m or less, and still more preferably 50 mN / m or less.
　脱離成分のハンセン溶解度パラメータ（ＨＳＰ）ベクトルの：
（ｉ）分散項成分（ｄ成分）は、１４．０～２０．０であることが好ましく、１５．０～１９．０であることがより好ましく、１６．０～１９．５であることがさらに好ましい；
（ｉｉ）極性項成分（ｐ成分）は、２．０～９．０であることが好ましく、３．０～６．０であることがより好ましく、３．５～５．０であることがさらに好ましい；
（ｉｉｉ）水素結合項成分（ｈ成分）は、３．０～１２．０であることが好ましく、４．７～７．０であることがより好ましく、５．０～６．５であることがさらに好ましい。 For the Hansen Solubility Parameter (HSP) vector of the desorption component:
(I) The dispersion term component (component d) is preferably 14.0 to 20.0, more preferably 15.0 to 19.0, and more preferably 16.0 to 19.5. Even more preferred;
(Ii) The polar term component (p component) is preferably from 2.0 to 9.0, more preferably from 3.0 to 6.0, and preferably from 3.5 to 5.0. Even more preferred;
(Iii) The hydrogen bond term component (component h) is preferably 3.0 to 12.0, more preferably 4.7 to 7.0, and more preferably 5.0 to 6.5. Is more preferable.
＜＜特定のポリマー＞＞
　本発明において用いられるポリマー（以下、このポリマーを特定のポリマーと呼ぶことがある）は、この特定のポリマーを含むインプリント用下層膜形成組成物を膜状にし、８０～２５０℃でベークした場合、ポリマーから脱離成分を脱離するポリマーを広く用いることができる。特定のポリマーは、より具体的には、脱離成分となる基を側鎖に有するポリマーであることが好ましい。
　本発明においては、ポリマーを構成する全構成単位の好ましくは３０質量％以上が、より好ましくは４０質量％以上が脱離成分を脱離可能な構成単位である。上限値は特に定めるものではなく、１００質量％であってもよい。尚、本発明では、脱離成分を脱離可能な基を有する構成単位のすべてが８０～２５０℃での加熱で脱離する必要はなく、少なくとも７０質量％が脱離すればよく、８０質量％以上が脱離することが好ましく、９０質量％以上が脱離することがさらに好ましく、９９質量％以上が脱離することが一層好ましい。
　また、本発明では、特定のポリマーの質量の好ましくは２０質量％以上、より好ましくは３０質量％以上、さらに好ましくは５０質量％以上の脱離成分を脱離する。上限値は特に定めるものではないが、例えば、８０質量％以下であり、好ましくは７０質量％以下、より好ましくは６０質量％以下、さらに好ましくは５０質量％以下である。
　特定のポリマーは下記式（Ｒ－１）～（Ｒ－４）のいずれかで表される置換基を含むことが好ましい。
Figure JPOXMLDOC01-appb-C000013
 << Specific polymer >>
The polymer used in the present invention (hereinafter, this polymer may be referred to as a specific polymer) is obtained when the underlayer film forming composition for imprinting containing this specific polymer is formed into a film and baked at 80 to 250 ° C. A wide variety of polymers can be used that desorb the desorbing component from the polymer. More specifically, the specific polymer is preferably a polymer having a group serving as a leaving component in the side chain.
In the present invention, preferably 30% by mass or more, more preferably 40% by mass or more of all structural units constituting the polymer are structural units capable of desorbing a desorbing component. The upper limit is not particularly defined, and may be 100% by mass. In the present invention, it is not necessary for all of the structural units having a group capable of detaching the leaving component to be detached by heating at 80 to 250 ° C., and at least 70% by weight may be removed, and 80% by weight. % Or more is preferably desorbed, more preferably 90% by mass or more is desorbed, and even more preferably 99% by mass or more is desorbed.
In the present invention, the desorbing component 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 mass of the specific polymer. The upper limit is not particularly defined, but is, for example, 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less.
The specific polymer preferably contains a substituent represented by any of the following formulas (R-1) to (R-4).
Figure JPOXMLDOC01-appb-C000013
　式中、Ｒ１～Ｒ３はそれぞれ独立に１価の置換基であり、Ｒ４～Ｒ１２はそれぞれ独立に水素原子または１価の置換基であり、Ｘはポリマーの主鎖への結合位置を表す。 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 is a bonding position to the main chain of the polymer. Represents.
　式（Ｒ－２）～（Ｒ－４）において、Ｒ４～Ｒ６、Ｒ７～Ｒ９、Ｒ１０～Ｒ１２はすべてが水素原子ではないことが好ましい。式（Ｒ－１）における酸素原子と結合する炭素原子、つまりＲ１～Ｒ３が置換する炭素原子（以下、この位置の炭素原子を各式においてα炭素原子と呼ぶ）を含む基は第二級アルキル基または第三級アルキル基であることが好ましい。このことは式（Ｒ－２）も同様であり、α炭素原子を含む基は第二級アルキル基または第三級アルキル基であることが好ましい。これとは異なり、式（Ｒ－３）および（Ｒ－４）におけるα炭素原子を含む基は第一級アルキル基または第二級アルキル基であることが好ましい。 In the formulas (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. A group containing a carbon atom bonded to an oxygen atom in formula (R-1), that is, a carbon atom substituted by R 1 to R 3 (hereinafter, the carbon atom at this position is referred to as an α carbon atom in each formula) is a second group. A primary alkyl group or a tertiary alkyl group is preferred. The same applies to formula (R-2), and the group containing an α carbon atom is preferably a secondary alkyl group or a tertiary alkyl group. In contrast, the group containing the α carbon atom in the formulas (R-3) and (R-4) is preferably a primary alkyl group or a secondary alkyl group.
　Ｒ１～Ｒ３は少なくとも１つが置換基であることが好ましく、少なくとも２つが置換基であることが好ましい。Ｒ４～Ｒ６は少なくとも１つが置換基であることが好ましく、少なくとも２つが置換基であることが好ましい。Ｒ７～Ｒ９は少なくとも１つが置換基であることが好ましく、２つが水素原子で１つが置換基であることが好ましい。Ｒ１０～Ｒ１２は少なくとも１つが置換基であることが好ましく、２つが水素原子で１つが置換基であることが好ましい。Ｒ１～Ｒ３、Ｒ４～Ｒ６、Ｒ７～Ｒ９、Ｒ１０～Ｒ１２が置換基であるとき、この置換基としては、上記Ｒｒ１と同義の基が挙げられ、好ましい範囲も同じである。
　Ｒ１～Ｒ３、Ｒ４～Ｒ６、Ｒ７～Ｒ９、Ｒ１０～Ｒ１２はそれぞれ互いに結合して環を形成していてもよい。Ｒ１～Ｒ１２が置換基であるとき、本発明の効果を奏する範囲でさらに置換基Ｔを有していてもよい。例えば、アルキル基、アルケニル基、アリール基、アリールアルキル基等はさらにハロゲン原子（フッ素原子が好ましい）で置換されていてもよい。 At least one of R 1 to R 3 is preferably a substituent, and at least two are preferably substituents. At least one of R 4 to R 6 is preferably a substituent, and at least two are preferably substituents. At least one of R 7 to R 9 is preferably a substituent, preferably two are hydrogen atoms and one is a substituent. At least one of R 10 to R 12 is preferably a substituent, preferably two are hydrogen atoms and one is a substituent. When R 1 to R 3 , R 4 to R 6 , R 7 to R 9 , R 10 to R 12 are substituents, examples of the substituent include the same groups as R r1 described above, and preferred ranges are also included. 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 as long as the effects of the present invention are exhibited. For example, the alkyl group, alkenyl group, aryl group, arylalkyl group and the like may be further substituted with a halogen atom (a fluorine atom is preferred).
　本発明では、式（Ｒ－１）～（Ｒ－４）のいずれかで表される置換基を含むポリマーから、式中のＣ－Ｏ結合が分解して、式（ｒ１）または（ｒ２）あるいは式（ｒ１－１）で表され、かつ、分子量２１０以上の化合物が脱離することが好ましい。
　特に、式（ｒ１）のＲｒ１およびＲｒ２が置換する炭素原子（Ｒｒ３に含まれる炭素原子を１位として２位の炭素原子）が、脱離前に、式（Ｒ－１）のＲ１～Ｒ３が置換する炭素原子（α炭素原子）であることが好ましい。また、式（ｒ１）の上記２位の炭素原子は、脱離前に、式（Ｒ－２）のＲ４～Ｒ６が置換する炭素原子であることが好ましい。式（ｒ２）については、Ｒｒ４～Ｒｒ６が置換する第三級炭素原子が、脱離前に、上記各α炭素原子、つまり式（Ｒ－１）のＲ１～Ｒ３が置換する炭素原子あるいは式（Ｒ－２）のＲ４～Ｒ６が置換する炭素原子であることが好ましい。 In the present invention, the C—O bond in the formula is decomposed from the polymer containing a substituent represented by any one of the formulas (R-1) to (R-4), and the formula (r1) or (r2) Alternatively, a compound represented by the formula (r1-1) and having a molecular weight of 210 or more is preferably eliminated.
In particular, the carbon atom substituted by R r1 and R r2 in formula (r1) (the carbon atom in the second position with the carbon atom contained in R r3 as the first position) is removed from the R in formula (R-1) before the elimination. 1 to R 3 is preferably a carbon atom (α carbon atom) to be substituted. The carbon atom at the 2-position of the formula (r1) is preferably a carbon atom substituted by R 4 to R 6 of the formula (R-2) before elimination. In the formula (r2), the tertiary carbon atom substituted by R r4 to R r6 is a carbon atom substituted by each of the α carbon atoms, that is, R 1 to R 3 in the formula (R-1) before elimination. An atom or R 4 to R 6 in formula (R-2) is preferably a carbon atom to be substituted.
　式（Ｒ－１）においてＣ－Ｏの位置で分解し、脱離成分側の脱離位置（α炭素原子の位置）に二重結合が形成されるよう、Ｒ１～Ｒ３の少なくとも１つが、アルキル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい）であることが好ましく、エチル基であることがより好ましく、メチル基であることがさらに好ましい。式（Ｒ－２）も同様で、Ｒ４～Ｒ６の少なくとも１つがアルキル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい）であることが好ましく、エチル基であることがより好ましく、メチル基であることがさらに好ましい。 In formula (R-1), at least one of R 1 to R 3 is decomposed at the position of C—O, and a double bond is formed at the elimination position (alpha carbon atom position) on the elimination component side. , Preferably an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), more preferably an ethyl group, and further preferably a methyl group. The same applies to formula (R-2), and at least one of R 4 to R 6 is preferably an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and even more preferably 1 to 3), It is more preferably an ethyl group, and further preferably a methyl group.
　特定のポリマーは、また、重合性基を含むことが好ましく、重合性基は重合性基Ｐｓであることが好ましく、（メタ）アクリロイル基を含むことがより好ましい。重合性基は、脱離成分を脱離可能な基を有する構成単位が有していてもよいし、他の構成単位が有していてもよい。本発明では、少なくとも、脱離成分を脱離可能な基を有する構成単位以外の構成単位が重合性基を有することが好ましい。
　特定のポリマーにおいて、重合性基を有する構成単位の割合は、全構成単位の１０～１００モル％であることが好ましく、５０～１００モル％であることがより好ましく、８０～１００モル％であることがさらに好ましい。 The specific polymer also preferably contains a polymerizable group, the polymerizable group is preferably a polymerizable group Ps, and more preferably contains a (meth) acryloyl group. The polymerizable group may have a constituent unit having a group capable of leaving the leaving component, or may have another constituent unit. In the present invention, it is preferable that at least a constituent unit other than the constituent unit having a group capable of leaving the leaving component has a polymerizable group.
In the specific polymer, the proportion of the structural unit having a polymerizable group is preferably 10 to 100 mol%, more preferably 50 to 100 mol%, and more preferably 80 to 100 mol% of the total structural units. More preferably.
　また、特定のポリマーは、芳香環を含むことが好ましく、芳香環は環ａＣｙまたはｈＣｙであることが好ましい。芳香環は、脱離成分を脱離可能な基を有する構成単位が有していてもよいし、他の構成単位が有していてもよい。本発明では、少なくとも、脱離成分を脱離可能な基を有する構成単位が芳香環を有することが好ましい。
　特定のポリマーにおいて、芳香環を含む構成単位の割合は、全構成単位の１０～１００モル％であることが好ましく、４０～１００モル％であることがより好ましい。 The specific polymer preferably includes an aromatic ring, and the aromatic ring is preferably a ring aCy or hCy. The aromatic ring may be contained in a constituent unit having a group capable of leaving the leaving component, or may be contained in another constituent unit. In the present invention, it is preferable that at least the structural unit having a group capable of leaving the leaving component has an aromatic ring.
In the specific polymer, the proportion of the structural unit containing an aromatic ring is preferably 10 to 100 mol%, and more preferably 40 to 100 mol% of the total structural units.
　特定のポリマーの種類は特に限定されないが、例えば、（メタ）アクリレート樹脂、ポリオレフィン樹脂、ポリスチレン樹脂、フェノール樹脂（ノボラック樹脂）、環状ポリオレフィン樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリアセタール樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリウレタン樹脂、シリコーン樹脂等が挙げられる。 The type of the specific polymer is not particularly limited. For example, (meth) acrylate resin, polyolefin resin, polystyrene resin, phenol resin (novolak resin), cyclic polyolefin resin, polyamide resin, polyimide resin, polyacetal resin, polycarbonate resin, polyester resin , Polyurethane resin, silicone resin and the like.
　特定のポリマーは、下記式（１）～式（６）のいずれかで表される構成単位の少なくとも１種を含むことがさらに好ましい。
Figure JPOXMLDOC01-appb-C000014
 The specific polymer further preferably includes at least one structural unit represented by any of the following formulas (1) to (6).
Figure JPOXMLDOC01-appb-C000014
　ＲＰ４は水素原子またはメチル基である。
　ＲＰ１は、式（ｒ１）または（ｒ２）で表される化合物あるいは式（ｒ１－１）で表される化合物を脱離可能な基を表し、好ましくは、式（Ｒ－１）～（Ｒ－４）で表される基を含む基である。ＲＰ１において、式（Ｒ－１）～（Ｒ－４）のＸと主鎖の原子との間には連結基が介在していてもよい。連結基としては連結基Ｌの例が挙げられる。なお、このときの連結基は３価以上であってもよい。その場合、連結基を介して、ポリマーの構成単位が、式（Ｒ－１）～（Ｒ－４）で表される基を複数ともなっていることとなる。３価以上の連結基としては、芳香環（ａＣｙ、ｈＣｙ）構造の基、アルカン構造の基（炭素数１～４０が好ましく、１～３０がより好ましく、１～２０がさらに好ましい）、アルケン構造の基（炭素数２～４０が好ましく、２～３０がより好ましく、２～２０がさらに好ましい）、アルキン構造の基（炭素数２～４０が好ましく、２～３０がより好ましく、２～２０がさらに好ましい）、またはこれらの組合せに係る基、あるいはこれらと連結基Ｌｈとの組合せに係る基が挙げられる。アルカン構造の基、アルケン構造の基、アルキン構造の基は、鎖状でも環状でもよく、直鎖でも分岐でもよい。以下、この３価以上の連結基を連結基Ｌｍと称する。 R P4 is a hydrogen atom or a methyl group.
R P1 represents a group capable of leaving the compound represented by the formula (r1) or (r2) or the compound represented by the formula (r1-1), and is preferably a group represented by the formula (R-1) to (R -4). In R P1 , a linking group may be interposed between X in the formulas (R-1) to (R-4) and the main chain atom. Examples of the linking group include the linking group L. In this case, the linking group may be trivalent or more. In that case, the structural unit of the polymer has a plurality of groups represented by the formulas (R-1) to (R-4) through the linking group. Examples of the trivalent or higher linking group include a group having an aromatic ring (aCy, hCy) structure, a group having an alkane structure (preferably having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and further preferably 1 to 20 carbon atoms), A group having 2 to 40 carbon atoms (preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms), and an alkyne structure group (2 to 40 carbon atoms are preferable, 2 to 30 carbon atoms are more preferable, and 2 to 20 carbon atoms are And a group according to a combination thereof, or a group according to a combination of these and a linking group Lh. The group having an alkane structure, the group having an alkene structure, or the group having an alkyne structure may be linear or cyclic, and may be linear or branched. Hereinafter, this trivalent or higher valent linking group is referred to as a linking group Lm.
　式（１）～式（６）中、置換基ＲＰ１は同一の構成単位に２つ以上が置換していてもよい。例えば、式（１）、（２）においては、ベンゼン環に２つ以上のＲＰ１が置換しているものも、本発明の好ましい実施形態として挙げられる。 In the formulas (1) to (6), two or more substituents R P1 may be substituted on the same structural unit. For example, in the formulas (1) and (2), those in which two or more R P1 are substituted on the benzene ring are also exemplified as preferred embodiments of the present invention.
　式（１）～（６）中のポリマーの主鎖および置換基ＲＰ１は本発明の効果を奏する範囲で置換基Ｔを有していてもよい。 The polymer main chain and the substituent R P1 in the formulas (1) to (6) may have a substituent T as long as the effects of the present invention are exhibited.
　上記特定のポリマーは、共重合体であることも好ましい。共重合成分は、下記式（１－１）～（１－６）のいずれかで表される構成単位（以下、他の構成単位と称することがある）の少なくとも１種を含むことが好ましい。
Figure JPOXMLDOC01-appb-C000015
 　式（１－１）～式（１－６）中、置換基ＲＰ２はそれぞれ独立に重合性基を含む置換基であり、ＲＰ４は水素原子またはメチル基である。ＲＰ２に含まれる重合性基は上記Ｐｓであることが好ましい。ＲＰ２は重合性基と主鎖との間に連結基をともなっていてもよく、２価の連結基の場合は連結基Ｌの例が挙げられ、３価以上の連結基の場合は連結基Ｌｍの例が挙げられる。式（１－１）～式（１－６）におけるＲＰ２が２つ以上ある場合、すなわち（ＲＰ２）ｎ（ｎは１以上の自然数）となるとき、複数のＲＰ２は互いに結合して環を形成していてもよい。また、ＲＰ２は主鎖に結合して環を形成していてもよい。また、式（１－１）～式（１－６）の主鎖および置換基ＲＰ２には本発明の効果を奏する範囲で置換基Ｔが置換していてもよい。
　ＲＰ２としては下記式（Ｔ２）であることが好ましい。ＲＰ２の式量は、８０以上１０００以下が好ましく、１００以上８００以下がより好ましく、１５０以上６００以下がさらに好ましい。
　　－（Ｌ４）ｎ６－（Ｐ）ｎ７　　　　　（Ｔ２）
　Ｌ４は上記の連結基ＬまたはＬｍであり、なかでもアルキレン基、アリーレン基、(オリゴ)アルキレンオキシ基、カルボニル基、酸素原子、アルカン構造の基、アルケン構造の基、アリール構造の基、これらの組合せに係る連結基が好ましい。ｎ６は０～６の整数である。Ｐは重合性基Ｐｓである。ｎ７は１～６の整数であり、１または２が好ましい。なお、ｎ７が３以上のときは、末端のＬ４が４価以上の連結基になってすべてのＰが置換していてもよいが、２つ以上のＬ４にＰが置換していてもよい。
　特定のポリマーが式（１）で表される構成単位を含む場合、他の構成単位としては、式（１－１）で表される構成単位が好ましい。式（２）～式（６）についても、同様に、それぞれ、式（１－２）～式（１－６）で表される構成単位を含むことが好ましい。 The specific polymer is preferably a copolymer. The copolymer component preferably contains at least one of structural units represented by any of the following formulas (1-1) to (1-6) (hereinafter sometimes referred to as other structural units).
Figure JPOXMLDOC01-appb-C000015
 In formulas (1-1) to (1-6), each of the substituents R P2 is 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 above Ps. RP2 may have a linking group between the polymerizable group and the main chain, and in the case of a divalent linking group, examples of the linking group L are mentioned. An example of Lm is given. When there are two or more R P2 in the formulas (1-1) to (1-6), that is, (R P2 ) n (n is a natural number of 1 or more), a plurality of R P2 are bonded to each other. A ring may be formed. Also, R P2 may form a ring attached to the backbone. Further, the formula (1-1) backbone and substituent T to the extent that the effect of the present invention is the substituent R P2 of to Formula (1-6) may be substituted.
RP2 is preferably the following formula (T2). The formula weight of RP2 is preferably 80 or more and 1000 or less, more preferably 100 or more and 800 or less, and further preferably 150 or more and 600 or less.
-(L 4 ) n6- (P) n7 (T2)
L 4 is the above-described linking group L or Lm, among which an alkylene group, an arylene group, an (oligo) alkyleneoxy group, a carbonyl group, an oxygen atom, an alkane structure group, an alkene structure group, an aryl structure group, The linking group according to the combination is preferable. n6 is an integer of 0-6. P is a polymerizable group Ps. n7 is an integer of 1 to 6, preferably 1 or 2. When n7 is 3 or more, the terminal L 4 may be a tetravalent or higher linking group and all P may be substituted, but two or more L 4 may be substituted with P. Good.
When the specific polymer includes a structural unit represented by the formula (1), the other structural unit is preferably a structural unit represented by the formula (1-1). Similarly, the formulas (2) to (6) preferably include structural units represented by the formulas (1-2) to (1-6), respectively.
　特定のポリマーは、さらに重合性基のない構成単位（「さらに他の構成単位」ということがある）を含むことも好ましい。さらに他の構成単位は、上記他の構成単位で規定した式（１－１）～（１－６）の骨格を有することが好ましい。ただし、置換基ＲＰ２は重合性基のない置換基ＲＰ３となる。さらに他の構成単位である式（１－１）、（１－２）、（１－４）、（１－６）におけるＲＰ２は２つ以上が環構造基に置換していてもよい。なお、さらに他の構成単位にはその主鎖の部分およびＲＰ３に本発明の効果を奏する範囲で置換基Ｔが置換していてもよい。
　ＲＰ３は下記式（Ｔ３）であることが好ましい。ＲＰ３の式量は、８０以上１０００以下が好ましく、１００以上８００以下がより好ましく、１５０以上６００　以下がさらに好ましい。
　　－（Ｌ５）ｎ８－（Ｔ１）ｎ９　　　　　（Ｔ３）
　Ｌ５は上記の連結基ＬまたはＬｍであり、なかでもアルキレン基、アリーレン基、(オリゴ)アルキレンオキシ基、カルボニル基、酸素原子、アルカン構造の基、アルケン構造の基、アリール構造の基、これらの組合せに係る連結基が好ましい。Ｔ１は上記置換基Ｔであり、例えばアルキル基、アリール基、アルコキシ基、アシル基などが挙げられる。ｎ９は１～６の整数であり、１または２が好ましい。ｎ９が３以上のときは、末端のＬ５が４価以上の連結基になってすべてのＴ１が置換していてもよいが、２つ以上のＬ５にＴ１が置換していてもよい。 It is also preferable that the specific polymer further includes a structural unit having no polymerizable group (sometimes referred to as “further structural unit”). Further, the other structural unit preferably has a skeleton of the formulas (1-1) to (1-6) defined in the other structural unit. However, the substituent R P2 becomes a substituent R P3 having no polymerizable group. Furthermore, two or more of R P2 in the other structural units (1-1), (1-2), (1-4), and (1-6) may be substituted with a ring structure group. In addition, the substituent T may be substituted on the other structural unit within the range in which the effect of the present invention is exerted on the main chain portion and R P3 .
RP3 is preferably the following formula (T3). The formula weight of RP3 is preferably 80 or more and 1000 or less, more preferably 100 or more and 800 or less, and further preferably 150 or more and 600 or less.
- (L 5) n8 - ( T 1) n9 (T3)
L 5 is the above linking group L or Lm, among which an alkylene group, an arylene group, an (oligo) alkyleneoxy group, a carbonyl group, an oxygen atom, an alkane structure group, an alkene structure group, an aryl structure group, The linking group according to the combination is preferable. T 1 is the above-described substituent T, and examples thereof include an alkyl group, an aryl group, an alkoxy group, and an acyl group. n9 is an integer of 1 to 6, preferably 1 or 2. When n9 is 3 or more, the terminal L 5 may be a tetravalent or higher linking group and all T 1 may be substituted, but two or more L 5 may be substituted with T 1. Good.
　式Ｔ２，Ｔ３において、Ｌ４、Ｌ５、Ｐ、Ｔ１は本発明の効果を奏する範囲で上記置換基Ｔを有していてもよい。例えば、アルカン構造の基、アルケン構造の基、アリール構造の基等はさらにハロゲン原子（フッ素原子が好ましい）で置換されていてもよい。 In the formulas T2 and T3, L 4 , L 5 , P and T 1 may have the substituent T as long as the effects of the present invention are exhibited. For example, an alkane structure group, an alkene structure group, an aryl structure group, or the like may be further substituted with a halogen atom (a fluorine atom is preferred).
　特定のポリマーにおいて、式（１）～式（６）のいずれかで表される構成単位は、ポリマーのすべてを構成していても（構成比率１００モル％のホモポリマー）、その他の構成単位やさらにその他の構成単位との共重合体となっていてもよい。 In the specific polymer, the structural unit represented by any one of the formulas (1) to (6) may constitute all of the polymer (homopolymer having a structural ratio of 100 mol%), Furthermore, it may be a copolymer with other structural units.
　特定のポリマーにおいて、脱離成分を脱離可能な基を有する構成単位（例えば、式（１）～式（６）で表される構成単位）／その他の構成単位（重合性基を有する構成単位）／さらにその他の構成単位の構成比率は、モル比基準で、１０～１００／０～８０／０～５０が好ましく、３０～１００／０～７０／０～３０がより好ましく、５０～１００／０～５０／０～１０が一層好ましく、５０～９０／１０～５０／０～１０であってもよい。
　特定のポリマーにおいて、脱離成分を脱離可能な基を有する構成単位、その他の構成単位（重合性基を有する構成単位）、さらにその他の構成単位を、それぞれ、１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合は、合計が上記割合となることが好ましい。
　また、本発明では、脱離成分を脱離可能な基を有する構成単位および重合性基を有する構成単位以外のさらにその他の構成単位を実質的に含まない構成とすることも好ましい。実質的に含まないとは、例えば、全構成単位の５質量％以下であることをいい、３質量％以下であることが好ましく、１質量％以下であることがさらに好ましい。 In a specific polymer, a structural unit having a group capable of leaving a leaving component (for example, a structural unit represented by formula (1) to formula (6)) / other structural unit (a structural unit having a polymerizable group) ) / The composition ratio of other structural units is preferably 10 to 100/0 to 80/0 to 50, more preferably 30 to 100/0 to 70/0 to 30, and more preferably 50 to 100 / 0 to 50/0 to 10 is more preferable, and may be 50 to 90/10 to 50/0 to 10.
The specific polymer may contain only one kind of each of a structural unit having a group capable of leaving a leaving component, another structural unit (a structural unit having a polymerizable group), and another structural unit. And 2 or more types may be included. When 2 or more types are included, the total is preferably the above ratio.
Further, in the present invention, it is also preferable that the constitutional unit is substantially free of other constitutional units other than the constitutional unit having a group capable of leaving the leaving component and the constitutional unit having a polymerizable group. “Substantially not contained” means, for example, 5% by mass or less of all structural units, preferably 3% by mass or less, and more preferably 1% by mass or less.
　特定のポリマーの重量平均分子量は、４，０００以上が好ましく、５，０００以上がより好ましく、７，０００以上がさらに好ましく、１０，０００以上がより一層好ましい。上限としては、２，０００，０００以下が好ましく、１，５００，０００以下がより好ましく、１，０００，０００以下がさらに好ましい。重量平均分子量の測定方法は、下記の実施例で示した方法によるものとする。 The weight average molecular weight of the specific polymer is preferably 4,000 or more, more preferably 5,000 or more, further preferably 7,000 or more, and even more preferably 10,000 or more. As an upper limit, 2,000,000 or less is preferable, 1,500,000 or less is more preferable, and 1,000,000 or less is more preferable. The measuring method of a weight average molecular weight shall be based on the method shown in the following Example.
　インプリント用下層膜形成組成物中における、特定のポリマーの含有率は、０．１質量％以上であることが好ましく、０．５質量％以上であることがより好ましく、１．０質量％以上であることがさらに好ましく、１．５質量％以上であることがより一層好ましい。上限としては、１０質量％以下であることが好ましく、７質量％以下であることがより好ましく、５質量％以下であることがさらに好ましく、４質量％以下であることがより一層好ましく、３質量％以下であることがさらに一層好ましい。この量を上記下限値以上とすることで、ポリマーを配合したことによる効果を好適に発揮させることができ、また、均一な薄膜を調製しやすくなる。一方上記上限値以下とすることにより、溶剤を用いた効果が好適に発揮され、広い面積に均一な膜を形成しやすくなる。
　また、インプリント用下層膜形成組成物中の不揮発性成分（組成物中の溶剤を除いた固形分を意味する）に対する、特定のポリマーの含有率は、９０質量％以上であることが好ましく、９５質量％以上であることがより好ましく、９９質量％以上であることがさらに好ましい。上限値としては、１００質量％である。この量を上記下限値以上とすることで、ポリマーを配合したことによる効果を好適に発揮させることができ、また、均一な薄膜を調製しやすくなる。一方上記上限値以下とすることにより、溶剤を用いた効果が好適に発揮され、広い面積に均一な膜を形成しやすくなる。
　特定のポリマーは、１種のみ用いてもよいし、２種以上用いてもよい。２種以上用いる場合、合計量が上記範囲となることが好ましい。 The content of the specific polymer in the composition for forming a lower layer film for imprinting is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1.0% by mass or more. It is more preferable that it is 1.5 mass% or more. As an upper limit, it is preferable that it is 10 mass% or less, It is more preferable that it is 7 mass% or less, It is further more preferable that it is 5 mass% or less, It is still more preferable that it is 4 mass% or less, 3 mass % Or less is even more preferable. By making this quantity more than the said lower limit, the effect by having mix | blended the polymer can be exhibited suitably, and it becomes easy to prepare a uniform thin film. On the other hand, when the amount is not more than the above upper limit value, the effect of using the solvent is suitably exhibited, and it becomes easy to form a uniform film over a wide area.
Further, the content of the specific polymer with respect to the non-volatile component (meaning the solid content excluding the solvent in the composition) in the underlayer film-forming composition for imprints is preferably 90% by mass or more, It is more preferably 95% by mass or more, and further preferably 99% by mass or more. The upper limit is 100% by mass. By making this quantity more than the said lower limit, the effect by having mix | blended the polymer can be exhibited suitably, and it becomes easy to prepare a uniform thin film. On the other hand, when the amount is not more than the above upper limit value, the effect of using the solvent is suitably exhibited, and it becomes easy to form a uniform film over a wide area.
One kind of specific polymer may be used, or two or more kinds thereof may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
　上記のポリマーにおいて脱離成分をなす置換基ＲＰ１は主鎖に常法により導入することができる。 In the above polymer, the substituent R P1 which forms a leaving component can be introduced into the main chain by a conventional method.
＜＜脱離反応促進剤またはその前駆体＞＞
　脱離反応促進剤は、系内で特定のポリマーと共存することにより、所定のきっかけにより特定のポリマーにはたらきかけ、特定のポリマーから脱離成分を脱離させる反応を促す化合物である。脱離反応促進剤は、酸性官能基または、塩基性官能基を有する化合物である。脱離反応促進剤は、組成物中ではその前駆体として存在することが好ましい。前駆体としては例えば熱や光などの外部からのエネルギーの付与により反応し、脱離反応促進剤化合物に変換される化合物が挙げられる。具体例には、熱酸発生剤、光酸発生剤、熱塩基発生剤、光塩基発生剤などが挙げられ、熱酸発生剤、光酸発生剤、が好ましく、熱酸発生剤がより好ましい。
　脱離反応促進剤としては、酸性官能基を有する場合、脱離促進剤のｐＫａは、２以下が好ましく、１以下がより好ましく、０以下がさらに好ましい。下限値としては、特に定めるものではないが、例えば－１０以上であってもよい。塩基性官能基を有する場合、その共役酸のｐＫａは、５以上が好ましく、７以上がより好ましく、８以上がさらに好ましい。上限値としては、特に定めるものではないが、例えば、１５以下であってもよい。
　本発明では、脱離反応促進剤またはその前駆体の具体例としては、特開２０１４－０４７３２９号公報の段落００１２、００１７、００２６～００３７に記載の酸増殖剤、段落００３８～００４０に記載の光酸発生剤、段落００４１に記載の熱酸発生剤、特開２０１２－２３７７７６号公報の段落００２９～００６６に記載の光塩基増殖剤、段落００７３～００８７に記載の光塩基発生剤、段落００８７～００９０に記載の熱塩基発生剤、特許第５６８７４４２号公報の段落００１２～００１５、００２３～００２９に記載の光酸発生剤、国際公開第２００９／１２３１２２号の段落００３３～００７５に記載の塩基発生剤、特開２０１１－２３６４１６号公報の段落００３８～００６９に記載の塩基発生剤を用いることができ、これらの内容は本明細書に組み込まれる。 << Elimination reaction accelerator or precursor thereof >>
A desorption reaction accelerator is a compound that, when coexisting with a specific polymer in the system, acts on a specific polymer by a predetermined trigger and promotes a reaction for desorbing a desorbing component from the specific polymer. The elimination reaction accelerator is a compound having an acidic functional group or a basic functional group. The elimination reaction accelerator is preferably present as a precursor in the composition. Examples of the precursor include a compound that reacts by applying external energy such as heat and light, and is converted into an elimination reaction accelerator compound. Specific examples include thermal acid generators, photoacid generators, thermal base generators, photobase generators, thermal acid generators and photoacid generators are preferred, and thermal acid generators are more preferred.
When the elimination reaction accelerator has an acidic functional group, the pKa of the elimination accelerator is preferably 2 or less, more preferably 1 or less, and even more preferably 0 or less. The lower limit is not particularly defined, but may be, for example, −10 or more. In the case of having a basic functional group, the pKa of the conjugate acid is preferably 5 or more, more preferably 7 or more, and still more preferably 8 or more. The upper limit value is not particularly defined, but may be 15 or less, for example.
In the present invention, specific examples of the elimination reaction accelerator or its precursor include acid proliferators described in paragraphs 0012, 0017, and 0026 to 0037 of JP 2014-047329 A, and light described in paragraphs 0038 to 0040. Acid generator, thermal acid generator described in paragraph 0041, photobase proliferating agent described in paragraphs 0029 to 0066 of JP2012-237776, photobase generator described in paragraphs 0073 to 0087, paragraphs 0087 to 0090 A thermal base generator described in paragraphs 0012 to 0015 and 0023 to 0029 of Japanese Patent No. 5687442; a photoacid generator described in paragraphs 0033 to 0075 of WO 2009/123122; The base generators described in paragraphs 0038 to 0069 of Kai 2011-236416 can be used, and among these, Of which are incorporated herein.
　脱離反応促進剤またはその前駆体の含有量は、不揮発性成分の０．１質量％以上であることが好ましく、１.０質量％以上であることがより好ましく、２.０質量％以上であることがさらに好ましい。上限としては、１０．０質量％以下であることが実際的であり、５.０質量％以下であってもよい。
　脱離反応促進剤またはその前駆体は、１種のみ用いてもよいし、２種以上用いてもよい。２種以上用いる場合、合計量が上記範囲となることが好ましい。 The content of the elimination 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 2.0% by mass or more. More preferably it is. As an upper limit, it is practical that it is 10.0 mass% or less, and may be 5.0 mass% or less.
Only one type of elimination reaction accelerator or its precursor may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
＜＜アルキレングリコール化合物＞＞
　インプリント用下層膜形成組成物は、アルキレングリコール化合物を含んでいてもよい。アルキレングリコール化合物は、アルキレングリコール構成単位を３～１０００個有していることが好ましく、４～５００個有していることがより好ましく、５～１００個有していることがさらに好ましく、５～５０個有していることが一層好ましい。アルキレングリコール化合物の重量平均分子量（Ｍｗ）は１５０～１００００が好ましく、２００～５０００がより好ましく、３００～３０００がさらに好ましく、３００～１０００が一層好ましい。
　アルキレングリコール化合物は、ポリエチレングリコール、ポリプロピレングリコール、これらのモノまたはジメチルエーテル、モノまたはジオクチルエーテル、モノまたはジノニルエーテル、モノまたはジデシルエーテル、モノステアリン酸エステル、モノオレイン酸エステル、モノアジピン酸エステル、モノコハク酸エステルが例示され、ポリエチレングリコール、ポリプロピレングリコールが好ましい。
　アルキレングリコール化合物の２３℃における表面張力は、３８．０ｍＮ/ｍ以上であることが好ましく、４０．０ｍＮ/ｍ以上であることがより好ましい。表面張力の上限は特に定めるものではないが、例えば４８．０ｍＮ/ｍ以下である。このような化合物を配合することにより、下層膜の直上に設けるインプリント用硬化性組成物の濡れ性をより向上させることができる。 << Alkylene glycol compound >>
The undercoat film-forming composition for imprinting may contain an alkylene glycol compound. The alkylene glycol compound preferably has 3 to 1000 alkylene glycol structural units, more preferably 4 to 500, still more preferably 5 to 100, and more preferably 5 to It is more preferable to have 50 pieces. The weight average molecular weight (Mw) of the alkylene glycol compound is preferably 150 to 10,000, more preferably 200 to 5,000, still more preferably 300 to 3,000, and even more preferably 300 to 1,000.
The alkylene glycol compounds are polyethylene glycol, polypropylene glycol, mono- or dimethyl ether, mono- or dioctyl ether, mono- or dinonyl ether, mono- or didecyl ether, monostearate, monooleate, monoadipate, monosuccinate. Examples of the acid ester include polyethylene glycol and polypropylene glycol.
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 defined, but is, for example, 48.0 mN / m or less. By blending such a compound, the wettability of the curable composition for imprints provided immediately above the lower layer film can be further improved.
　アルキレングリコール化合物は、含有する場合、不揮発性成分の４０質量％以下であり、３０質量％以下であることが好ましく、２０質量％以下であることがより好ましく、１～１５質量％であることがさらに好ましい。
　アルキレングリコール化合物は、１種のみ用いてもよいし、２種以上用いてもよい。２種以上用いる場合、合計量が上記範囲となることが好ましい。 When the alkylene glycol compound is contained, it is 40% by mass or less of the nonvolatile component, preferably 30% by mass or less, more preferably 20% by mass or less, and preferably 1 to 15% by mass. Further preferred.
One type of alkylene glycol compound may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
＜＜重合開始剤＞＞
　不揮発性成分として、重合開始剤を含んでいてもよい。重合開始剤としては熱重合開始剤や光重合開始剤等が挙げられるが、インプリント用硬化性組成物との架橋反応性を向上させる観点から光重合開始剤が好ましい。光重合開始剤としては、ラジカル重合開始剤、カチオン重合開始剤が好ましく、ラジカル重合開始剤がより好ましい。また、本発明において、光重合開始剤は複数種を併用してもよい。 << Polymerization initiator >>
As a non-volatile component, a polymerization initiator may be included. Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator, and a photopolymerization initiator is preferred from the viewpoint of improving the crosslinking reactivity with the curable composition for imprints. 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.
　光重合開始剤としては、公知の化合物を任意に使用できる。例えば、ハロゲン化炭化水素誘導体（例えば、トリアジン骨格を含む化合物、オキサジアゾール骨格を含む化合物、トリハロメチル基を含む化合物など）、アシルホスフィンオキサイド等のアシルホスフィン化合物、ヘキサアリールビイミダゾール、オキシム誘導体等のオキシム化合物、有機過酸化物、チオ化合物、ケトン化合物、芳香族オニウム塩、ケトオキシムエーテル、アミノアセトフェノン化合物、ヒドロキシアセトフェノン、アゾ系化合物、アジド化合物、メタロセン化合物、有機ホウ素化合物、鉄アレーン錯体などが挙げられる。これらの中でもオキシム化合物が好ましい。これらの詳細については、特開２０１６－０２７３５７号公報の段落０１６５～０１８２の記載を参酌でき、この内容は本明細書に組み込まれる。
　アシルホスフィン化合物としては、２，４，６－トリメチルベンゾイル－ジフェニル－ホスフィンオキサイドなどが挙げられる。また、市販品であるＩＲＧＡＣＵＲＥ－８１９やＩＲＧＡＣＵＲＥ１１７３、ＩＲＧＡＣＵＲＥ－ＴＰＯ（商品名：いずれもＢＡＳＦ製）を用いることができる。 As the photopolymerization initiator, known compounds can be arbitrarily used. For example, halogenated hydrocarbon derivatives (eg, compounds containing a triazine skeleton, compounds containing an oxadiazole skeleton, compounds containing a trihalomethyl group), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives, etc. Oxime compounds, 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, etc. Can be mentioned. Of these, oxime compounds are preferred. With respect to these details, reference can be made to the descriptions in paragraphs 0165 to 0182 of JP-A-2016-027357, the contents of which are incorporated herein.
Examples of the acylphosphine compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Commercially available products such as IRGACURE-819, IRGACURE1173, and IRGACURE-TPO (trade names: all manufactured by BASF) can be used.
　上記インプリント用下層膜形成組成物に用いられる光重合開始剤の含有量は、配合する場合、不揮発性成分中、例えば、０．０１～１５質量％であり、好ましくは０．１～１２質量％であり、さらに好ましくは０．２～７質量％である。２種以上の光重合開始剤を用いる場合は、その合計量が上記範囲となる。 When blended, the content of the photopolymerization initiator used in the above-described imprint lower layer film-forming composition is, for example, 0.01 to 15% by mass, preferably 0.1 to 12% by mass in the nonvolatile component. %, More preferably 0.2 to 7% by mass. When using 2 or more types of photoinitiators, the total amount becomes the said range.
＜＜重合禁止剤＞＞
　不揮発性成分として、重合禁止剤を含んでいてもよい。本実施形態に係る重合禁止剤（Ｂ）は、硬化性主剤（Ａ）で発生したラジカルが成長反応を起こす前に、そのラジカルをトラップする能力をもつ化合物である。これにより、重合禁止剤（Ｂ）は、硬化性主剤（Ａ）の重合を阻害するように作用する。 << Polymerization inhibitor >>
As a non-volatile component, a polymerization inhibitor may be included. The polymerization inhibitor (B) according to the present embodiment is a compound having the ability to trap radicals generated in the curable main agent (A) before they undergo a growth reaction. Thereby, a polymerization inhibitor (B) acts so that superposition | polymerization of a sclerosing | hardenable main ingredient (A) may be inhibited.
　重合禁止剤（Ｂ）は、ヒドロキノン類、カテコール類、フェノチアジン、フェノキサジンのいずれかでありうる。重合禁止剤（Ｂ）の具体例としては、４－メトキシフェノール、４－メトキシ－１－ナフトール、４－ｔｅｒｔ－ブチルカテコール、２，６－ジ－ｔｅｒｔ－ブチルフェノール、２，６－ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール、２－ｔｅｒｔ－ブチル－４，６－ジメチルフェノール、２，４，６－トリ－ｔｅｒｔ－ブチルフェノール、ヒドロキノン、ｔｅｒｔ－ブチルヒドロキノンなどのフェノール系化合物を挙げることができる。重合禁止剤（Ｂ）の具体例としては、ナフトキノン、ベンゾキノンなどのキノン系化合物を挙げることもできる。重合禁止剤（Ｂ）の具体例としては、フェノチアジン、フェノキサジン、４－ヒドロキシ－２，２，６，６－テトラメチルピペリジンなどのアミン系化合物を挙げることもできる。重合禁止剤（Ｂ）の具体例としては、２，２，６，６－テトラメチルピペリジン－Ｎ－オキシル、４－ヒドロキシ－２，２，６，６－テトラメチルピペリジン－Ｎ－オキシルなどのＮ－オキシル系化合物を挙げることもできる。ここで挙げた化合物は例示に過ぎず、重合禁止剤（Ｂ）は、他の化合物であってもよい。 The polymerization inhibitor (B) can be any of hydroquinones, catechols, phenothiazines, and phenoxazines. Specific examples of the polymerization inhibitor (B) include 4-methoxyphenol, 4-methoxy-1-naphthol, 4-tert-butylcatechol, 2,6-di-tert-butylphenol, 2,6-di-tert- Mention may be made of phenolic compounds such as butyl-p-cresol, 2-tert-butyl-4,6-dimethylphenol, 2,4,6-tri-tert-butylphenol, hydroquinone and tert-butylhydroquinone. Specific examples of the polymerization inhibitor (B) include quinone compounds such as naphthoquinone and benzoquinone. Specific examples of the polymerization inhibitor (B) include amine compounds such as phenothiazine, phenoxazine, and 4-hydroxy-2,2,6,6-tetramethylpiperidine. Specific examples of the polymerization inhibitor (B) include N, such as 2,2,6,6-tetramethylpiperidine-N-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl. -Oxyl compounds can also be mentioned. The compounds listed here are merely examples, and the polymerization inhibitor (B) may be other compounds.
　重合禁止剤の含有量は、固形成分の０．０００１質量％以上１０.０質量％以下であることが好ましく、０．００１質量％以上１.０質量％以下であることがより好ましく、０．００５質量％以上０.１質量％以下であることがさらに好ましい。重合禁止剤は、１種のみ用いてもよいし、２種以上用いてもよい。２種以上用いる場合、それらの合計量が上記範囲となることが好ましい。 The content of the polymerization inhibitor is preferably 0.0001% by mass or more and 10.0% by mass or less of the solid component, more preferably 0.001% by mass or more and 1.0% by mass or less. More preferably, it is 005 mass% or more and 0.1 mass% or less. Only one type of polymerization inhibitor may be used, or two or more types may be used. When using 2 or more types, it is preferable that those total amounts become the said range.
＜＜その他の成分＞＞
　インプリント用下層膜形成組成物に配合される不揮発性成分としては、上記化合物の他に、熱重合開始剤、酸化防止剤、レベリング剤、増粘剤、界面活性剤等を１種または２種以上含んでいてもよい。
　熱重合開始剤等については、特開２０１３－０３６０２７号公報、特開２０１４－０９０１３３号公報、特開２０１３－１８９５３７号公報に記載の各成分を用いることができる。含有量等についても、上記公報の記載を参酌できる。
　また、本発明では、インプリント用下層膜形成組成物が実質的に界面活性剤を含まない構成とすることもできる。実質的に含まないとは、インプリント用下層膜形成組成物中の不揮発性成分の０．１質量％以下であることをいう。 << Other ingredients >>
As a non-volatile component mix | blended with the underlayer film forming composition for imprints, in addition to the said compound, 1 type or 2 types of thermal polymerization initiators, antioxidants, leveling agents, thickeners, surfactants, etc. The above may be included.
Regarding the thermal polymerization initiator and the like, each component described in JP2013-036027A, JP2014-090133A, JP2013-189537A can be used. Regarding the content and the like, the description in the above publication can be referred to.
Moreover, in this invention, it can also be set as the structure which does not contain surfactant substantially in the underlayer film forming composition for imprints. “Substantially not contained” means 0.1% by mass or less of the nonvolatile component in the composition for forming a lower layer film for imprinting.
＜＜下層膜用溶剤＞＞
　インプリント用下層膜形成組成物は溶剤を含む。溶剤は例えば、２３℃で液体であって沸点が２５０℃以下の化合物（下層膜用溶剤）を７０．０質量％以上の割合で含むことが好ましい。通常、不揮発性成分が最終的に下層膜を形成する。インプリント用下層膜形成組成物は、下層膜用溶剤を８０．０質量％以上含むことが好ましく、９０．０質量％以上であることがより好ましく、９３．０質量％以上であることがより好ましく、９４．０質量％以上であることがさらに好ましく、９５．０質量％以上、９８．０質量％以上、９９．０質量％以上であってもよい。
　溶剤は、インプリント用下層膜形成組成物に、１種のみ含まれていてもよいし、２種以上含まれていてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。
　下層膜用溶剤の沸点は、２３０℃以下であることが好ましく、２００℃以下であることがより好ましく、１８０℃以下であることがさらに好ましく、１６０℃以下であることが一層好ましく、１３０℃以下であることがより一層好ましい。下限値は２３℃であるが、６０℃以上であることが実際的である。沸点を上記の範囲とすることにより、下層膜から溶剤を容易に除去でき好ましい。 << Solvent for Underlayer Film >>
The underlayer film forming composition for imprints contains a solvent. The solvent preferably contains, for example, a compound having a boiling point of 250 ° C. or lower (solvent for the lower layer film) at a rate of 70.0% by mass or more at 23 ° C. Usually, the nonvolatile component finally forms the lower layer film. The lower film forming composition for imprinting preferably contains 80.0% by mass or more of the solvent for the lower layer film, more preferably 90.0% by mass or more, and more preferably 93.0% by mass or more. Preferably, it is 94.0 mass% or more, and 95.0 mass% or more, 98.0 mass% or more, and 99.0 mass% or more may be sufficient.
As for the solvent, only 1 type may be contained in the underlayer film forming composition for imprint, and 2 or more types may be contained. When 2 or more types are included, the total amount is preferably within the above range.
The boiling point of the solvent for the lower layer film is preferably 230 ° C. or less, more preferably 200 ° C. or less, further preferably 180 ° C. or less, further preferably 160 ° C. or less, and 130 ° C. or less. Is more preferable. The lower limit is 23 ° C., but practically 60 ° C. or higher. By setting the boiling point within the above range, the solvent can be easily removed from the lower layer film, which is preferable.
　下層膜用溶剤は、有機溶剤が好ましい。溶剤は、好ましくはエステル基、カルボニル基、ヒドロキシル基およびエーテル基のいずれか１つ以上を含む溶剤である。なかでも、非プロトン性極性溶剤を用いることが好ましい。 The solvent for the lower layer film is preferably an organic solvent. The solvent is preferably a solvent containing any one or more of an ester group, a carbonyl group, a hydroxyl group and an ether group. Among these, it is preferable to use an aprotic polar solvent.
　具体例としては、アルコキシアルコール、プロピレングリコールモノアルキルエーテルカルボキシレート、プロピレングリコールモノアルキルエーテル、乳酸エステル、酢酸エステル、アルコキシプロピオン酸エステル、鎖状ケトン、環状ケトン、ラクトン、およびアルキレンカーボネートが選択される。 As specific examples, alkoxy alcohol, propylene glycol monoalkyl ether carboxylate, propylene glycol monoalkyl ether, lactic acid ester, acetic acid ester, alkoxypropionic acid ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate are selected.
　アルコキシアルコールとしては、メトキシエタノール、エトキシエタノール、メトキシプロパノール（例えば、１－メトキシ－２－プロパノール）、エトキシプロパノール（例えば、１－エトキシ－２－プロパノール）、プロポキシプロパノール（例えば、１－プロポキシ－２－プロパノール）、メトキシブタノール（例えば、１－メトキシ－２－ブタノール、１－メトキシ－３－ブタノール）、エトキシブタノール（例えば、１－エトキシ－２－ブタノール、１－エトキシ－３－ブタノール）、メチルペンタノール（例えば、４－メチル－２－ペンタノール）などが挙げられる。 Examples of the alkoxy alcohol include methoxyethanol, ethoxyethanol, methoxypropanol (eg 1-methoxy-2-propanol), ethoxypropanol (eg 1-ethoxy-2-propanol), propoxypropanol (eg 1-propoxy-2- Propanol), methoxybutanol (eg 1-methoxy-2-butanol, 1-methoxy-3-butanol), ethoxybutanol (eg 1-ethoxy-2-butanol, 1-ethoxy-3-butanol), methylpentanol (For example, 4-methyl-2-pentanol).
　プロピレングリコールモノアルキルエーテルカルボキシレートとしては、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルプロピオネート、および、プロピレングリコールモノエチルエーテルアセテートからなる群より選択される少なくとも１つが好ましく、プロピレングリコールモノメチルエーテルアセテートであることが特に好ましい。 The propylene glycol monoalkyl ether carboxylate is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate. It is particularly preferred.
　また、プロピレングリコールモノアルキルエーテルとしては、プロピレングリコールモノメチルエーテルまたはプロピレングリコールモノエチルエーテルが好ましい。
　乳酸エステルとしては、乳酸エチル、乳酸ブチル、または乳酸プロピルが好ましい。
　酢酸エステルとしては、酢酸メチル、酢酸エチル、酢酸ブチル、酢酸イソブチル、酢酸プロピル、酢酸イソアミル、蟻酸メチル、蟻酸エチル、蟻酸ブチル、蟻酸プロピル、または酢酸３－メトキシブチルが好ましい。
　アルコキシプロピオン酸エステルとしては、３－メトキシプロピオン酸メチル（ＭＭＰ）、または、３－エトキシプロピオン酸エチル（ＥＥＰ）が好ましい。
　鎖状ケトンとしては、１－オクタノン、２－オクタノン、１－ノナノン、２－ノナノン、アセトン、４－ヘプタノン、１－ヘキサノン、２－ヘキサノン、ジイソブチルケトン、フェニルアセトン、メチルエチルケトン、メチルイソブチルケトン、アセチルアセトン、アセトニルアセトン、イオノン、ジアセトニルアルコール、アセチルカービノール、アセトフェノン、メチルナフチルケトンまたはメチルアミルケトンが好ましい。
　環状ケトンとしては、メチルシクロヘキサノン、イソホロンまたはシクロヘキサノンが好ましい。
　ラクトンとしては、γ－ブチロラクトンが好ましい。
　アルキレンカーボネートとしては、プロピレンカーボネートが好ましい。 Moreover, as propylene glycol monoalkyl ether, propylene glycol monomethyl ether or propylene glycol monoethyl ether is preferable.
As the lactic acid ester, ethyl lactate, butyl lactate or propyl lactate is preferable.
As the 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 preferable.
Examples of chain ketones include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, Acetonyl acetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone or methyl amyl ketone are preferred.
As the cyclic ketone, methylcyclohexanone, isophorone or cyclohexanone is preferable.
As the lactone, γ-butyrolactone is preferable.
As the alkylene carbonate, propylene carbonate is preferable.
　上記成分の他、炭素数が７以上（７～１４が好ましく、７～１２がより好ましく、７～１０がさらに好ましい）、かつ、ヘテロ原子数が２以下のエステル系溶剤を用いることが好ましい。 In addition to the above components, it is preferable to use an ester solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, more preferably 7 to 10) and a hetero atom number of 2 or less.
　炭素数が７以上かつヘテロ原子数が２以下のエステル系溶剤の好ましい例としては、酢酸アミル、酢酸２－メチルブチル、酢酸１-メチルブチル、酢酸ヘキシル、プロピオン酸ペンチル、プロピオン酸ヘキシル、プロピオン酸ブチル、イソ酪酸イソブチル、プロピオン酸ヘプチル、ブタン酸ブチルなどが挙げられ、酢酸イソアミルを用いることが特に好ましい。 Preferred examples of the ester solvent having 7 or more carbon atoms and 2 or less hetero atoms include amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, butyl propionate, Examples thereof include isobutyl isobutyrate, heptyl propionate, and butyl butanoate, and it is particularly preferable to use isoamyl acetate.
　また、引火点（以下、ｆｐともいう）が３０℃以上である溶剤を用いることも好ましい。このような成分としては、プロピレングリコールモノメチルエーテル（ｆｐ：４７℃）、乳酸エチル（ｆｐ：５３℃）、３－エトキシプロピオン酸エチル（ｆｐ：４９℃）、メチルアミルケトン（ｆｐ：４２℃）、シクロヘキサノン（ｆｐ：３０℃）、酢酸ペンチル（ｆｐ：４５℃）、２－ヒドロキシイソ酪酸メチル（ｆｐ：４５℃）、γ－ブチロラクトン（ｆｐ：１０１℃）またはプロピレンカーボネート（ｆｐ：１３２℃）が好ましい。これらのうち、プロピレングリコールモノエチルエーテル、乳酸エチル、酢酸ペンチルまたはシクロヘキサノンがさらに好ましく、プロピレングリコールモノエチルエーテルまたは乳酸エチルが特に好ましい。 It is also preferable to use a solvent having a flash point (hereinafter also referred to as fp) of 30 ° C. or higher. Examples of such components include propylene glycol monomethyl ether (fp: 47 ° C.), ethyl lactate (fp: 53 ° C.), ethyl 3-ethoxypropionate (fp: 49 ° C.), methyl amyl ketone (fp: 42 ° C.), Cyclohexanone (fp: 30 ° C.), pentyl acetate (fp: 45 ° C.), methyl 2-hydroxyisobutyrate (fp: 45 ° C.), γ-butyrolactone (fp: 101 ° C.) or propylene carbonate (fp: 132 ° C.) is preferred. . Of these, propylene glycol monoethyl ether, ethyl lactate, pentyl acetate or cyclohexanone is more preferred, and propylene glycol monoethyl ether or ethyl lactate is particularly preferred.
　下層膜用溶剤として中でも好ましい溶剤としては、水、１－メトキシ－２－プロパノール、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）、エトキシエチルプロピオネート、シクロヘキサノン、２－ヘプタノン、γ－ブチロラクトン、酢酸ブチル、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）、乳酸エチルおよび４－メチル－２－ペンタノールからなる群から選択される少なくとも１種であり、１－メトキシ－２－プロパノール、ＰＧＭＥＡ、酢酸ブチルからなる群から選択される少なくとも１種がさらに好ましい。 Among the solvents for the lower layer film, water, 1-methoxy-2-propanol, propylene glycol monomethyl ether acetate (PGMEA), ethoxyethyl propionate, cyclohexanone, 2-heptanone, γ-butyrolactone, butyl acetate, propylene At least one selected from the group consisting of glycol monomethyl ether (PGME), ethyl lactate and 4-methyl-2-pentanol, selected from the group consisting of 1-methoxy-2-propanol, PGMEA and butyl acetate At least one is more preferable.
　インプリント用下層膜形成組成物の収容容器としては従来公知の収容容器を用いることができる。また、収容容器としては、原材料や組成物中への不純物混入を抑制することを目的に、容器内壁を６種６層の樹脂で構成された多層ボトルや、６種の樹脂を７層構造にしたボトルを使用することも好ましい。このような容器としては例えば特開２０１５－１２３３５１号公報に記載の容器が挙げられる。 A conventionally known storage container can be used as the storage container for the composition for forming an underlayer film for imprint. In addition, as a container, for the purpose of suppressing contamination of raw materials and compositions, the inner wall of the container is a multi-layer bottle composed of 6 types and 6 layers of resin, and 6 types of resins are made into a 7 layer structure. It is also preferred to use bottles that have been used. Examples of such a container include a container described in JP-A-2015-123351.
＜インプリント用硬化性組成物＞
＜＜重合性化合物＞＞
　インプリント用硬化性組成物は、重合性化合物を含むことが好ましく、芳香環を有する重合性化合物を含むことが好ましい。重合性化合物は、単官能重合性化合物であってもよいし、多官能重合性化合物であってよい。また、単官能重合性化合物と多官能重合性化合物の両方を含むことが好ましい。 <Curable composition for imprint>
<< polymerizable compound >>
The curable composition for imprints preferably contains a polymerizable compound, and preferably contains a polymerizable compound having an aromatic ring. The polymerizable compound may be a monofunctional polymerizable compound or a polyfunctional polymerizable compound. Moreover, it is preferable that both a monofunctional polymerizable compound and a polyfunctional polymerizable compound are included.
＜＜＜単官能重合性化合物＞＞＞
　インプリント用硬化性組成物に用いる単官能重合性化合物の分子量は、５０以上が好ましく、１００以上がより好ましく、１５０以上がさらに好ましい。分子量は、また、１,０００以下が好ましく、８００以下がより好ましく、３００以下がさらに好ましく、２７０以下が一層好ましい。分子量を上記下限値以上とすることで、揮発性を抑制できる傾向がある。分子量を上記上限値以下とすることで、粘度を低減できる傾向がある。
　インプリント用硬化性組成物に用いる単官能重合性化合物の沸点は、８５℃以上であることが好ましく、１１０℃以上がより好ましく、１３０℃以上がさらに好ましい。沸点を上記下限値以上とすることで、揮発性を抑制することができる。沸点の上限値については、特に定めるものでは無いが、例えば、沸点を３５０℃以下とすることができる。 <<< monofunctional polymerizable compound >>>
The molecular weight of the monofunctional polymerizable compound used in the curable composition for imprints is preferably 50 or more, more preferably 100 or more, and still more preferably 150 or more. The molecular weight is preferably 1,000 or less, more preferably 800 or less, further preferably 300 or less, and even more preferably 270 or less. There exists a tendency which can suppress volatility by making molecular weight more than the said lower limit. By setting the molecular weight to the above upper limit or less, the viscosity tends to be reduced.
The boiling point of the monofunctional polymerizable compound used in the curable composition for imprints is preferably 85 ° C. or higher, more preferably 110 ° C. or higher, and further preferably 130 ° C. or higher. By setting the boiling point to the above lower limit or more, volatility can be suppressed. The upper limit of the boiling point is not particularly defined, but for example, the boiling point can be 350 ° C. or lower.
　インプリント用硬化性組成物に用いる単官能重合性化合物が有する重合性基の種類は特に定めるものでは無いが、エチレン性不飽和基、エポキシ基等が例示され、エチレン性不飽和基が好ましい。エチレン性不飽和基としては、（メタ）アクリロイル基が好ましく、アクリロイル基がより好ましい。 The type of polymerizable group possessed by the monofunctional polymerizable compound used in the curable composition for imprints is not particularly defined, and examples thereof include ethylenically unsaturated groups and epoxy groups, with ethylenically unsaturated groups being preferred. As the ethylenically unsaturated group, a (meth) acryloyl group is preferable, and an acryloyl group is more preferable.
　インプリント用硬化性組成物に用いる単官能重合性化合物を構成する原子の種類は特に定めるものでは無いが、炭素原子、酸素原子、水素原子およびハロゲン原子から選択される原子のみで構成されることが好ましく、炭素原子、酸素原子および水素原子から選択される原子のみで構成されることがより好ましい。 The type of atoms constituting the monofunctional polymerizable compound used in the curable composition for imprints is not particularly defined, but should be composed only of atoms selected from carbon atoms, oxygen atoms, hydrogen atoms and halogen atoms. Is preferable, and it is more preferably composed of only an atom selected from a carbon atom, an oxygen atom and a hydrogen atom.
　インプリント用硬化性組成物に用いる単官能重合性化合物の好ましい第一の実施形態は、炭素数４以上の直鎖または分岐の炭化水素鎖を有する化合物である。
　本発明における炭化水素鎖とは、アルキル鎖、アルケニル鎖、アルキニル鎖を表し、アルキル鎖、アルケニル鎖が好ましく、アルキル鎖がより好ましい。
　本発明において、アルキル鎖とは、アルキル基およびアルキレン基を表す。同様に、アルケニル鎖とは、アルケニル基およびアルケニレン基を表し、アルキニル鎖とはアルキニル基およびアルキニレン基を表す。これらの中でも、直鎖または分岐のアルキル基、アルケニル基がより好ましく、直鎖または分岐のアルキル基がさらに好ましく、直鎖のアルキル基が一層好ましい。
　上記直鎖または分岐の炭化水素鎖（好ましくは、アルキル基）は、炭素数４以上であり、炭素数６以上が好ましく、炭素数８以上がより好ましく、炭素数１０以上がさらに好ましく、炭素数１２以上が一層好ましい。炭素数の上限値については、特に定めるものではないが、例えば、炭素数２５以下とすることができる。
　上記直鎖または分岐の炭化水素鎖は、エーテル基（－Ｏ－）を含んでいてもよいが、エーテル基を含んでいない方が離型性向上の観点から好ましい。
　このような炭化水素鎖を有する単官能重合性化合物を用いることで、比較的少ない添加量で、硬化物（パターン）の弾性率を低減し、離型性が向上する。また、直鎖または分岐のアルキル基を有する単官能重合性化合物を用いると、モールドと硬化物（パターン）の界面エネルギーを低減して、さらに離型性を向上することができる。
　インプリント用硬化性組成物に用いる単官能重合性化合物が有する好ましい炭化水素基として、（１）～（３）を挙げることができる。
（１）炭素数８以上の直鎖アルキル基
（２）炭素数１０以上の分岐アルキル基
（３）炭素数１以上の直鎖または分岐のアルキル基が置換した脂環、芳香族環または芳香族複素環 A preferred first embodiment of the monofunctional polymerizable compound used in the curable composition for imprints is a compound having a linear or branched hydrocarbon chain having 4 or more carbon atoms.
The hydrocarbon chain in the present invention represents an alkyl chain, an alkenyl chain, or an alkynyl chain, preferably an alkyl chain or alkenyl chain, and more preferably an alkyl chain.
In the present invention, the alkyl chain represents an alkyl group and an alkylene group. Similarly, an alkenyl chain represents an alkenyl group and an alkenylene group, and an alkynyl chain represents an alkynyl group and an alkynylene group. Among these, a linear or branched alkyl group or an alkenyl group is more preferable, a linear or branched alkyl group is more preferable, and a linear alkyl group is more preferable.
The linear or branched hydrocarbon chain (preferably an alkyl group) has 4 or more carbon atoms, preferably 6 or more carbon atoms, more preferably 8 or more carbon atoms, still more preferably 10 or more carbon atoms, and more carbon atoms. 12 or more is more preferable. The upper limit value of the carbon number is not particularly defined, but can be, for example, 25 or less.
The linear or branched hydrocarbon chain may contain an ether group (—O—), but preferably does not contain an ether group from the viewpoint of improving releasability.
By using such a monofunctional polymerizable compound having a hydrocarbon chain, the elastic modulus of the cured product (pattern) is reduced and the releasability is improved with a relatively small addition amount. Further, when a monofunctional polymerizable compound having a linear or branched alkyl group is used, the interfacial energy between the mold and the cured product (pattern) can be reduced, and the releasability can be further improved.
As preferred hydrocarbon groups possessed by the monofunctional polymerizable compound used in the curable composition for imprints, (1) to (3) can be mentioned.
(1) a linear alkyl group having 8 or more carbon atoms (2) a branched alkyl group having 10 or more carbon atoms (3) an alicyclic ring, an aromatic ring or an aromatic group substituted by a linear or branched alkyl group having 1 or more carbon atoms Heterocycle
（１）炭素数８以上の直鎖アルキル基
　炭素数８以上の直鎖アルキル基は、炭素数１０以上のものがより好ましく、炭素数１１以上がさらに好ましく、炭素数１２以上が一層好ましい。また、炭素数２０以下が好ましく、炭素数１８以下がより好ましく、炭素数１６以下がさらに好ましく、炭素数１４以下が一層好ましい。
（２）炭素数１０以上の分岐アルキル基
　上記炭素数１０以上の分岐アルキル基は、炭素数１０～２０のものが好ましく、炭素数１０～１６がより好ましく、炭素数１０～１４がさらに好ましく、炭素数１０～１２が一層好ましい。
（３）炭素数１以上の直鎖または分岐のアルキル基が置換した脂環、芳香族環または芳香族複素環
　炭素数１以上の直鎖または分岐のアルキル基は、直鎖のアルキル基がより好ましい。アルキル基の炭素数は、１４以下が好ましく、１２以下がより好ましく、１０以下がさらに好ましい。
　脂環、芳香族環または芳香族複素環の環は、単環であっても縮環であってもよいが、単環であることが好ましい。縮環である場合は、環の数は、２つまたは３つが好ましい。環は、３～８員環が好ましく、５員環または６員環がより好ましく、６員環がさらに好ましい。環の具体例としては、後述する環Ｃｚの例が挙げられる。 (1) Linear alkyl group having 8 or more carbon atoms The linear alkyl group having 8 or more carbon atoms is more preferably one having 10 or more carbon atoms, further preferably 11 or more carbon atoms, and still more preferably 12 or more carbon atoms. Moreover, 20 or less carbon atoms are preferable, 18 or less carbon atoms are more preferable, 16 or less carbon atoms are more preferable, and 14 or less carbon atoms are still more preferable.
(2) Branched alkyl group having 10 or more carbon atoms The branched alkyl group having 10 or more carbon atoms is preferably one having 10 to 20 carbon atoms, more preferably 10 to 16 carbon atoms, still more preferably 10 to 14 carbon atoms, More preferably, the number of carbon atoms is 10 to 12.
(3) Aliphatic ring, aromatic ring or aromatic heterocyclic ring substituted with a linear or branched alkyl group having 1 or more carbon atoms. A linear or branched alkyl group having 1 or more carbon atoms is more preferably a linear alkyl group. preferable. 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 alicyclic ring, aromatic ring or aromatic heterocyclic ring may be a monocyclic ring or a condensed ring, but is preferably a monocyclic ring. In the case of a condensed ring, the number of rings is preferably 2 or 3. The ring is preferably a 3- to 8-membered ring, more preferably a 5-membered ring or a 6-membered ring, and even more preferably a 6-membered ring. Specific examples of the ring include an example of the ring Cz described later.
　インプリント用硬化性組成物に用いる単官能重合性化合物は、炭素数４以上の直鎖または分岐の炭化水素鎖と重合性基が、直接にまたは連結基を介して結合している化合物が好ましく、上記（１）～（３）の基のいずれか１つと、重合性基が直接に結合している化合物がより好ましい。連結基としては、－Ｏ－、－Ｃ（＝Ｏ）－、－ＣＨ２－またはこれらの組み合わせが例示される。本発明で用いる単官能重合性化合物としては、（１）炭素数８以上の直鎖アルキル基と、（メタ）アクリロイルオキシ基とが直接結合している、直鎖アルキル（メタ）アクリレートが、特に好ましい。 The monofunctional polymerizable compound used in the curable composition for imprints is preferably a compound in which a linear or branched hydrocarbon chain having 4 or more carbon atoms and a polymerizable group are bonded directly or via a linking group. A compound in which any one of the above groups (1) to (3) and a polymerizable group are directly bonded is more preferable. Examples of the linking group include —O—, —C (═O) —, —CH 2 —, or a combination thereof. The monofunctional polymerizable compound used in the present invention includes (1) a linear alkyl (meth) acrylate in which a linear alkyl group having 8 or more carbon atoms and a (meth) acryloyloxy group are directly bonded. preferable.
　単官能重合性化合物は下記式（Ｉ－１）で表される化合物が好ましい。
Figure JPOXMLDOC01-appb-C000016
 　Ｒ１２は、アルキル基（炭素数１～３６が好ましく、１～３０がより好ましく、１～２４がさらに好ましい）、脂環（炭素数３～２４が好ましく、３～１２がより好ましく、３～６がさらに好ましい）、芳香族環（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）および芳香族複素環（炭素数２～１２が好ましく、２～６がより好ましく、２～５がさらに好ましい）から選ばれる少なくとも１種、またはそれらの組合せによる基を表す。Ｒ１１は水素原子またはメチル基を表す。Ｌ１１は単結合または上記連結基Ｌを表し、アルキレン基またはアルケニレン基が好ましい。Ｒ１２とＬ１１は連結基Ｌを介してまたは介さずに結合して環を形成していてもよい。Ｒ１２、Ｌ１１は上記置換基Ｔを有していてもよい。置換基Ｔは複数が結合して環を形成してもよく、Ｒ１２と結合して、またはＬ１１と結合して環を形成してもよい。置換基Ｔが複数あるとき互いに同じでも異なっていてもよい。Ｒ１２における脂環、芳香族環または芳香族複素環の好ましい範囲は、後述する環Ｃｚと同様である。 The monofunctional polymerizable compound is preferably a compound represented by the following formula (I-1).
Figure JPOXMLDOC01-appb-C000016
 R 12 is an alkyl group (preferably having a carbon number of 1 to 36, preferably 1 to 30, more preferably 1 to 24), or an alicyclic ring (preferably having 3 to 24 carbon atoms, more preferably 3 to 12 carbon atoms). 6 is more preferred), an aromatic ring (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms) and an aromatic heterocyclic ring (preferably having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms). More preferably, it represents a group of at least one selected from 2-5, or a combination thereof. R 11 represents a hydrogen atom or a methyl group. L 11 represents a single bond or the linking group L, and is preferably an alkylene group or an alkenylene group. R 12 and L 11 may combine with or without a linking group L to form a ring. R 12 and L 11 may have the substituent T. A plurality of substituents T may be bonded to form a ring, may be bonded to R 12 , or may be bonded to L 11 to form a ring. When there are a plurality of substituents T, they may be the same or different. The preferred range of the alicyclic ring, aromatic ring or aromatic heterocyclic ring for R 12 is the same as ring Cz described later.
　第一の実施形態の単官能重合性化合物としては、下記第１群および第２群を例示することができる。しかしながら、本発明がこれらに限定されるものでは無いことは言うまでもない。また、第１群の方が第２群よりもより好ましい。
第１群
Figure JPOXMLDOC01-appb-C000017
 Examples of the monofunctional polymerizable compound of the first embodiment include the following first group and second group. However, it goes without saying that the present invention is not limited to these examples. The first group is more preferable than the second group.
First group
Figure JPOXMLDOC01-appb-C000017
第２群
Figure JPOXMLDOC01-appb-C000018
 Second group
Figure JPOXMLDOC01-appb-C000018
　インプリント用硬化性組成物に用いる単官能重合性化合物の好ましい第二の実施形態は、環状構造を有する化合物である。環状構造としては、３～８員環の単環または縮合環が好ましい。上記縮合環を構成する環の数は、２つまたは３つが好ましい。環状構造は、５員環または６員環がより好ましく、６員環がさらに好ましい。また、単環がより好ましい。
　重合性化合物一分子中の環状構造の数は、１つであっても、２つ以上であってもよいが、１つまたは２つが好ましく、１つがより好ましい。尚、縮合環の場合は、縮合環を１つの環状構造として考える。 A preferred second embodiment of the monofunctional polymerizable compound used in the curable composition for imprints is a compound having a cyclic structure. The cyclic structure is preferably a 3- to 8-membered monocyclic ring or condensed ring. The number of rings constituting the fused ring is preferably 2 or 3. The cyclic structure is more preferably a 5-membered ring or a 6-membered ring, and even more preferably a 6-membered ring. Moreover, a single ring is more preferable.
The number of cyclic structures in one molecule of the polymerizable compound may be one or two or more, but one or two is preferable, and one is more preferable. In the case of a condensed ring, the condensed ring is considered as one cyclic structure.
　第二の実施形態の単官能重合性化合物としては、下記化合物を例示することができる。しかしながら、本発明がこれらに限定されるものでは無いことは言うまでもない。また、上記第一の実施形態で述べた化合物のうち、環状構造を有する化合物も本実施形態の好ましい化合物として例示される。
Figure JPOXMLDOC01-appb-C000019
 Examples of the monofunctional polymerizable compound according to the second embodiment include the following compounds. However, it goes without saying that the present invention is not limited to these examples. Of the compounds described in the first embodiment, compounds having a cyclic structure are also exemplified as preferred compounds of this embodiment.
Figure JPOXMLDOC01-appb-C000019
　本発明では、本発明の趣旨を逸脱しない限り、上記単官能重合性化合物以外の単官能重合性化合物を用いてもよく、特開２０１４－１７０９４９号公報に記載の重合性化合物のうちの単官能重合性化合物が例示され、これらの内容は本明細書に含まれる。 In the present invention, a monofunctional polymerizable compound other than the above monofunctional polymerizable compound may be used as long as it does not depart from the spirit of the present invention, and monofunctional polymerizable compounds described in JP-A-2014-170949 can be used. Examples of the polymerizable compound are included in the present specification.
　インプリント用硬化性組成物に用いる単官能重合性化合物の全重合性化合物に対する含有量は、含有する場合、６質量％以上が好ましく、８質量％以上がより好ましく、１０質量％以上がさらに好ましく、１２質量％以上が一層好ましい。また、上記含有量は、６０質量％以下がより好ましく、５５質量％以下であってもよい。
　本発明では単官能重合性化合物を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 The content of the monofunctional polymerizable compound used in the curable composition for imprints with respect to the total polymerizable compound is preferably 6% by mass or more, more preferably 8% by mass or more, and even more preferably 10% by mass or more. 12 mass% or more is more preferable. The content is more preferably 60% by mass or less, and may be 55% by mass or less.
In the present invention, only one monofunctional polymerizable compound may be contained, or two or more kinds may be contained. When 2 or more types are included, the total amount is preferably within the above range.
＜＜＜多官能重合性化合物＞＞＞
　インプリント用硬化性組成物に用いる多官能重合性化合物は、特に定めるものではないが、脂環、芳香族環および芳香族複素環の少なくとも１種を含むことが好ましく、芳香族環および芳香族複素環の少なくとも１種を含むことがより好ましい。脂環、芳香族環および芳香族複素環の少なくとも１種を含む化合物を、以下の説明において、環含有多官能重合性化合物ということがある。 <<< Polyfunctional polymerizable compound >>>
The polyfunctional polymerizable compound used in the curable composition for imprints is not particularly defined, but preferably contains at least one of an alicyclic ring, an aromatic ring and an aromatic heterocyclic ring. More preferably, it contains at least one heterocyclic ring. 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.
　インプリント用硬化性組成物に用いる環含有多官能重合性化合物の分子量は、１,０００以下であることが好ましく、８００以下であることがより好ましく、５００以下がさらに好ましく、３５０以下が一層好ましい。分子量の上限値を１,０００以下とすることで、粘度を低減できる傾向がある。分子量の下限値については、特に定めるものでは無いが、例えば、２００以上とすることができる。 The molecular weight of the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints is preferably 1,000 or less, more preferably 800 or less, further preferably 500 or less, and further preferably 350 or less. . By setting the upper limit of the molecular weight to 1,000 or less, the viscosity tends to be reduced. The lower limit of the molecular weight is not particularly defined, but can be, for example, 200 or more.
　インプリント用硬化性組成物に用いる環含有多官能重合性化合物が有する重合性基の数は、２以上であり、２～７が好ましく、２～４がより好ましく、２または３がさらに好ましく、２が一層好ましい。 The number of polymerizable groups contained in the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints is 2 or more, preferably 2 to 7, more preferably 2 to 4, more preferably 2 or 3. 2 is more preferable.
　インプリント用硬化性組成物に用いる環含有多官能重合性化合物が有する重合性基の種類は特に定めるものでは無いが、エチレン性不飽和基、エポキシ基等が例示され、エチレン性不飽和基が好ましい。エチレン性不飽和基としては、（メタ）アクリロイル基がより好ましく、アクリロイル基がさらに好ましい。１つの分子中に２種以上の重合性基を含んでいてもよいし、同じ種類の重合性基を２つ以上含んでいてもよい。 The type of polymerizable group possessed by the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints is not particularly defined, but examples thereof include ethylenically unsaturated groups and epoxy groups. preferable. As the ethylenically unsaturated group, a (meth) acryloyl group is more preferable, and an acryloyl group is more preferable. Two or more polymerizable groups may be contained in one molecule, or two or more polymerizable groups of the same type may be contained.
　インプリント用硬化性組成物に用いる環含有多官能重合性化合物を構成する原子の種類は特に定めるものでは無いが、炭素原子、酸素原子、水素原子およびハロゲン原子から選択される原子のみで構成されることが好ましく、炭素原子、酸素原子および水素原子から選択される原子のみで構成されることがより好ましい。 The type of atoms constituting the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints is not particularly defined, but is composed only of atoms selected from carbon atoms, oxygen atoms, hydrogen atoms and halogen atoms. It is preferable that it is composed only of atoms selected from a carbon atom, an oxygen atom and a hydrogen atom.
　インプリント用硬化性組成物に用いる環含有多官能重合性化合物に含まれる環は、単環であっても縮環であってもよいが、単環であることが好ましい。縮環である場合は、環の数は、２つまたは３つが好ましい。環は、３～８員環が好ましく、５員環または６員環がより好ましく、６員環がさらに好ましい。また、環は、脂環であっても、芳香族環または芳香族複素環であってもよいが、芳香族環または芳香族複素環であることが好ましく、芳香族環であることがさらに好ましい。環の具体例としては、環Ｃｚの例が挙げられる。
　インプリント用硬化性組成物に用いる環含有多官能重合性化合物における環の数は、１つであっても、２つ以上であってもよいが、１つまたは２つが好ましく、１つがより好ましい。尚、縮合環の場合は、縮合環を１つとして考える。
　インプリント用硬化性組成物に用いる環含有多官能重合性化合物の構造は、（重合性基）－（単結合または２価の連結基）－（環を有する２価の基）－（単結合または２価の連結基）－（重合性基）で表されることが好ましい。ここで、連結基としては、アルキレン基がより好ましく、炭素数１～３のアルキレン基がさらに好ましい。 The ring contained in the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints may be monocyclic or condensed, but is preferably monocyclic. In the case of a condensed ring, the number of rings is preferably 2 or 3. The ring is preferably a 3- to 8-membered ring, more preferably a 5-membered ring or a 6-membered ring, and even more preferably a 6-membered ring. Further, the ring may be an alicyclic ring, an aromatic ring or an aromatic heterocyclic ring, but is preferably an aromatic ring or an aromatic heterocyclic ring, more preferably an aromatic ring. . Specific examples of the ring include an example of the ring Cz.
The number of rings in the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints may be one or two or more, but preferably one or two, more preferably one. . In the case of a condensed ring, one condensed ring is considered.
The structure of the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints is (polymerizable group)-(single bond or divalent linking group)-(divalent group having a ring)-(single bond). Or a divalent linking group)-(polymerizable group). Here, the linking group is preferably an alkylene group, more preferably an alkylene group having 1 to 3 carbon atoms.
　インプリント用硬化性組成物に用いる環含有多官能重合性化合物は、下記式（Ｉ－２）で表されることが好ましい。
Figure JPOXMLDOC01-appb-C000020
 　Ｑは、脂環（炭素数３～２４が好ましく、３～１２がより好ましく、３～６がさらに好ましい）、芳香族環（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）および芳香族複素環（炭素数２～１２が好ましく、２～６がより好ましく、２～５がさらに好ましい）から選ばれる少なくとも１種を有する１＋ｑ価の基を表す。Ｒ２１およびＲ２２はそれぞれ独立に水素原子またはメチル基を表す。Ｌ２１およびＬ２２はそれぞれ独立に単結合または上記連結基Ｌを表す。ＱとＬ２１またはＬ２２は連結基Ｌを介してまたは介さずに結合して環を形成していてもよい。Ｑ、Ｌ２１およびＬ２２は上記置換基Ｔを有していてもよい。置換基Ｔは複数が結合して環を形成してもよく、Ｑと結合して、またはＬ２１またはＬ２２と結合して環を形成してもよい。置換基Ｔが複数あるとき互いに同じでも異なっていてもよい。Ｑにおける脂環、芳香族環または芳香族複素環の好ましい範囲は、後述する環Ｃｚが挙げられる。ｑは１～５の整数であり、１～３の整数が好ましく、１または２がより好ましく、１がさらに好ましい。
　Ｑは、複数の脂環、複数の芳香族環、複数の芳香族複素環、脂環と芳香族環、脂環と芳香族複素環、芳香族環と芳香族複素環が連結した構造を有していてもよい。芳香族環が連結した構造としては、上記式Ａｒ１～Ａｒ５の構造が挙げられる。 The ring-containing polyfunctional polymerizable compound used in the curable composition for imprints is preferably represented by the following formula (I-2).
Figure JPOXMLDOC01-appb-C000020
 Q is an alicyclic ring (preferably having 3 to 24 carbon atoms, more preferably 3 to 12 carbon atoms, still more preferably 3 to 6 carbon atoms) or an aromatic ring (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 10 represents a 1 + q-valent group having at least one selected from 10 and more preferably an aromatic heterocyclic ring (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and further preferably 2 to 5 carbon atoms). R 21 and R 22 each independently represents a hydrogen atom or a methyl group. L 21 and L 22 each independently represent a single bond or the above linking group L. Q and L 21 or L 22 may combine with or without a linking group L to form a ring. Q, L 21 and L 22 may have the substituent T. A plurality of substituents T may be bonded to form a ring, may be bonded to Q, or may be bonded to L 21 or L 22 to form a ring. When there are a plurality of substituents T, they may be the same or different. The preferable range of the alicyclic ring, aromatic ring or aromatic heterocyclic ring in Q includes ring Cz described later. q is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1.
Q has 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 connected. You may do it. Examples of the structure in which the aromatic rings are linked include the structures of the above formulas Ar1 to Ar5.
　インプリント用硬化性組成物に用いる多官能重合性化合物としては、下記第１群および第２群を例示することができる。しかし、本発明がこれらに限定されるものでは無いことは言うまでもない。第１群の方がより好ましい。
第１群
Figure JPOXMLDOC01-appb-C000021
 第２群
Figure JPOXMLDOC01-appb-C000022
 Examples of the polyfunctional polymerizable compound used in the curable composition for imprints include the following first group and second group. However, it goes without saying that the present invention is not limited to these examples. The first group is more preferable.
First group
Figure JPOXMLDOC01-appb-C000021
 Second group
Figure JPOXMLDOC01-appb-C000022
　インプリント用硬化性組成物は、上記環含有多官能重合性化合物以外の他の多官能重合性化合物を含んでいてもよい。他の多官能重合性化合物としては、下記式（Ｉ－３）で表される化合物が好ましい。
Figure JPOXMLDOC01-appb-C000023
 　Ｌ３０は、直鎖もしくは分岐のアルカン構造の基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい）、直鎖もしくは分岐のアルケン構造の基（炭素数２～１２が好ましく、２～６がより好ましく、２～３がさらに好ましい）、直鎖もしくは分岐のアルキン構造の基（炭素数２～１２が好ましく、２～６がより好ましく、２～３がさらに好ましい）から選ばれる少なくとも１種を有する１＋ｒ価の基を表す。Ｒ２５およびＲ２６はそれぞれ独立に水素原子またはメチル基を表す。Ｌ２５およびＬ２６はそれぞれ独立に単結合または上記連結基Ｌを表す。Ｌ３０とＬ２５またはＬ２６とは連結基Ｌを介してまたは介さずに結合して環を形成していてもよい。Ｌ２５、Ｌ２６およびＬ３０は上記置換基Ｔを有していてもよい。置換基Ｔは複数が結合して環を形成してもよく、他の連結基と結合して環を形成してもよい。置換基Ｔが複数あるとき互いに同じでも異なっていてもよい。ｒは１～４の整数であり、１～３の整数が好ましく、１または２がより好ましく、１がさらに好ましい。なお、Ｌ３０にはヘテロ連結基（Ｏ、Ｓ、ＮＲＮ）が介在していてもよい。ヘテロ連結基が介在する数は、Ｌ３０の炭素数１～６個に１つの割合であることが好ましい。 The curable composition for imprints may contain a polyfunctional polymerizable compound other than the ring-containing polyfunctional polymerizable compound. As other polyfunctional polymerizable compounds, compounds represented by the following formula (I-3) are preferable.
Figure JPOXMLDOC01-appb-C000023
 L 30 is a group having a linear or branched alkane structure (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and further preferably 1 to 3), or a group having a linear or branched alkene structure (having 2 carbon atoms). To 12 are preferable, 2 to 6 are more preferable, and 2 to 3 are more preferable. A linear or branched alkyne structure group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6, more preferably 2 to 3). 1 + r-valent group having at least one selected from (preferably). R 25 and R 26 each independently represents a hydrogen atom or a methyl group. L 25 and L 26 each independently represent a single bond or the above linking group L. L 30 and L 25 or L 26 may combine with or without a linking group L to form a ring. L 25 , L 26 and L 30 may have the substituent T. A plurality of substituents T may be bonded to form a ring, or may be bonded to another linking group to form a ring. When there are a plurality of substituents T, they may be the same or different. r is an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1. In addition, a hetero linking group (O, S, NR N ) may be interposed in L 30 . The number of intervening hetero linking group is preferably a rate of one having 1 to 6 carbon atoms, L 30.
　インプリント用硬化性組成物に用いる他の多官能重合性化合物としては、特開２０１４－１７０９４９号公報に記載の重合性化合物のうち、環を有さない多官能重合性化合物が例示され、これらの内容は本明細書に含まれる。より具体的には、例えば、下記化合物が例示される。
Figure JPOXMLDOC01-appb-C000024
 Examples of other polyfunctional polymerizable compounds used in the curable composition for imprints include polyfunctional polymerizable compounds having no ring among the polymerizable compounds described in JP-A No. 2014-170949. Is included herein. More specifically, for example, the following compounds are exemplified.
Figure JPOXMLDOC01-appb-C000024
　環Ｃｚとしては、以下の芳香族環、芳香族複素環および脂環が例示される。
　芳香族環を含む化合物に含まれる芳香族環としては、炭素数６～２２のものが好ましく、６～１８がより好ましく、６～１０がさらに好ましい。芳香族環の具体例としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、フェナレン環、フルオレン環、アセナフチレン環、ビフェニレン環、インデン環、インダン環、トリフェニレン環、ピレン環、クリセン環、ペリレン環、テトラヒドロナフタレン環などが挙げられる。なかでも、ベンゼン環またはナフタレン環が好ましく、ベンゼン環がより好ましい。芳香族環は複数が連結した構造を取っていてもよく、例えば、ビフェニル環、ビスフェニル環が挙げられる。
　芳香族複素環としては、炭素数１～１２のものが好ましく、１～６がより好ましく、１～５がさらに好ましい。その具体例としては、チオフェン環、フラン環、ピロール環、イミダゾール環、ピラゾール環、トリアゾール環、テトラゾール環、チアゾール環、オキサゾール環、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環、イソインドール環、インドール環、インダゾール環、プリン環、キノリジン環、イソキノリン環、キノリン環、フタラジン環、ナフチリジン環、キノキサリン環、キナゾリン環、シンノリン環、カルバゾール環、アクリジン環、フェナジン環、フェノチアジン環、フェノキサジン環などが挙げられる。
　脂環としては炭素数３～２２のものが好ましく、４～１８がより好ましく、６～１０がさらに好ましい。その具体例としては、シクロプロパン環、シクロブタン環、シクロブテン環、シクロペンタン環、シクロヘキサン環、シクロヘキセン環、シクロヘプタン環、シクロオクタン環、ジシクロペンタジエン環、テトラヒドロジシクロペンタジエン環、オクタヒドロナフタレン環、デカヒドロナフタレン環、ヘキサヒドロインダン環、ボルナン環、ノルボルナン環、ノルボルネン環、イソボルナン環、トリシクロデカン環、テトラシクロドデカン環、アダマンタン環などが挙げられる。 Examples of the ring Cz include the following aromatic rings, aromatic heterocyclic rings and alicyclic rings.
The aromatic ring contained in the compound containing an aromatic ring is preferably one having 6 to 22 carbon atoms, more preferably 6 to 18 and even more preferably 6 to 10. Specific examples of the aromatic ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, phenalene ring, fluorene ring, acenaphthylene ring, biphenylene ring, indene ring, indane ring, triphenylene ring, pyrene ring, chrysene ring, perylene ring. And tetrahydronaphthalene ring. Of these, a benzene ring or a naphthalene ring is preferable, and a benzene ring is more preferable. The aromatic ring may have a structure in which a plurality of aromatic rings are connected, and examples thereof include a biphenyl ring and a bisphenyl ring.
The aromatic heterocyclic ring preferably has 1 to 12 carbon atoms, more preferably 1 to 6 and even more preferably 1 to 5. Specific examples thereof include thiophene ring, furan ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, oxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, isoindole ring, indole. Ring, indazole ring, purine ring, quinolidine ring, isoquinoline ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, carbazole ring, acridine ring, phenazine ring, phenothiazine ring, phenoxazine ring, etc. It is done.
The alicyclic ring preferably has 3 to 22 carbon atoms, more preferably 4 to 18 and even more preferably 6 to 10. Specific examples thereof include cyclopropane ring, cyclobutane ring, cyclobutene ring, cyclopentane ring, cyclohexane ring, cyclohexene ring, cycloheptane ring, cyclooctane ring, dicyclopentadiene ring, tetrahydrodicyclopentadiene ring, octahydronaphthalene ring, Examples include a decahydronaphthalene ring, a hexahydroindane ring, a bornane ring, a norbornane ring, a norbornene ring, an isobornane ring, a tricyclodecane ring, a tetracyclododecane ring, and an adamantane ring.
　多官能重合性化合物は、インプリント用硬化性組成物中の全重合性化合物に対して、３０質量％以上含有することが好ましく、４５質量％以上がより好ましく、５０質量％以上がさらに好ましく、５５質量％以上が一層好ましく、６０質量％以上であってもよく、さらに７０質量％以上であってもよい。また、上限値は、９５質量％未満であることが好ましく、９０質量％以下であることがさらに好ましく、８５質量％以下とすることもできる。
　インプリント用硬化性組成物は、多官能重合性化合物を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 The polyfunctional polymerizable compound is preferably contained in an amount of 30% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, based on the total polymerizable compound in the curable composition for imprints. 55 mass% or more is still more preferable, 60 mass% or more may be sufficient, and 70 mass% or more may be sufficient. Moreover, it is preferable that an upper limit is less than 95 mass%, it is further more preferable that it is 90 mass% or less, and it can also be 85 mass% or less.
The curable composition for imprints may contain only one type of polyfunctional polymerizable compound or two or more types. When 2 or more types are included, the total amount is preferably within the above range.
　本発明で用いるインプリント用硬化性組成物は、組成物の８５質量％以上が重合性化合物であることが好ましく、９０質量％以上が重合性化合物であることがより好ましく、９３質量％以上が重合性化合物であることがさらに好ましい。 In the curable composition for imprints used in the present invention, 85% by mass or more of the composition is preferably a polymerizable compound, more preferably 90% by mass or more is a polymerizable compound, and 93% by mass or more. More preferably, it is a polymerizable compound.
　インプリント用硬化性組成物のハンセン溶解度パラメータ（ＨＳＰ）ベクトルの：
（ｉ）分散項成分（ｄ成分）は、１４．０～２０．０であることが好ましく、１５．０～１９．０であることがより好ましく、１６．０～１８．５であることがさらに好ましい；
（ｉｉ）極性項成分（ｐ成分）は、３．５～８．０であることが好ましく、３．８～６．０であることがより好ましく、４．０～５．０であることがさらに好ましい；
（ｉｉｉ）水素結合項成分（ｈ成分）は、４．０～８．０であることが好ましく、４．７～７．０であることがより好ましく、５．２～６．５であることがさらに好ましい。
　上記インプリント用硬化性組成物の、ＨＳＰベクトルの分散項成分、極性項成分、水素結合項成分は、それぞれ、後述する実施例に記載の方法で設定される。 For the Hansen Solubility Parameter (HSP) vector of the curable composition for imprints:
(I) The dispersion term component (component d) is preferably 14.0 to 20.0, more preferably 15.0 to 19.0, and more preferably 16.0 to 18.5. Even more preferred;
(Ii) The polar term component (p component) is preferably 3.5 to 8.0, more preferably 3.8 to 6.0, and 4.0 to 5.0. Even more preferred;
(Iii) The hydrogen bond term component (component h) is preferably 4.0 to 8.0, more preferably 4.7 to 7.0, and 5.2 to 6.5. Is more preferable.
The dispersion term component, polar term component, and hydrogen bond term component of the HSP vector of the curable composition for imprints are set by the methods described in the examples described later.
＜＜他の成分＞＞
　インプリント用硬化性組成物は、重合性化合物以外の添加剤を含有してもよい。他の添加剤として、重合開始剤、界面活性剤、増感剤、離型剤、酸化防止剤、重合禁止剤等を含んでいてもよい。
　本発明で用いることができるインプリント用硬化性組成物の具体例としては、特開２０１３－０３６０２７号公報、特開２０１４－０９０１３３号公報、特開２０１３－１８９５３７号公報に記載の組成物が例示され、これらの内容は本明細書に組み込まれる。また、インプリント用硬化性組成物の調製、膜（パターン形成層）の形成方法についても、上記公報の記載を参酌でき、これらの内容は本明細書に組み込まれる。 << other ingredients >>
The curable composition for imprints may contain additives other than the polymerizable compound. As other additives, a polymerization initiator, a surfactant, a sensitizer, a release agent, an antioxidant, a polymerization inhibitor and the like may be included.
Specific examples of the curable composition for imprints that can be used in the present invention include the compositions described in JP2013-036027A, JP2014-090133A, and JP2013-189537A. The contents of which are incorporated herein. The description of the above publication can be referred to for the preparation of the curable composition for imprints and the method for forming the film (pattern forming layer), and the contents thereof are incorporated in the present specification.
＜＜物性値等＞＞
　インプリント用硬化性組成物の粘度は、２０．０ｍＰａ・ｓ以下であることが好ましく、１５．０ｍＰａ・ｓ以下であることがより好ましく、１１．０ｍＰａ・ｓ以下であってもよく、さらには９．０ｍＰａ・ｓ以下であってもよい。上記粘度の下限値としては、特に限定されるものでは無いが、例えば、４．０ｍＰａ・以上、さらには５．０ｍＰａ・ｓ以上とすることができる。 << Physical property values >>
The viscosity of the curable composition for imprints 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, It may be 9.0 mPa · s or less. Although it does not specifically limit as a lower limit of the said viscosity, For example, it can be 4.0 mPa * s or more, Furthermore, it can be 5.0 mPa * s or more.
　インプリント用硬化性組成物の表面張力（γＲｅｓｉｓｔ）は２９．０ｍＮ/ｍ以上であることが好ましく、３０．０ｍＮ/ｍ以上であることがより好ましく、３１．０ｍＮ／ｍ以上であることがさらに好ましい。表面張力の高いインプリント用硬化性組成物を用いることで毛細管力が上昇し、モールドパターンへのインプリント用硬化性組成物の高速な充填が可能となる。上記表面張力の上限値としては、特に限定されるものではないが、下層膜との関係およびインクジェット適性を付与するという観点では、４２．０ｍＮ/ｍ以下であることが好ましく、４０．０ｍＮ/ｍ以下であることがより好ましく、３８．０ｍＮ/ｍ以下であってもよい。 The surface tension (γ Resist) of the curable composition for imprints is preferably 29.0 mN / m or more, more preferably 30.0 mN / m or more, and further preferably 31.0 mN / m or more. preferable. By using the curable composition for imprints having a high surface tension, the capillary force increases, and the mold pattern can be filled with the curable composition for imprints at a high speed. The upper limit of the surface tension is not particularly limited, but it is preferably 42.0 mN / m or less from the viewpoint of imparting the relationship with the lower layer film and inkjet suitability. More preferably, it may be 38.0 mN / m or less.
　インプリント用硬化性組成物の大西パラメータは、５．０以下であることが好ましく、４．０以下であることがより好ましく、３．７以下であることがさらに好ましい。インプリント用硬化性組成物の大西パラメータの下限値は、特に定めるものではないが、例えば、１．０以上、さらには、２．０以上であってもよい。
　大西パラメータはインプリント用硬化性組成物の重合性化合物について、それぞれ、全構成成分の炭素原子、水素原子および酸素原子の数を下記式に代入して求めることができる。
　大西パラメータ＝炭素原子、水素原子および酸素原子の数の和／（炭素原子の数－酸素原子の数） The Onishi parameter of the curable composition for imprints is preferably 5.0 or less, more preferably 4.0 or less, and still more preferably 3.7 or less. The lower limit value of the Onishi parameter of the curable composition for imprints is not particularly defined, but may be, for example, 1.0 or more, or 2.0 or more.
The Onishi parameter can be obtained by substituting the numbers of carbon atoms, hydrogen atoms, and oxygen atoms of all constituent components into the following formulas for the polymerizable compound of the curable composition for imprints.
Onishi parameter = sum of the number of carbon, hydrogen and oxygen atoms / (number of carbon atoms-number of oxygen atoms)
　インプリント用硬化性組成物に含まれる重合性化合物のハンセン溶解度パラメータ（ＨＳＰ）ベクトルの：
（ｉ）分散項成分（ｄ成分）は、１４．０～２０．０であることが好ましく、１５．０～１９．０であることがより好ましく、１６．０～１８．５であることがさらに好ましい；
（ｉｉ）極性項成分（ｐ成分）は、３．５～８．０であることが好ましく、３．８～６．０であることがより好ましく、４．０～５．０であることがさらに好ましい；
（ｉｉｉ）水素結合項成分（ｈ成分）は、４．０～８．０であることが好ましく、４．７～７．０であることがより好ましく、５．２～６．５であることがさらに好ましい。
　ＨＳＰベクトルの分散項成分、極性項成分、水素結合項成分は、それぞれ、後述する実施例に記載の方法で設定される。ＨＳＰベクトルの算出にあたって該当成分が複数ある場合には、少なくとも１種が上記の範囲を満たすことが好ましく、最多量成分が上記の範囲を満たすことがより好ましい。 The Hansen Solubility Parameter (HSP) vector of the polymerizable compound contained in the curable composition for imprints:
(I) The dispersion term component (component d) is preferably 14.0 to 20.0, more preferably 15.0 to 19.0, and more preferably 16.0 to 18.5. Even more preferred;
(Ii) The polar term component (p component) is preferably 3.5 to 8.0, more preferably 3.8 to 6.0, and 4.0 to 5.0. Even more preferred;
(Iii) The hydrogen bond term component (component h) is preferably 4.0 to 8.0, more preferably 4.7 to 7.0, and 5.2 to 6.5. Is more preferable.
The dispersion term component, polar term component, and hydrogen bond term component of the HSP vector are each set by the method described in the examples described later. When there are a plurality of corresponding components in calculating the HSP vector, it is preferable that at least one of the components satisfies the above range, and the most abundant component satisfies the above range.
　本発明では、インプリント用硬化性組成物における溶剤の含有量は、インプリント用硬化性組成物の５質量％以下であることが好ましく、３質量％以下であることがより好ましく、１質量％以下であることがさらに好ましい。
　インプリント用硬化性組成物は、ポリマー（好ましくは、重量平均分子量が１,０００を超える、より好ましくは重量平均分子量が２，０００を超える、さらに好ましくは重量平均分子量が１０，０００以上のポリマー）を実質的に含有しない態様とすることもできる。ポリマーを実質的に含有しないとは、例えば、ポリマーの含有量がインプリント用硬化性組成物の０．０１質量％以下であることをいい、０．００５質量％以下が好ましく、全く含有しないことがより好ましい。 In the present invention, the content of the solvent in the curable composition for imprints is preferably 5% by mass or less of the curable composition for imprints, more preferably 3% by mass or less, and 1% by mass. More preferably, it is as follows.
The curable composition for imprints is a polymer (preferably a polymer having a weight average molecular weight of more than 1,000, more preferably a weight average molecular weight of more than 2,000, and still more preferably a weight average molecular weight of 10,000 or more. ) May not be substantially contained. “Containing substantially no polymer” means, for example, that the polymer content is 0.01% by mass or less of the curable composition for imprints, preferably 0.005% by mass or less, and not contained at all. Is more preferable.
　本発明で用いるインプリント用硬化性組成物の収容容器としては従来公知の収容容器を用いることができる。また、収容容器としては、原材料や組成物中への不純物混入を抑制することを目的に、容器内壁を６種６層の樹脂で構成された多層ボトルや、６種の樹脂を７層構造にしたボトルを使用することも好ましい。このような容器としては例えば特開２０１５－１２３３５１号公報に記載の容器が挙げられる。 As the container for the curable composition for imprints used in the present invention, a conventionally known container can be used. In addition, as a container, for the purpose of suppressing contamination of raw materials and compositions, the inner wall of the container is a multi-layer bottle composed of 6 types and 6 layers of resin, and 6 types of resins are made into a 7 layer structure. It is also preferred to use bottles that have been used. Examples of such a container include a container described in JP-A-2015-123351.
＜キット＞
　本発明は、インプリント用下層膜形成組成物と重合性化合物を含むインプリント用硬化性組成物とを含むキットを開示する。
　本発明のキットは、脱離成分（式（ｒ１）または（ｒ２）で表される化合物あるいは式（ｒ１－１）で表される化合物）のハンセン溶解度パラメータとインプリント用硬化性組成物のハンセン溶解度パラメータとに基づき下記数式（Ｈ１）で算出されるΔＨＳＰ値が５以下であることが好ましく、７．０以下であることがより好ましく、５．０以下であることがさらに好ましく、４．０以下であることが一層好ましい。下限値としては、０であってもよいが、０．１以上であることが実際的である。
　　ΔＨＳＰ＝（４．０×ΔＤ２＋ΔＰ２＋ΔＨ２）０．５　　　　（Ｈ１）
　ΔＤは、インプリント用硬化性組成物のハンセン溶解度パラメータベクトルの分散項成分と、脱離成分のハンセン溶解度パラメータベクトルの分散項成分の差である。
　ΔＰは、インプリント用硬化性組成物のハンセン溶解度パラメータベクトルの極性項成分と、脱離成分のハンセン溶解度パラメータベクトルの極性項成分の差である。
　ΔＨは、インプリント用硬化性組成物のハンセン溶解度パラメータベクトルの水素結合項成分と、脱離成分のハンセン溶解度パラメータベクトルの水素結合項成分の差である。 <Kit>
The present invention discloses a kit comprising a composition for forming an underlayer film for imprinting and a curable composition for imprinting containing a polymerizable compound.
The kit of the present invention comprises a Hansen solubility parameter of a desorbing component (a compound represented by formula (r1) or (r2) or a compound represented by formula (r1-1)) and Hansen of a curable composition for imprints. The ΔHSP value calculated by the following mathematical formula (H1) based on the solubility parameter is preferably 5 or less, more preferably 7.0 or less, further preferably 5.0 or less, and 4.0. More preferably, it is as follows. The lower limit may be 0, but is practically 0.1 or more.
ΔHSP = (4.0 × ΔD 2 + ΔP 2 + ΔH 2 ) 0.5 (H1)
ΔD is the difference between the dispersion term component of the Hansen solubility parameter vector of the curable composition for imprints and the dispersion term component of the Hansen solubility parameter vector of the elimination component.
ΔP is the difference between the polar term component of the Hansen solubility parameter vector of the curable composition for imprints and the polar term component of the Hansen solubility parameter vector of the elimination component.
ΔH is the difference between the hydrogen bond term component of the Hansen solubility parameter vector of the imprint curable composition and the hydrogen bond term component of the Hansen solubility parameter vector of the desorption component.
＜積層体およびその製造方法＞
　本発明のキットの好ましい実施形態として、このキットから形成される積層体が挙げられる。本実施形態の積層体は、上記インプリント用下層膜形成組成物から形成された下層膜と、上記インプリント用硬化性組成物から形成され、上記下層膜の表面に位置するインプリント層とを有することが好ましい。その製造方法は特に限定されないが、上記のキットを用いて、インプリント用下層膜形成組成物から形成された下層膜の表面に、インプリント用硬化性組成物を適用することを含む製造方法が挙げられる。このとき、インプリント用硬化性組成物は、インクジェット法（ＩＪ法）により、上記下層膜の表面に適用することが好ましい。さらに、積層体の製造方法は、上記インプリント用下層膜形成組成物を基板上に層状に適用する工程を含み、上記層状に適用したインプリント用下層膜形成組成物を８０～２５０℃（好ましくは１５０～２５０℃）（工程温度）で加熱（ベーク）することを含むことが好ましい。 <Laminated body and manufacturing method thereof>
A preferred embodiment of the kit of the present invention includes a laminate formed from the kit. The laminate of the present embodiment comprises an underlayer film formed from the above-described imprint underlayer film-forming composition, and an imprint layer formed from the above-mentioned curable composition for imprints and located on the surface of the underlayer film. It is preferable to have. Although the manufacturing method is not particularly limited, a manufacturing method including applying the curable composition for imprints to the surface of the lower layer film formed from the lower layer film forming composition for imprints using the kit described above. Can be mentioned. At this time, the curable composition for imprints is preferably applied to the surface of the lower layer film by an inkjet method (IJ method). Furthermore, the method for producing a laminate includes a step of applying the above-described imprint lower layer film-forming composition in a layer form on a substrate. Preferably includes heating (baking) at 150 to 250 ° C. (process temperature).
＜硬化物パターンおよびその製造方法＞
　本発明の好ましい実施形態にかかる硬化物パターンの製造方法は、上記のキットを用いて硬化物パターンを製造する方法であって、基板上に、インプリント用下層膜形成組成物を適用して下層膜を形成する下層膜形成工程と、上記下層膜の表面に、インプリント用硬化性組成物を適用する適用工程と、上記インプリント用硬化性組成物と、パターン形状を転写するためのパターンを有するモールドとを接触させるモールド接触工程と、上記インプリント用硬化性組成物に光を照射して硬化物を形成する光照射工程と、上記硬化物と上記モールドとを引き離す離型工程と、を有する。
　以下、硬化物パターンを形成する方法（硬化物パターンの製造方法）について、図１に従って説明する。本発明の構成が図面により限定されるものではないことは言うまでもない。 <Hardened product pattern and manufacturing method thereof>
A method for producing a cured product pattern according to a preferred embodiment of the present invention is a method for producing a cured product pattern using the above-described kit, wherein a lower layer film-forming composition for imprinting is applied to a lower layer on a substrate. An underlayer film forming step of forming a film, an application step of applying the curable composition for imprints to the surface of the underlayer film, the curable composition for imprints, and a pattern for transferring the pattern shape A mold contact step for bringing the mold into contact, a light irradiation step for irradiating the curable composition for imprints with light to form a cured product, and a release step for separating the cured product from the mold. Have.
Hereinafter, a method for forming a cured product pattern (a method for producing a cured product pattern) will be described with reference to FIG. It goes without saying that the configuration of the present invention is not limited by the drawings.
＜＜下層膜形成工程＞＞
　下層膜形成工程では、図１（１）および（２）に示す様に、基板１上に、下層膜２を形成する。下層膜は、インプリント用下層膜形成組成物を基板上に層状に適用して形成することが好ましい。 << Lower layer formation process >>
In the lower layer film forming step, the lower layer film 2 is formed on the substrate 1 as shown in FIGS. 1 (1) and (2). The lower layer film is preferably formed by applying the lower film forming composition for imprinting in a layer form on the substrate.
　基板上へのインプリント用下層膜形成組成物の適用方法としては、特に定めるものではなく、一般によく知られた適用方法を採用できる。具体的には、適用方法としては、例えば、ディップコート法、エアーナイフコート法、カーテンコート法、ワイヤーバーコート法、グラビアコート法、エクストルージョンコート法、スピンコート法、スリットスキャン法、あるいはインクジェット法が例示され、スピンコート法が好ましい。
　また、基板上にインプリント用下層膜形成組成物を層状に適用した後、好ましくは、熱によって溶剤を揮発（乾燥）させて、薄膜である下層膜を形成する。 The application method of the composition for forming an underlayer film for imprinting on the substrate is not particularly defined, and generally known application methods can be employed. Specifically, as an application method, for example, dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spin coating method, slit scanning method, or ink jet method And a spin coating method is preferable.
Moreover, after applying the lower film | membrane formation composition for imprints on a board | substrate in a layer form, Preferably, a solvent is volatilized (dried) with a heat | fever, and the lower layer film which is a thin film is formed.
　下層膜２の厚さは、２ｎｍ以上であることが好ましく、３ｎｍ以上であることがより好ましく、４ｎｍ以上であることがさらに好ましく、５ｎｍ以上であってもよく、７ｎｍ以上であってもよい。また、下層膜の厚さは、４０ｎｍ以下であることが好ましく、３０ｎｍ以下であることがより好ましく、２０ｎｍ以下であることがさらに好ましく、１５ｎｍ以下であってもよく、さらには１０ｎｍ以下であってもよい。膜厚を上記下限値以上とすることにより、インプリント用硬化性組成物の下層膜上での拡張性（濡れ性）が向上し、インプリント後の均一な残膜形成が可能となる。膜厚を上記上限値以下とすることにより、インプリント後の残膜が薄くなり、膜厚ムラが発生しにくくなり、残膜均一性が向上する傾向にある。 The thickness of the lower layer film 2 is preferably 2 nm or more, more preferably 3 nm or more, further preferably 4 nm or more, and may be 5 nm or more, or 7 nm or more. Further, the thickness of the lower layer film is preferably 40 nm or less, more preferably 30 nm or less, further preferably 20 nm or less, may be 15 nm or less, and further 10 nm or less. Also good. By setting the film thickness to be equal to or more than the above lower limit value, the expandability (wetting property) on the lower layer film of the curable composition for imprinting is improved, and a uniform residual film after imprinting can be formed. By setting the film thickness to be equal to or less than the above upper limit value, the remaining film after imprinting becomes thin, film thickness unevenness hardly occurs, and the remaining film uniformity tends to be improved.
　基板の材質としては、特に定めるものでは無く、特開２０１０－１０９０９２号公報（対応ＵＳ出願の公開番号は、米国特許出願公開第２０１１／０１８３１２７号明細書）の段落０１０３の記載を参酌でき、これらの内容は本明細書に組み込まれる。本発明では、シリコン基板、ガラス基板、石英基板、サファイア基板、シリコンカーバイド（炭化ケイ素）基板、窒化ガリウム基板、アルミニウム基板、アモルファス酸化アルミニウム基板、多結晶酸化アルミニウム基板、ならびに、ＧａＡｓＰ、ＧａＰ、ＡｌＧａＡｓ、ＩｎＧａＮ、ＧａＮ、ＡｌＧａＮ、ＺｎＳｅ、ＡｌＧａ、ＩｎＰ、または、ＺｎＯから構成される基板が挙げられる。なお、ガラス基板の具体的な材料例としては、アルミノシリケートガラス、アルミノホウケイ酸ガラス、バリウムホウケイ酸ガラスが挙げられる。本発明では、シリコン基板が好ましい。 The material of the substrate is not particularly defined, and the description in paragraph 0103 of JP 2010-109092 A (the publication number of the corresponding US application is US Patent Application Publication No. 2011/0183127) can be referred to. Is incorporated herein by reference. In the present invention, a silicon substrate, a glass substrate, a quartz substrate, a sapphire substrate, a silicon carbide (silicon carbide) substrate, a gallium nitride substrate, an aluminum substrate, an amorphous aluminum oxide substrate, a polycrystalline aluminum oxide substrate, GaAsP, GaP, AlGaAs, Examples include a substrate made of InGaN, GaN, AlGaN, ZnSe, AlGa, InP, or ZnO. Specific examples of materials for the glass substrate include aluminosilicate glass, aluminoborosilicate glass, and barium borosilicate glass. In the present invention, a silicon substrate is preferable.
＜＜適用工程＞＞
　適用工程では、例えば、図１（３）に示すように、上記下層膜２の表面に、インプリント用硬化性組成物３を適用する。
　インプリント用硬化性組成物の適用方法としては、特に定めるものでは無く、特開２０１０－１０９０９２号公報（対応ＵＳ出願の公開番号は、米国特許出願公開第２０１１／０１９９５９２号明細書）の段落０１０２の記載を参酌でき、この内容は本明細書に組み込まれる。上記インプリント用硬化性組成物は、インクジェット法により、上記下層膜の表面に適用することが好ましい。また、インプリント用硬化性組成物を、多重塗布により塗布してもよい。インクジェット法などにより下層膜の表面に液滴を配置する方法において、液滴の量は１～２０ｐＬ程度が好ましく、液滴間隔をあけて下層膜表面に配置することが好ましい。液滴間隔としては、１０～１０００μｍの間隔が好ましい。液滴間隔は、インクジェット法の場合は、インクジェットのノズルの配置間隔とする。
　さらに、下層膜２と、下層膜上に適用した膜状のインプリント用硬化性組成物３の体積比は、１：１～５００であることが好ましく、１：１０～３００であることがより好ましく、１：５０～２００であることがさらに好ましい。
　また、本発明の好ましい実施形態に係る積層体の製造方法は、本発明のキットを用いて製造する方法であって、上記インプリント用下層膜形成組成物から形成された下層膜の表面に、インプリント用硬化性組成物を適用することを含む。さらに、本発明の好ましい実施形態に係る積層体の製造方法は、上記インプリント用下層膜形成組成物を基板上に層状に適用する工程を含み、上記層状に適用したインプリント用下層膜形成組成物を８０～２５０℃（好ましくは、１５０℃以上、また、２５０℃以下）で、加熱（ベーク）することを含むことが好ましい。加熱時間は、３０秒～５分とすることができる。 << Applicable process >>
In the application step, for example, as shown in FIG. 1 (3), the curable composition 3 for imprinting is applied to the surface of the lower layer film 2.
The method for applying the curable composition for imprints is not particularly defined, and paragraph 0102 of JP 2010-109092 A (the publication number of the corresponding US application is US Patent Application Publication No. 2011/0199592). The contents of which are incorporated herein by reference. The curable composition for imprints is preferably applied to the surface of the lower layer film by an inkjet method. Moreover, you may apply | coat the curable composition for imprint by multiple application | coating. In the method of disposing droplets on the surface of the lower layer film by an inkjet method or the like, the amount of the droplets is preferably about 1 to 20 pL, and it is preferable to dispose the droplets on the surface of the lower layer film with an interval between the droplets. The interval between the droplets is preferably 10 to 1000 μm. In the case of the ink jet method, the liquid drop interval is the arrangement interval of the ink jet nozzles.
Furthermore, the volume ratio of the lower film 2 and the film-like curable composition for imprint 3 applied on the lower film is preferably 1: 1 to 500, more preferably 1:10 to 300. A ratio of 1:50 to 200 is more preferable.
Moreover, the manufacturing method of the laminated body which concerns on preferable embodiment of this invention is a method of manufacturing using the kit of this invention, Comprising: On the surface of the lower layer film formed from the said lower layer film formation composition for imprints, Applying a curable composition for imprints. Furthermore, the manufacturing method of the laminated body which concerns on preferable embodiment of this invention includes the process of applying the said underlayer film formation composition for imprints on a board | substrate on a layer form, The underlayer film formation composition for imprints applied to the said layer form It is preferable to include heating (baking) the product at 80 to 250 ° C. (preferably 150 ° C. or more and 250 ° C. or less). The heating time can be 30 seconds to 5 minutes.
＜＜モールド接触工程＞＞
　モールド接触工程では、例えば、図１（４）に示すように、上記インプリント用硬化性組成物３とパターン形状を転写するためのパターンを有するモールド４とを接触させる。このような工程を経ることにより、所望の硬化物パターン（インプリントパターン）が得られる。
　具体的には、膜状のインプリント用硬化性組成物に所望のパターンを転写するために、膜状のインプリント用硬化性組成物３の表面にモールド４を押接する。 << Mold contact process >>
In the mold contact step, for example, as shown in FIG. 1 (4), the curable composition for imprints 3 is brought into contact with the mold 4 having a pattern for transferring the pattern shape. Through such a process, a desired cured product pattern (imprint pattern) is obtained.
Specifically, in order to transfer a desired pattern to the film-shaped curable composition for imprints, the mold 4 is pressed against the surface of the film-shaped curable composition for imprints 3.
　モールドは、光透過性のモールドであってもよいし、光非透過性のモールドであってもよい。光透過性のモールドを用いる場合は、モールド側からインプリント用硬化性組成物３に光を照射することが好ましい。一方、光非透過性のモールドを用いる場合は、基板として、光透過性基板を用い、基板側から光を照射することが好ましい。本発明では、光透過性モールドを用い、モールド側から光を照射することがより好ましい。
　本発明で用いることのできるモールドは、転写されるべきパターンを有するモールドである。上記モールドが有するパターンは、例えば、フォトリソグラフィや電子線描画法等によって、所望する加工精度に応じて形成できるが、本発明では、モールドパターン製造方法は特に制限されない。また、本発明の好ましい実施形態に係る硬化物パターン製造方法によって形成したパターンをモールドとして用いることもできる。
　本発明において用いられる光透過性モールドを構成する材料は、特に限定されないが、ガラス、石英、ポリメチルメタクリレート（ＰＭＭＡ）、ポリカーボネート樹脂などの光透過性樹脂、透明金属蒸着膜、ポリジメチルシロキサンなどの柔軟膜、光硬化膜、金属膜等が例示され、石英が好ましい。
　本発明において光透過性の基板を用いた場合に使われる非光透過型モールド材としては、特に限定されないが、所定の強度を有するものであればよい。具体的には、セラミック材料、蒸着膜、磁性膜、反射膜、Ｎｉ、Ｃｕ、Ｃｒ、Ｆｅなどの金属基板、ＳｉＣ、シリコン、窒化シリコン、ポリシリコン、酸化シリコン、アモルファスシリコンなどの基板などが例示され、特に制約されない。 The mold may be a light transmissive mold or a light non-transmissive mold. When using a light-transmitting mold, it is preferable to irradiate the curable composition 3 for imprinting with light from the mold side. On the other hand, when using a light-impermeable 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 transmissive mold and irradiate light from the mold side.
The mold that can be used in the present invention is a mold having a pattern to be transferred. Although the pattern which the said mold has can be formed according to the processing precision desired, for example by photolithography, an electron beam drawing method, etc., in this invention, the mold pattern manufacturing method in particular is not restrict | limited. Moreover, the pattern formed by the hardened | cured material pattern manufacturing method which concerns on preferable embodiment of this invention can also be used as a mold.
The material constituting the light-transmitting mold used in the present invention is not particularly limited, but includes a light-transmitting resin such as glass, quartz, polymethyl methacrylate (PMMA), and polycarbonate resin, a transparent metal vapor-deposited film, and polydimethylsiloxane. Examples thereof include a flexible film, a photocured film, and a metal film, and quartz is preferable.
In the present invention, the non-light-transmitting mold material used when a light-transmitting substrate is used is not particularly limited as long as it has a predetermined strength. Specific examples include ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, and substrates such as SiC, silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon. There are no particular restrictions.
　上記硬化物パターンの製造方法では、インプリント用硬化性組成物を用いてインプリントリソグラフィを行うに際し、モールド圧力を１０気圧以下とするのが好ましい。モールド圧力を１０気圧以下とすることにより、モールドや基板が変形しにくくパターン精度が向上する傾向にある。また、加圧が低いため装置を縮小できる傾向にある点からも好ましい。モールド圧力は、モールド凸部にあたるインプリント用硬化性組成物の残膜が少なくなる一方で、モールド転写の均一性が確保できる範囲から選択することが好ましい。
　また、インプリント用硬化性組成物とモールドとの接触を、ヘリウムガスまたは凝縮性ガス、あるいはヘリウムガスと凝縮性ガスの両方を含む雰囲気下で行うことも好ましい。 In the manufacturing method of the said hardened | cured material pattern, when performing imprint lithography using the curable composition for imprints, it is preferable to make a mold pressure into 10 atmospheres or less. By setting the mold pressure to 10 atm or less, the mold and the substrate are hardly deformed and the pattern accuracy tends to be improved. Further, it is preferable from the viewpoint that the apparatus can be reduced because the pressure is low. The mold pressure is preferably selected from a range in which the residual film of the curable composition for imprint hitting the mold convexity is reduced while ensuring the uniformity of mold transfer.
Moreover, it is also preferable to perform contact between the curable composition for imprints and the mold in an atmosphere containing helium gas or condensable gas, or both helium gas and condensable gas.
＜＜光照射工程＞＞
　光照射工程では、上記インプリント用硬化性組成物に光を照射して硬化物を形成する。光照射工程における光照射の照射量は、硬化に必要な最小限の照射量よりも十分大きければよい。硬化に必要な照射量は、インプリント用硬化性組成物の不飽和結合の消費量などを調べて適宜決定される。
　照射する光の種類は特に定めるものではないが、紫外光が例示される。
　また、本発明に適用されるインプリントリソグラフィにおいては、光照射の際の基板温度は、通常、室温とするが、反応性を高めるために加熱をしながら光照射してもよい。光照射の前段階として、真空状態にしておくと、気泡混入防止、酸素混入による反応性低下の抑制、モールドとインプリント用硬化性組成物との密着性向上に効果があるため、真空状態で光照射してもよい。また、上記硬化物パターン製造方法中、光照射時における好ましい真空度は、１０-1Ｐａから常圧の範囲である。
　露光に際しては、露光照度を１～５００ｍＷ／ｃｍ２の範囲にすることが好ましく、１０～４００ｍＷ／ｃｍ２の範囲にすることがより好ましい。露光の時間は特に限定されないが、０．０１～１０秒であることが好ましく、０．５～１秒であることがより好ましい。露光量は、５～１０００ｍＪ／ｃｍ２の範囲にすることが好ましく、１０～５００ｍＪ／ｃｍ２の範囲にすることがより好ましい。
　上記硬化物パターン製造方法においては、光照射により膜状のインプリント用硬化性組成物（パターン形成層）を硬化させた後、必要に応じて、硬化させたパターンに熱を加えてさらに硬化させる工程を含んでいてもよい。光照射後にインプリント用硬化性組成物を加熱硬化させるための温度としては、１５０～２８０℃が好ましく、２００～２５０℃がより好ましい。また、熱を付与する時間としては、５～６０分間が好ましく、１５～４５分間がさらに好ましい。 << Light irradiation process >>
In the light irradiation step, the curable composition for imprints is irradiated with light to form a cured product. The irradiation amount of light irradiation in the light irradiation step may be sufficiently larger than the minimum irradiation amount necessary for curing. The amount of irradiation necessary for curing is appropriately determined by examining the consumption of unsaturated bonds of the curable composition for imprints.
Although the kind of light to irradiate is not specifically defined, an ultraviolet light is illustrated.
In the imprint lithography applied to the present invention, the substrate temperature at the time of light irradiation is usually room temperature, but light irradiation may be performed while heating in order to increase the reactivity. As a pre-stage of light irradiation, if it is in a vacuum state, it is effective in preventing bubble mixing, suppressing the decrease in reactivity due to oxygen mixing, and improving the adhesion between the mold and the curable composition for imprinting. It may be irradiated with light. In the cured product pattern manufacturing method, a preferable degree of vacuum at the time of light irradiation is in the range of 10 −1 Pa to normal pressure.
In exposure, the exposure illuminance is preferably in the range of 1 to 500 mW / cm 2 , and more preferably in the range of 10 to 400 mW / cm 2 . The exposure time is not particularly limited, but is preferably 0.01 to 10 seconds, and more preferably 0.5 to 1 second. Exposure amount is preferably in a range of 5 ~ 1000mJ / cm 2, and more preferably in the range of 10 ~ 500mJ / cm 2.
In the cured product pattern manufacturing method, the film-shaped curable composition for imprints (pattern forming layer) is cured by light irradiation, and then is further cured by applying heat to the cured pattern as necessary. A process may be included. The temperature for heat-curing the curable composition for imprints after light irradiation is preferably 150 to 280 ° C, more preferably 200 to 250 ° C. The time for applying heat is preferably 5 to 60 minutes, more preferably 15 to 45 minutes.
＜＜離型工程＞＞
　離型工程では、上記硬化物と上記モールドとを引き離す（図１（５））。得られた硬化物パターンは後述する通り各種用途に利用できる。
　すなわち、本発明では、上記下層膜の表面に、さらに、インプリント用硬化性組成物から形成される硬化物パターンを有する、積層体が開示される。また、本発明で用いるインプリント用硬化性組成物からなるパターン形成層の膜厚は、使用する用途によって異なるが、０．０１μｍ～３０μｍ程度である。
　さらに、後述するとおり、エッチング等を行うこともできる。 << Mold release process >>
In the release step, the cured product and the mold are separated (FIG. 1 (5)). The obtained cured product pattern can be used for various applications as described later.
That is, in this invention, the laminated body which has further the hardened | cured material pattern formed from the curable composition for imprints on the surface of the said lower layer film is disclosed. Further, the film thickness of the pattern forming layer made of the curable composition for imprints used in the present invention is about 0.01 μm to 30 μm, although it varies depending on the intended use.
Further, as described later, etching or the like can be performed.
＜硬化物パターンとその応用＞
　上述のように上記硬化物パターンの製造方法によって形成された硬化物パターンは、液晶表示装置（ＬＣＤ）などに用いられる永久膜や、半導体素子製造用のエッチングレジスト（リソグラフィ用マスク）として使用することができる。
　特に、本発明では、本発明の好ましい実施形態に係る硬化物パターンの製造方法により硬化物パターンを得る工程を含む、回路基板の製造方法を開示する。さらに、本発明の好ましい実施形態に係る回路基板の製造方法では、上記硬化物パターンの製造方法により得られた硬化物パターンをマスクとして基板にエッチングまたはイオン注入を行う工程と、電子部材を形成する工程と、を有していてもよい。上記回路基板は、半導体素子であることが好ましい。さらに、本発明では、上記回路基板の製造方法により回路基板を得る工程と、上記回路基板と上記回路基板を制御する制御機構とを接続する工程と、を有する電子機器の製造方法を開示する。
　また、上記硬化物パターン製造方法によって形成されたパターンを利用して液晶表示装置のガラス基板にグリッドパターンを形成し、反射や吸収が少なく、大画面サイズ（例えば５５インチ、６０インチ超）の偏光板を安価に製造することが可能である。例えば、特開２０１５－１３２８２５号公報や国際公開第２０１１／１３２６４９号に記載の偏光板が製造できる。なお、１インチは２５．４ｍｍである。
　本発明で形成された硬化物パターンは、図１（６）（７）に示す通り、エッチングレジスト（リソグラフィ用マスク）としても有用である。硬化物パターンをエッチングレジストとして利用する場合には、まず、基板として例えばＳｉＯ２等の薄膜が形成されたシリコン基板（シリコンウェハ等）等を用い、基板上に上記硬化物パターン製造方法によって、例えば、ナノまたはミクロンオーダーの微細な硬化物パターンを形成する。本発明では特にナノオーダーの微細パターンを形成でき、さらにはサイズが５０ｎｍ以下、特には３０ｎｍ以下のパターンも形成できる点で有益である。上記硬化物パターン製造方法で形成する硬化物パターンのサイズの下限値については特に定めるものでは無いが、例えば、１ｎｍ以上とすることができる。
　基板上に、硬化物パターンの製造方法により硬化物パターンを得る工程と、得られた上記硬化物パターンを用いて上記基板にエッチングを行う工程と、を有する、インプリント用モールドの製造方法も好ましい実施形態として挙げられる。
　ウェットエッチングの場合にはフッ化水素等、ドライエッチングの場合にはＣＦ４等のエッチングガスを用いてエッチングすることにより、基板上に所望の硬化物パターンを形成することができる。硬化物パターンは、特にドライエッチングに対するエッチング耐性が良好である。すなわち、上記硬化物パターン製造方法によって形成されたパターンは、リソグラフィ用マスクとして好ましく用いられる。 <Hardened product pattern and its application>
As described above, the cured product pattern formed by the method for producing a cured product pattern is used as a permanent film used for a liquid crystal display (LCD) or the like, or as an etching resist (lithography mask) for manufacturing a semiconductor element. Can do.
In particular, the present invention discloses a circuit board manufacturing method including a step of obtaining a cured product pattern by a cured product pattern manufacturing method according to a preferred embodiment of the present invention. Furthermore, in the method for manufacturing a circuit board according to a preferred embodiment of the present invention, the step of performing etching or ion implantation on the substrate using the cured product pattern obtained by the method for manufacturing a cured product pattern as a mask, and the formation of the electronic member are formed. You may have a process. The circuit board is preferably a semiconductor element. Furthermore, the present invention discloses a method for manufacturing an electronic device, which includes a step of obtaining a circuit board by the method for manufacturing a circuit board, and a step of connecting the circuit board and a control mechanism for controlling the circuit board.
In addition, a grid pattern is formed on the glass substrate of the liquid crystal display device using the pattern formed by the above-described cured product pattern manufacturing method, and polarized light having a large screen size (for example, 55 inches or more than 60 inches) with little reflection and absorption. It is possible to manufacture the plate at a low cost. For example, a polarizing plate described in JP-A-2015-132825 and International Publication No. 2011-132649 can be produced. One inch is 25.4 mm.
The cured product pattern formed in the present invention is also useful as an etching resist (lithographic mask) as shown in FIGS. When using the cured product pattern as an etching resist, first, for example, a silicon substrate (such as a silicon wafer) on which a thin film such as SiO 2 is formed as a substrate, and the cured product pattern manufacturing method on the substrate, for example, A fine cured material pattern of nano or micron order is formed. In the present invention, it is particularly advantageous in that a nano-order fine pattern can be formed, and a pattern having a size of 50 nm or less, particularly 30 nm or less can be formed. The lower limit of the size of the cured product pattern formed by the cured product pattern manufacturing method is not particularly defined, but can be, for example, 1 nm or more.
Also preferred is a method for producing an imprint mold, comprising: a step of obtaining a cured product pattern by a method of producing a cured product pattern on a substrate; and a step of etching the substrate using the obtained cured product pattern. As an embodiment.
A desired cured product pattern can be formed on the substrate by etching using an etching gas such as hydrogen fluoride in the case of wet etching or CF 4 in the case of dry etching. The cured product pattern has particularly good etching resistance against dry etching. That is, the pattern formed by the cured product pattern manufacturing method is preferably used as a lithography mask.
　図２は、下層膜の表面にインプリント用硬化性組成物をインクジェット法により塗布した場合の、インプリント用硬化性組成物の濡れ広がりの状態を模式的に示す平面図である。インプリント用硬化性組成物がインクジェット（ＩＪ）法により適用される場合、例えば、同図に示すように、下層膜２１の表面にインプリント用硬化性組成物２２の液滴を等間隔に滴下する（図２（ａ））。そこに、モールドを接触させると、上記液滴が下層膜２１上で広がり、膜状のインプリント用硬化性組成物２２ａ、２２ｂ、２２ｃとなっていく（図２（ｂ）、（ｃ）、（ｄ））。しかし、インプリント用硬化性組成物が均一に広がらないで、例えば、図２（ｃ）で濡れ広がりが止まってしまうと、下層膜２１上にはインプリント用硬化性組成物２２ｂの状態の完全に広がっていない膜が形成される。つまり、膜厚が薄いあるいは膜のない領域２３が生じてしまう場合がある。このようになると、モールドのパターンにインプリント用硬化性組成物が十分に充填されない部分が生じ、インプリント層にパターンのない部分ができてしまう。例えば、このような一部において欠損あるいは厚みの不十分な部分のあるインプリント層のパターンをマスクにしてエッチングを実施した場合、膜厚の薄い領域ないし膜のない領域２３とそれ以外の領域２２ｂとでエッチングのムラが発生し、インプリント領域全面にわたって均一に所望のパターン形状をエッチングし転写することが困難となる。
　これに対し、本発明のインプリント用下層膜形成組成物によれば、これにより形成される下層膜とインプリント用硬化性組成物との界面張力が改善され濡れ性が向上している。そのため、より確実に図２（ｄ）の状態の隅々にまで広がったインプリント用硬化性組成物２２ｃとなる。その結果、全体にわたってインプリント用硬化性組成物がモールドに的確かつ十分に充填され、形成されたインプリント層において厚さにムラのない良好なパターニングを達成することができる。また、充填性の向上により高速のインプリントが可能となりスループットの改善にもつなげることができる。
　なお、上記の説明では、インクジェット法によりインプリント用硬化性組成物を下層膜上に適用する例を挙げて本発明の好ましい実施形態にかかる作用機序について説明したが、これにより本発明が限定して解釈されるものではない。例えば、スクリーン塗布やスピンコートなどにおいても、良好な濡れ性と優れた充填性は加工上および製品品質上の利点につながり、発明の効果を好適に発揮し得るものである。 FIG. 2 is a plan view schematically showing a wet spread state of the curable composition for imprints when the curable composition for imprints is applied to the surface of the lower layer film by an inkjet method. When the curable composition for imprints is applied by an inkjet (IJ) method, for example, as shown in the figure, droplets of the curable composition for imprints 22 are dropped on the surface of the lower layer film 21 at equal intervals. (FIG. 2A). When the mold is brought into contact therewith, the droplets spread on the lower layer film 21 and become film-shaped curable compositions for imprints 22a, 22b, 22c (FIGS. 2B, 2C, 2C). (D)). However, if the curable composition for imprints does not spread uniformly, for example, when wetting and spreading stops in FIG. 2C, the state of the curable composition for imprints 22b is completely on the lower layer film 21. A film that does not spread is formed. That is, a region 23 having a thin film thickness or no film may be generated. If it becomes like this, the part in which the curable composition for imprints is not fully filled will arise in the pattern of a mold, and the part without a pattern will be made in an imprint layer. For example, when etching is performed using a pattern of an imprint layer having a defect or an insufficiently thick portion in such a part as a mask, a thin region or a region 23 without a film and another region 22b. As a result, uneven etching occurs, and it becomes difficult to etch and transfer a desired pattern shape uniformly over the entire imprint region.
On the other hand, according to the lower layer film forming composition for imprints of the present invention, the interfacial tension between the lower layer film formed thereby and the curable composition for imprints is improved, and the wettability is improved. Therefore, the curable composition for imprint 22c is more reliably spread to every corner of the state of FIG. As a result, the curable composition for imprints can be filled in the mold accurately and sufficiently, and good patterning with uniform thickness can be achieved in the formed imprint layer. In addition, the improvement of filling property enables high-speed imprinting, which can lead to an improvement in throughput.
In the above description, the mechanism of action according to a preferred embodiment of the present invention has been described with reference to an example in which the curable composition for imprints is applied onto the lower layer film by an inkjet method, but the present invention is limited thereby. It is not to be interpreted as. For example, also in screen coating and spin coating, good wettability and excellent filling properties lead to advantages in processing and product quality, and the effects of the invention can be suitably exhibited.
　本発明で形成されたパターンは、具体的には、磁気ディスク等の記録媒体、固体撮像素子等の受光素子、ＬＥＤ（light emitting ｄioｄe）や有機ＥＬ（有機エレクトロルミネッセンス）等の発光素子、液晶表示装置（ＬＣＤ）等の光デバイス、回折格子、レリーフホログラム、光導波路、光学フィルタ、マイクロレンズアレイ等の光学部品、薄膜トランジスタ、有機トランジスタ、カラーフィルタ、反射防止膜、偏光板、偏光素子、光学フィルム、柱材等のフラットパネルディスプレイ用部材、ナノバイオデバイス、免疫分析チップ、デオキシリボ核酸（ＤＮＡ）分離チップ、マイクロリアクター、フォトニック液晶、ブロックコポリマーの自己組織化を用いた微細パターン形成（ｄｉｒｅｃｔｅｄ　ｓｅｌｆ－ａｓｓｅｍｂｌｙ、ＤＳＡ）のためのガイドパターン等の作製に好ましく用いることができる。 Specifically, the pattern formed in the present invention includes a recording medium such as a magnetic disk, a light receiving element such as a solid-state image sensor, a light emitting element such as an LED (light emitting diode) or an organic EL (organic electroluminescence), a liquid crystal display. Optical devices such as devices (LCD), optical components such as diffraction gratings, relief holograms, optical waveguides, optical filters, microlens arrays, thin film transistors, organic transistors, color filters, antireflection films, polarizing plates, polarizing elements, optical films, Flat panel display members such as pillars, nanobiodevices, immunoassay chips, deoxyribonucleic acid (DNA) separation chips, microreactors, photonic liquid crystals, micropattern formation using self-assembly of block copolymers (directed self-assembly, DSA) It can be preferably used in the preparation of the guide pattern, etc. for.
　以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。 The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
＜ポリマーＧ－１の合成例＞
　Ｎ2フローしている三口フラスコにメタノール（ＭｅＯＨ）（３００ｇ）、５－Ｂｒｏｍｏｉｓｏｐｈｔｈａｌｉｃ　Ａｃｉｄ（東京化成工業（株）製、１０ｇ）、濃硫酸（１ｍＬ）を加え、９０℃に加温し４時間熟成を行った。その後、減圧濃縮した。分液ロートに濃縮物と酢酸エチル（５００ｇ）、３％炭酸水素ナトリウム水溶液（３００ｇ）を加え、撹拌した。有機層を濃縮し、目的の化合物（中間体Ｇ－１Ａ）を合成した。 <Synthesis example of polymer G-1>
Methanol (MeOH) (300 g), 5-Bromoisophthalic Acid (manufactured by Tokyo Chemical Industry Co., Ltd., 10 g) and concentrated sulfuric acid (1 mL) are added to a three-necked flask with N 2 flow, and the mixture is heated to 90 ° C. and aged for 4 hours. Went. Then, it concentrated under reduced pressure. The concentrate and ethyl acetate (500 g) and 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).
　Ｎ2フローしている三口フラスコにテトラヒドロフラン（ＴＨＦ）（３００ｇ）、Ｇ－１Ａ（１０ｇ）を加え、０℃に冷却し、ＬｉＡｌＨ４（富士フイルム和光純薬（株）製、３ｇ）を少しずつ加え、２時間熟成を行った。その後、水（３ｇ）、１５％水酸化ナトリウム水溶液（３ｇ）、水（９ｇ）を加え、１時間熟成した。その後、濾過を行いろ液を濃縮することで目的の化合物（中間体Ｇ－１Ｂ）を合成した。 Tetrahydrofuran (THF) (300 g) and G-1A (10 g) are added to a three-necked flask with N 2 flow, cooled to 0 ° C., and LiAlH 4 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., 3 g) is gradually added. In addition, aging was performed for 2 hours. Thereafter, water (3 g), a 15% aqueous sodium hydroxide solution (3 g) and water (9 g) were added and aged for 1 hour. Then, the target compound (intermediate G-1B) was synthesized by filtering and concentrating the filtrate.
　Ｎ2フローしている三口フラスコにＤＭＦ（３００ｇ）、イミダゾール（８ｇ）、Ｇ－１Ｂ（１０ｇ）を加え、０℃に冷却し、ｔｅｒｔ－Ｂｕｔｙｌｄｉｍｅｔｈｙｌｃｈｌｏｒｏｓｉｌａｎｅ（東京化成工業（株）製、１８ｇ）を少しずつ加え、２時間熟成を行った。その後、減圧濃縮した。分液ロートに濃縮物と酢酸エチル（５００ｇ）、３％炭酸水素ナトリウム水溶液（３００ｇ）を加え、撹拌した。有機層を濃縮し、シリカゲルクロマトグラフィで精製し目的の化合物（中間体Ｇ－１Ｃ）を合成した。 DMF (300 g), imidazole (8 g) and G-1B (10 g) are added to a N 2 flow three-necked flask, cooled to 0 ° C., and tert-Butyldimethylchlorosilane (manufactured by Tokyo Chemical Industry Co., Ltd., 18 g) is slightly added. Each was added and aged for 2 hours. Then, it concentrated under reduced pressure. The concentrate and ethyl acetate (500 g) and 3% aqueous sodium hydrogen carbonate solution (300 g) were added to the separatory funnel and stirred. The organic layer was concentrated and purified by silica gel chromatography to synthesize the target compound (Intermediate G-1C).
　Ｎ2フローしている三口フラスコにＭｇ（１ｇ）、Ｇ－１Ｃ（１０ｇ）、ＴＨＦ（１００ｇ）を加え、０℃に冷却し１時間熟成を行った。その後、アセトン（２ｇ）を少しずつ加え、２時間熟成を行った。その後、減圧濃縮した。分液ロートに濃縮物と酢酸エチル（５００ｇ）、３％炭酸水素ナトリウム水溶液（３００ｇ）を加え、撹拌した。有機層を濃縮し、シリカゲルクロマトグラフィで精製し目的の化合物（中間体Ｇ－１Ｄ）を合成した。 Mg (1 g), G-1C (10 g), and THF (100 g) were added to a N 2 flow three-necked flask, cooled to 0 ° C., and aged for 1 hour. Thereafter, acetone (2 g) was added little by little, and aging was performed for 2 hours. Then, it concentrated under reduced pressure. The concentrate and ethyl acetate (500 g) and 3% aqueous sodium hydrogen carbonate solution (300 g) were added to the separatory funnel and stirred. The organic layer was concentrated and purified by silica gel chromatography to synthesize the target compound (Intermediate G-1D).
　Ｎ2フローしている三口フラスコにＧ－１Ｄ（１０ｇ）、シクロヘキサン（１００ｇ）を加え、０℃に冷却し、２０％ブチルリチウムシクロヘキサン溶液（東京化成工業（株）製、１２ｍＬ）を滴下し１時間熟成を行った。その後、メタクリル酸クロリド（東京化成工業（株）製、３ｇ）を滴下し１時間熟成を行った。その後、ＴＨＦ（１００ｇ）、１Ｍ ＨＣｌ水溶液を加え、５時間熟成を行った。その後、酢酸エチル（１０００ｇ）、３％炭酸水素ナトリウム水溶液（３００ｇ）を加え、撹拌した。有機層を濃縮し、シリカゲルクロマトグラフィで精製し目的の化合物（中間体Ｇ－１Ｅ）を合成した。 G-1D (10 g) and cyclohexane (100 g) were added to a three-necked flask with N 2 flow, cooled to 0 ° C., and a 20% butyl lithium cyclohexane solution (Tokyo Chemical Industry Co., Ltd., 12 mL) was added dropwise. Aged for time. Thereafter, methacrylic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd., 3 g) was added dropwise and aging was performed for 1 hour. Thereafter, THF (100 g) and 1M HCl aqueous solution were added, and aging was performed for 5 hours. Then, ethyl acetate (1000 g) and 3% aqueous sodium hydrogen carbonate solution (300 g) were added and stirred. The organic layer was concentrated and purified by silica gel chromatography to synthesize the target compound (Intermediate G-1E).
　Ｎ2フローしている三口フラスコにＰＧＭＥＡ（３０ｇ）を加え、６０℃に加温した。２－Ｈｙｄｒｏｘｙｅｔｈｙｌ　Ｍｅｔｈａｃｒｙｌａｔｅ（東京化成工業（株）製、１３ｇ、１００ｍｍｏｌ）とＧ－１Ｅ（２６ｇ、１００．０ｍｍｏｌ）と光ラジカル重合開始剤（富士フイルム和光純薬（株）製、Ｖ－６５、１．０ｇ、４．０ｍｍｏｌ）をＰＧＭＥＡ（７０ｇ）に溶解し、得られた混合物を上記フラスコの内温が６５℃を超えない温度で２時間かけて滴下し、さらに９０℃で４時間熟成を行った。その後、２５℃まで冷却した。別の三口フラスコにジイソプロピルエーテル（４３５．５ｇ）とヘキサン（１８６．６ｇ）を加え０℃に冷却し撹拌した。これに上記フラスコ中の反応液を、５℃を超えない温度で３０分間かけて滴下し、１時間撹拌した。その後、１時間静止し、減圧濾過をした。得られた粉末を減圧乾燥することで目的の化合物（中間体Ｇ－１Ｆ）を合成した。） PGMEA (30 g) was added to a three-necked flask with N 2 flow and heated to 60 ° C. 2-Hydroxyethyl Methacrylate (Tokyo Chemical Industry Co., Ltd., 13 g, 100 mmol), G-1E (26 g, 100.0 mmol), photo radical polymerization initiator (Fuji Film Wako Pure Chemical Industries, Ltd., V-65, 1) 0.0 g, 4.0 mmol) was dissolved in PGMEA (70 g), and the resulting mixture was added dropwise over 2 hours at a temperature where the internal temperature of the flask did not exceed 65 ° C., followed by aging at 90 ° C. for 4 hours. It was. Then, it cooled to 25 degreeC. 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 said flask was dripped at this at the temperature which does not exceed 5 degreeC over 30 minutes, and it stirred for 1 hour. Then, it stood for 1 hour and filtered under reduced pressure. The obtained powder was dried under reduced pressure to synthesize the target compound (Intermediate G-1F). )
　Ｎ2フローしている三口フラスコにＰＧＭＥＡ（４５．３８ｇ）、中間体Ｇ－１Ｆ（１９．７ｇ、１００．０ｍｍｏｌ）トリエチルアミン（東京化成工業（株）製、１５ｇ、１５０．０ｍｍｏｌ）を加え、０℃に冷却した。ＰＧＭＥＡ（４５．３８ｇ）とＡｃｒｙｌｏｙｌ　Ｃｈｏｒｉｄｅ（１４ｇ、１５０．０ｍｍｏｌ）を混合し、上記フラスコの内温が１０℃を超えない温度で２時間かけて滴下し、さらに２０℃で４時間熟成を行った。その後、０℃まで冷却した。別の三口フラスコにジイソプロピルエーテル（４３５．５ｇ）とヘキサン（１８６．６ｇ）を加え０℃に冷却し撹拌した。これに上記フラスコ中の反応液を、５℃を超えない温度で３０分間かけて滴下し、１時間撹拌した。その後、１時間静止し、減圧濾過をした。得られた粉末を水洗し、減圧乾燥することで目的の化合物（Ｇ－１）を合成した。
　他のポリマーは、上記合成例にならって合成した。 PGMEA (45.38 g), intermediate G-1F (19.7 g, 100.0 mmol), triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd., 15 g, 150.0 mmol) were added to a N 2 -flowing three-necked flask. Cooled to ° C. PGMEA (45.38 g) and Acryloy Chylide (14 g, 150.0 mmol) were mixed, added dropwise over 2 hours at a temperature not exceeding 10 ° C., and further aged at 20 ° C. for 4 hours. . Then, it cooled to 0 degreeC. Diisopropyl ether (435.5 g) and hexane (186.6 g) were added to another three-necked flask, and the mixture was cooled to 0 ° C. and stirred. The reaction liquid in the said flask was dripped at this at the temperature which does not exceed 5 degreeC over 30 minutes, and it stirred for 1 hour. Then, it stood 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 according to the above synthesis example.
＜下層膜形成組成物の調製＞
　下表１～４に示した通り各成分を配合し、孔径０．１μｍのポリテトラフルオロエチレン（ＰＴＦＥ）フィルタと孔径０．００３μｍのＵＰＥフィルタ（超高分子量ポリエチレン）にて二段階ろ過を実施し、実施例および比較例に示すインプリント用下層膜形成組成物を調製した。表１～４には組み合わせて用いたインプリント用硬化性組成物の番号を併せて表記している。 <Preparation of composition for forming lower layer film>
Each component is blended as shown in Tables 1 to 4 below, and two-stage filtration is performed with a polytetrafluoroethylene (PTFE) filter having a pore size of 0.1 μm and a UPE filter (ultra high molecular weight polyethylene) having a pore size of 0.003 μm. The underlayer film forming compositions for imprints shown in Examples and Comparative Examples were prepared. Tables 1 to 4 also show the numbers of the curable compositions for imprints used in combination.
＜８０℃でベークしたときの脱離成分の確認方法＞
　シリコンウェハ（直径８インチ）上に、インプリント用下層膜形成組成物をスピンコートした。その後、８０℃、３分間、空気雰囲気下のベーク条件でホットプレートを用いて加熱し、ウェハ上に下層膜を形成した。得られた下層膜の厚さは約１０ｎｍであった。得られた下層膜をテトラヒドロフラン（ＴＨＦ）に３０分間浸漬し、得られたＴＨＦ溶液をＬＣ/ＭＳを用いて分析した。
　このようにして、式（ｒ１）または（ｒ２）あるいは、式（ｒ１－１）で表され、分子量が２１０以上の化合物の検出が確認されたか否かを確認した。
　後述するポリマーの下に点線で囲んだ化合物が脱離した化合物である。ポリマーＨ－１～Ｈ－３については、分子量２１０以上の化合物の脱離は認められなかった。ポリマーＨ－３については、式（ｒ１）または（ｒ２）で表される化合物あるいは式（ｒ１－１）で表される化合物の脱離が認められなかった。 <Method for confirming desorbed components when baked at 80 ° C.>
A composition for forming a lower layer film for imprinting was spin-coated on a silicon wafer (diameter 8 inches). Then, it heated using the hotplate on baking conditions of 80 degreeC and the air atmosphere for 3 minutes, and formed the lower layer film | membrane on the wafer. The thickness of the obtained lower layer film was about 10 nm. The obtained lower layer film was immersed in tetrahydrofuran (THF) for 30 minutes, and the obtained THF solution was analyzed using LC / MS.
In this way, it was confirmed whether detection of a compound represented by the formula (r1), (r2) or the formula (r1-1) and having a molecular weight of 210 or more was confirmed.
It is a compound in which a compound surrounded by a dotted line is removed under the polymer described later. For the polymers H-1 to H-3, the elimination of compounds having a molecular weight of 210 or more was not observed. With respect to polymer H-3, elimination of the compound represented by formula (r1) or (r2) or the compound represented by formula (r1-1) was not observed.
＜インプリント用硬化性組成物の調製＞
　表５に示す各化合物を混合し、さらに重合禁止剤として４－ヒドロキシ－２，２，６，６－テトラメチルピペリジン－１－オキシルフリーラジカル（東京化成製）を表に示す化合物のうち、重合性化合物の合計量に対して２００質量ｐｐｍ（０．０２質量％）となるように加えて調製し、インプリント用硬化性組成物を得た。これを孔径０．１μｍのポリテトラフルオロエチレン（ＰＴＦＥ）フィルタと孔径０．００３μｍのＵＰＥ（超高分子量ポリエチレン）フィルタにて二段階ろ過した。 <Preparation of curable composition for imprint>
Each compound shown in Table 5 was mixed, and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical (manufactured by Tokyo Chemical Industry) as a polymerization inhibitor was further polymerized among the compounds shown in the table. The curable composition for imprints was obtained by adding 200 mass ppm (0.02 mass%) to the total amount of the functional compound. This was two-stage filtered through a polytetrafluoroethylene (PTFE) filter having a pore size of 0.1 μm and a UPE (ultra high molecular weight polyethylene) filter having a pore size of 0.003 μm.
＜表面張力＞
　表面張力の測定は、協和界面科学（株）製、表面張力計　ＳＵＲＦＡＣＥＴＥＮＳＩＯＭＥＴＥＲ　ＣＢＶＰ－Ａ３を用い、ガラスプレートを用いて２３℃で行った。単位は、ｍＮ/ｍで示す。１水準につき２つの試料を作製し、それぞれ３回測定し、合計６回の算術平均値を評価値として採用した。 <Surface tension>
The surface tension was measured at 23 ° C. using a surface tension meter SURFACETENSOMETER CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd. using a glass plate. The unit is indicated by mN / m. Two samples were prepared for each level, measured three times each, and a total of six arithmetic average values were adopted as evaluation values.
＜ハンセン溶解度パラメータ間距離（ΔＨＳＰ）の算出＞
　ハンセン溶解度パラメータはＨＳＰ計算ソフトＨＳＰiＰにて計算した。
　各化合物の構造式をＳＭＩＬＥＳ形式にて上記ソフトに入力することで、ハンセン溶解度パラメータの各成分（ｄ成分、ｐ成分を、ｈ成分）を算出した。算出したハンセン溶解度パラメータについて、必要により、成分間のハンセン溶解度パラメータ間距離（ΔＨＳＰ：ΔＤ、ΔＰ、ΔＨ）を算出した。
　　ΔＨＳＰ＝（４．０×ΔＤ２＋ΔＰ２＋ΔＨ２）０．５　　　（Ｈ１）
　ハンセン溶解度パラメータは各算出対象成分において複数の化合物がある場合には（例えば、脱離成分が２種以上ある場合等）、該当する化合物のうち最多量成分（質量基準）の値を採用した。尚、最多量成分が２種以上ある場合には、（混合比による平均値）とする。
　表１～４に、式（Ｈ１）で算出した脱離成分と硬化性組成物とのハンセン溶解度パラメータの距離（ΔＨＳＰ）を示した。 <Calculation of distance between Hansen solubility parameters (ΔHSP)>
The Hansen solubility parameter was calculated with HSP calculation software HSPiP.
Each component of the Hansen solubility parameter (d component, p component, and h component) was calculated by inputting the structural formula of each compound into the above software in the SMILES format. For the calculated Hansen solubility parameter, the Hansen solubility parameter distance between components (ΔHSP: ΔD, ΔP, ΔH) was calculated as necessary.
ΔHSP = (4.0 × ΔD 2 + ΔP 2 + ΔH 2 ) 0.5 (H1)
As the Hansen solubility parameter, when there are a plurality of compounds in each calculation target component (for example, when there are two or more desorption components), the value of the most abundant component (mass basis) among the corresponding compounds is adopted. In addition, when there are two or more kinds of the most abundant components, the average value is determined according to the mixing ratio.
Tables 1 to 4 show the distance (ΔHSP) of the Hansen solubility parameter between the desorbing component and the curable composition calculated by the formula (H1).
＜分子量の測定方法＞
　ポリマーの重量平均分子量（Ｍｗ）は、ゲル浸透クロマトグラフィ（ＧＰＣ測定）に従い、ポリスチレン換算値として定義した。装置はＨＬＣ－８２２０（東ソー（株）製）を用い、カラムとしてガードカラムＨＺ－Ｌ、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺＭ－Ｍ、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ４０００、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ３０００およびＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ２０００（東ソー（株）製）を用いた。溶離液は、ＴＨＦ（テトラヒドロフラン）を用いた。検出は、ＵＶ線（紫外線）の波長２５４ｎｍ検出器を使用した。 <Measurement method of molecular weight>
The weight average molecular weight (Mw) of the polymer was defined as a polystyrene equivalent value according to gel permeation chromatography (GPC measurement). The apparatus used was HLC-8220 (manufactured by Tosoh Corporation), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation) were used as columns. . As eluent, THF (tetrahydrofuran) was used. For the detection, a UV ray (ultraviolet) wavelength 254 nm detector was used.
＜密着性＞
　シリコンウェハ（直径８インチ）上に、インプリント用下層膜形成組成物をスピンコートした。その後、１５０℃、３分間、空気雰囲気下のベーク条件でホットプレートを用いて加熱し、ウェハ上に下層膜を形成した。得られた下層膜の厚さは約１０ｎｍであった。
　下層膜の表面に、２３℃に温度調整したインプリント用硬化性組成物を、富士フイルムダイマティックス社製インクジェットプリンターＤＭＰ－２８３１を用いて、ノズルあたり１ｐＬの液滴量で吐出して、上記下層膜上に液滴が約１００μｍ間隔の正方配列となるように塗布した。
　その上から石英モールド（矩形ライン／スペースパターン（１／１）、線幅４０ｎｍ、溝深さ１００ｎｍ、ラインエッジラフネス３．５ｎｍ）をインプリント用硬化性組成物層と接するように載せ、石英ウェハ側から高圧水銀ランプを用い３００ｍＪ／ｃｍ2の条件で露光した。露光後、石英ウェハを離し、そのときの剥離力を測定した。
　この剥離力が密着力Ｆ（単位：Ｎ）に相当する。剥離力は特開２０１１－２０６９７７号公報の段落番号０１０２～０１０７に記載の比較例に記載の剥離力の測定方法に準じて測定を行った。すなわち、上記公報の図５の剥離ステップ１～６および１６～１８に従って行った。
　　Ａ：Ｆ≧４５Ｎ
　　Ｂ：４５Ｎ＞Ｆ≧３０Ｎ
　　Ｃ：３０Ｎ＞Ｆ≧２０Ｎ
　　Ｄ：２０Ｎ＞Ｆ <Adhesion>
A composition for forming a lower layer film for imprinting was spin-coated on a silicon wafer (diameter 8 inches). Then, it heated using the hotplate on baking conditions of 150 degreeC and the air atmosphere for 3 minutes, and formed the lower layer film | membrane on the wafer. The thickness of the obtained lower layer film was about 10 nm.
On the surface of the lower layer film, the curable composition for imprints adjusted to a temperature of 23 ° C. was ejected with a droplet amount of 1 pL per nozzle using an inkjet printer DMP-2831 manufactured by Fujifilm Dimatics, Inc. It apply | coated so that a droplet might become a square array of about 100 micrometer space | interval on a lower layer film | membrane.
A quartz mold (rectangular line / space pattern (1/1), line width 40 nm, groove depth 100 nm, line edge roughness 3.5 nm) is placed thereon so as to be in contact with the curable composition layer for imprinting, and a quartz wafer From the side, exposure was performed at 300 mJ / cm 2 using a high-pressure mercury lamp. After the exposure, the quartz wafer was separated and the peeling force at that time was measured.
This peeling force corresponds to the adhesion force F (unit: N). The peeling force was measured according to the method for measuring the peeling force described in Comparative Examples described in paragraph numbers 0102 to 0107 of JP 2011-209777 A. That is, it was performed according to the peeling steps 1 to 6 and 16 to 18 in FIG.
A: F ≧ 45N
B: 45N> F ≧ 30N
C: 30N> F ≧ 20N
D: 20N> F
＜濡れ性の評価＞
　シリコンウェハ（直径８インチ）上に、インプリント用下層膜形成組成物をスピンコートした。その後、１５０℃、３分間、空気雰囲気下のベーク条件でホットプレートを用いて加熱し、密着層上に下層膜を形成した。得られた下層膜の厚さは約１０ｎｍであった。
　下層膜の表面に、２３℃に温度調整したインプリント用硬化性組成物を、富士フイルムダイマティックス社製インクジェットプリンターＤＭＰ－２８３１を用いて、ノズルあたり１ｐＬの液滴量で吐出して、上記下層膜上に液滴が約１００μｍ間隔の正方配列となるように塗布した。
　塗布後３秒後の液滴形状を撮影し、液滴直径を測定した。１水準につき２つの試料を用い、それぞれ３回測定した。合計６回の算術平均値を評価値として採用した。結果を表１～４に示した。
　Ａ：ＩＪ液滴の平均直径＞５００μｍ
　Ｂ：４００μｍ＜ＩＪ液滴の平均直径≦５００μｍ
　Ｃ：３２０μｍ＜ＩＪ液滴の平均直径≦４００μｍ
　Ｄ：ＩＪ液滴の平均直径≦３２０μｍ <Evaluation of wettability>
A composition for forming a lower layer film for imprinting was spin-coated on a silicon wafer (diameter 8 inches). Thereafter, heating was performed using a hot plate at 150 ° C. for 3 minutes under baking conditions in an air atmosphere to form a lower layer film on the adhesion layer. The thickness of the obtained lower layer film was about 10 nm.
On the surface of the lower layer film, the curable composition for imprints adjusted to a temperature of 23 ° C. was ejected with a droplet amount of 1 pL per nozzle using an inkjet printer DMP-2831 manufactured by Fujifilm Dimatics, Inc. It apply | coated so that a droplet might become a square array of about 100 micrometer space | interval on a lower layer film | membrane.
The droplet shape 3 seconds after application was photographed, and the droplet diameter was measured. Two samples were used for each level, and each measurement was performed three times. A total of 6 arithmetic average values were adopted as evaluation values. The results are shown in Tables 1 to 4.
A: Average diameter of IJ droplet> 500 μm
B: 400 μm <IJ droplet average diameter ≦ 500 μm
C: 320 μm <IJ droplet average diameter ≦ 400 μm
D: Average diameter of IJ droplets ≦ 320 μm
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000028
ポリマー
Figure JPOXMLDOC01-appb-C000029
 　破線は脱離後の脱離成分を記載している（以下同様である）
　Molecular Weightは分子量を意味する。
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000037
 polymer
Figure JPOXMLDOC01-appb-C000029
 The broken line describes the desorbed component after desorption (the same applies hereinafter).
Molecular Weight means molecular weight.
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000037
脱離反応促進剤またはその前駆体
Ｔ－１、Ｔ－４、Ｔ－５、Ｔ－６およびＴ－７は光酸発生剤である。Ｔ－２は熱塩基発生剤である。Ｔ－３は熱酸発生剤である。
Figure JPOXMLDOC01-appb-C000038
 The elimination reaction accelerator or its precursors T-1, T-4, T-5, T-6 and T-7 are photoacid generators. T-2 is a thermal base generator. T-3 is a thermal acid generator.
Figure JPOXMLDOC01-appb-C000038
光重合開始剤
Figure JPOXMLDOC01-appb-C000039
 Photopolymerization initiator
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-T000040
Figure JPOXMLDOC01-appb-T000040
　上記結果から明らかなとおり、本発明のインプリント用下層膜形成組成物は、特定の脱離成分を脱離するポリマーを含有しており、インプリント用硬化性組成物と組み合わせて用いたときに、優れた濡れ性と良好な密着性を示すことが分かった（実施例１～２１）。一方、脱離成分が脱離しないか、脱離成分が脱離したとしても特定の化学構造をとらないものでは、濡れ性あるいは濡れ性に劣ることが分かった（比較例１～３）。 As is clear from the above results, the underlayer film forming composition for imprints of the present invention contains a polymer that desorbs a specific desorbing component, and when used in combination with the curable composition for imprints. It was found that excellent wettability and good adhesion were exhibited (Examples 1 to 21). On the other hand, it was found that if the desorbing component does not desorb, or even if the desorbing component desorbs, it does not take a specific chemical structure and is inferior in wettability or wettability (Comparative Examples 1 to 3).
　各実施例で作製したインプリント用硬化性組成物の膜に対して、幅５００ｎｍのパターンを施した石英製のモールドを接触させた。その後、モールド側から紫外線を照射して膜を硬化した。次いで、モールドを引き離し、モールドのパターンが転写された硬化物のパターンを得た。この結果、いずれの硬化物においても良好なパターンが形成できたことを確認した。 A quartz mold having a pattern with a width of 500 nm was brought into contact with the film of the curable composition for imprints produced in each example. Thereafter, the film was cured by irradiating ultraviolet rays from the mold side. Subsequently, the mold was pulled apart to obtain a cured product pattern to which the mold pattern was transferred. As a result, it was confirmed that a good pattern could be formed in any cured product.
１　　基板
２　　下層膜
３　　インプリント用硬化性組成物
４　　モールド
２１　下層膜
２２　インプリント用硬化性組成物
２３　膜のない領域
  DESCRIPTION OF SYMBOLS 1 Substrate 2 Lower layer film 3 Imprint curable composition 4 Mold 21 Lower layer film 22 Imprint curable composition 23 Area without film

Claims (27)

  1. 　ポリマーと溶剤とを含むインプリント用下層膜形成組成物であって、前記インプリント用下層膜形成組成物を膜状にし、８０℃でベークした場合、前記ポリマーから下記式（ｒ１）または（ｒ２）で表され、かつ、分子量が２１０以上である化合物が脱離する、インプリント用下層膜形成組成物；
    Figure JPOXMLDOC01-appb-C000001
     　式中、Ｒｒ１、Ｒｒ２、Ｒｒ４、Ｒｒ５、およびＲｒ６はそれぞれ独立に水素原子または１価の置換基であり、Ｒｒ１およびＲｒ２の少なくとも一方は置換基であり、Ｒｒ４、Ｒｒ５、およびＲｒ６の少なくとも１つは置換基であり、Ｒｒ３は２価の置換基である。     A composition for forming an underlayer film for imprinting comprising a polymer and a solvent, wherein when the underlayer film forming composition for imprinting is formed into a film and baked at 80 ° C., the following formula (r1) or (r2) is derived from the polymer: ) And a compound having a molecular weight of 210 or more is eliminated from the composition for forming an underlayer film for imprinting;
    Figure JPOXMLDOC01-appb-C000001
     In the formula, R r1 , R r2 , R r4 , R r5 , and R r6 are each independently a hydrogen atom or a monovalent substituent, and at least one of R r1 and R r2 is a substituent, R r4 , At least one of R r5 and R r6 is a substituent, and R r3 is a divalent substituent.
  2. 　前記式（ｒ１）または（ｒ２）で表される化合物が式（ｒ１－１）で表される、請求項１に記載のインプリント用下層膜形成組成物；
    Figure JPOXMLDOC01-appb-C000002
     　式中、Ｒｒ１およびＲｒ２はそれぞれ独立に水素原子または１価の置換基であり、Ｒｒ１およびＲｒ２の少なくとも一方は置換基である。     The underlayer film forming composition for imprints according to claim 1, wherein the compound represented by the formula (r1) or (r2) is represented by the formula (r1-1);
    Figure JPOXMLDOC01-appb-C000002
     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. 　前記ポリマーが下記式（Ｒ－１）～（Ｒ－４）のいずれかで表される基を含む、請求項１また２に記載のインプリント用下層膜形成組成物；
    Figure JPOXMLDOC01-appb-C000003
     　式中、Ｒ１～Ｒ３はそれぞれ独立に１価の置換基であり、Ｒ４～Ｒ１２はそれぞれ独立に水素原子または１価の置換基であり、Ｘはポリマーの主鎖への結合位置を表す。     The composition for forming an underlayer film for imprints according to claim 1 or 2, wherein the polymer contains a group represented by any of the following formulas (R-1) to (R-4);
    Figure JPOXMLDOC01-appb-C000003
     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 is a bonding position to the main chain of the polymer. Represents.
  4. 　前記式（Ｒ－１）～（Ｒ－４）のいずれかで表される置換基を含むポリマーから、式中のＣ－Ｏ結合が分解して、前記式（ｒ１）または（ｒ２）で表され、かつ、分子量２１０以上の化合物が脱離する、請求項３に記載のインプリント用下層膜形成組成物。 From the polymer containing a substituent represented by any one of the formulas (R-1) to (R-4), a C—O bond in the formula is decomposed, and the polymer is represented by the formula (r1) or (r2). The composition for forming an underlayer film for imprinting according to claim 3, wherein a compound having a molecular weight of 210 or more is eliminated.
  5. 　前記ポリマーが重合性基を含む、請求項１～４のいずれか１項に記載のインプリント用下層膜形成組成物。 The composition for forming a lower layer film for imprinting according to any one of claims 1 to 4, wherein the polymer contains a polymerizable group.
  6. 　前記重合性基が（メタ）アクリロイル基を含む、請求項５に記載のインプリント用下層膜形成組成物。 The underlayer film forming composition for imprints according to claim 5, wherein the polymerizable group contains a (meth) acryloyl group.
  7. 　前記ポリマーが芳香環を含む、請求項１～６のいずれか１項に記載のインプリント用下層膜形成組成物。 The underlayer film forming composition for imprints according to any one of claims 1 to 6, wherein the polymer contains an aromatic ring.
  8. 　前記ポリマーが下記式（１）～式（６）のいずれかで表される構成単位の少なくとも１種を含む、請求項１～７のいずれか１項に記載のインプリント用下層膜形成組成物；
    Figure JPOXMLDOC01-appb-C000004
     　式中、ＲＰ４は水素原子またはメチル基である；ＲＰ１は、式（ｒ１）または（ｒ２）で表される化合物を脱離可能な基を表す。     The composition for forming an underlayer film for imprints according to any one of claims 1 to 7, wherein the polymer contains at least one of structural units represented by any of the following formulas (1) to (6). ;
    Figure JPOXMLDOC01-appb-C000004
     In the formula, R P4 represents a hydrogen atom or a methyl group; R P1 represents a group capable of leaving the compound represented by the formula (r1) or (r2).
  9. 　前記式（ｒ１）または（ｒ２）で表される化合物が芳香環を含む、請求項１～８のいずれか１項に記載のインプリント用下層膜形成組成物。 The composition for forming an underlayer film for imprints according to any one of claims 1 to 8, wherein the compound represented by the formula (r1) or (r2) contains an aromatic ring.
  10. 　前記式（ｒ１）または（ｒ２）で表される化合物が重合性基を含む、請求項１～９のいずれか１項に記載のインプリント用下層膜形成組成物。 The composition for forming an underlayer film for imprints according to any one of claims 1 to 9, wherein the compound represented by the formula (r1) or (r2) contains a polymerizable group.
  11. 　前記重合性基が（メタ）アクリロイル基を含む、請求項１０に記載のインプリント用下層膜形成組成物。 The composition for forming a lower layer film for imprinting according to claim 10, wherein the polymerizable group contains a (meth) acryloyl group.
  12. 　前記式（ｒ１）のＲｒ１およびＲｒ２の少なくとも１つ、および、式（ｒ２）のＲｒ４～Ｒｒ６の少なくとも１つが重合性基を含む、請求項１～１１のいずれか１項に記載のインプリント用下層膜形成組成物。 The at least one of R r1 and R r2 of the formula (r1) and at least one of R r4 to R r6 of the formula (r2) include a polymerizable group. An underprint film-forming composition for imprinting.
  13. 　前記式（ｒ１）または（ｒ２）で表される化合物の分子量が１０００以下である、請求項１～１２のいずれか１項に記載のインプリント用下層膜形成組成物。 The composition for forming an underlayer film for imprints according to any one of claims 1 to 12, wherein the compound represented by the formula (r1) or (r2) has a molecular weight of 1000 or less.
  14. 　さらに、脱離反応促進剤またはその前駆体を含む、請求項１～１３のいずれか１項に記載のインプリント用下層膜形成組成物。 The composition for forming a lower layer film for imprinting according to any one of claims 1 to 13, further comprising an elimination reaction accelerator or a precursor thereof.
  15. 　さらに、光重合開始剤を含む、請求項１～１４のいずれか１項に記載のインプリント用下層膜形成組成物。 The composition for forming a lower layer film for imprinting according to any one of claims 1 to 14, further comprising a photopolymerization initiator.
  16. 　前記式（ｒ１）または（ｒ２）で表される化合物の表面張力が３５～５５ｍＮ／ｍである、請求項１～１５のいずれか１項に記載のインプリント用下層膜形成組成物。 The composition for forming an underlayer film for imprints according to any one of claims 1 to 15, wherein the compound represented by the formula (r1) or (r2) has a surface tension of 35 to 55 mN / m.
  17. 　溶剤を９５．０質量％以上の割合で含む、請求項１～１６のいずれか１項に記載のインプリント用下層膜形成組成物。 The composition for forming a lower layer film for imprints according to any one of claims 1 to 16, comprising a solvent in a proportion of 95.0% by mass or more.
  18. 　請求項１～１７のいずれか１項に記載のインプリント用下層膜形成組成物と組み合わせて用いる、重合性化合物を含むインプリント用硬化性組成物。 A curable composition for imprints containing a polymerizable compound, used in combination with the composition for forming an underprint film for imprints according to any one of claims 1 to 17.
  19. 　請求項１～１７のいずれか１項に記載のインプリント用下層膜形成組成物と、重合性化合物を含むインプリント用硬化性組成物とを含むキット。 A kit comprising the imprint underlayer film forming composition according to any one of claims 1 to 17, and an imprint curable composition comprising a polymerizable compound.
  20. 　前記式（ｒ１）または（ｒ２）で表される化合物のハンセン溶解度パラメータと前記インプリント用硬化性組成物のハンセン溶解度パラメータとに基づき下記数式（Ｈ１）で算出されるΔＨＳＰ値が５以下である、請求項１９に記載のキット；
    　　ΔＨＳＰ＝（４．０×ΔＤ２＋ΔＰ２＋ΔＨ２）０．５　　　　（Ｈ１）
    　上記ΔＤは、インプリント用硬化性組成物のハンセン溶解度パラメータベクトルの分散項成分と、式（ｒ１）または（ｒ２）で表される化合物のハンセン溶解度パラメータベクトルの分散項成分の差であり、上記ΔＰは、インプリント用硬化性組成物のハンセン溶解度パラメータベクトルの極性項成分と、式（ｒ１）または（ｒ２）で表される化合物のハンセン溶解度パラメータベクトルの極性項成分の差であり、上記ΔＨは、インプリント用硬化性組成物のハンセン溶解度パラメータベクトルの水素結合項成分と、式（ｒ１）または（ｒ２）で表される化合物のハンセン溶解度パラメータベクトルの水素結合項成分の差である。     Based on the Hansen solubility parameter of the compound represented by the formula (r1) or (r2) and the Hansen solubility parameter of the curable composition for imprints, the ΔHSP value calculated by the following formula (H1) is 5 or less. A kit according to claim 19;
    ΔHSP = (4.0 × ΔD 2 + ΔP 2 + ΔH 2 ) 0.5 (H1)
    ΔD is the difference between the dispersion term component of the Hansen solubility parameter vector of the curable composition for imprints and the dispersion term component of the Hansen solubility parameter vector of the compound represented by the formula (r1) or (r2), ΔP is the difference between the polar term component of the Hansen solubility parameter vector of the curable composition for imprints and the polar term component of the Hansen solubility parameter vector of the compound represented by the formula (r1) or (r2). Is the difference between the hydrogen bond term component of the Hansen solubility parameter vector of the curable composition for imprints and the hydrogen bond term component of the Hansen solubility parameter vector of the compound represented by the formula (r1) or (r2).
  21. 　請求項１～１７のいずれか１項に記載の下層膜形成組成物から形成された下層膜。 An underlayer film formed from the underlayer film forming composition according to any one of claims 1 to 17.
  22. 　請求項１９または２０に記載のキットから形成される積層体であって、
    　前記インプリント用下層膜形成組成物から形成された下層膜と、前記インプリント用硬化性組成物から形成され、前記下層膜の表面に位置するインプリント層とを有する、積層体。     A laminate formed from the kit according to claim 19 or 20,
    The laminated body which has the lower layer film formed from the said lower layer film formation composition for imprints, and the imprint layer formed from the said curable composition for imprints, and is located in the surface of the said lower layer film.
  23. 　請求項１９または２０に記載のキットを用いて積層体を製造する方法であって、前記インプリント用下層膜形成組成物から形成された下層膜の表面に、インプリント用硬化性組成物を適用することを含む、積層体の製造方法。 A method for producing a laminate using the kit according to claim 19 or 20, wherein the curable composition for imprints is applied to a surface of an underlayer film formed from the underlayer film forming composition for imprints. The manufacturing method of a laminated body including doing.
  24. 　前記インプリント用硬化性組成物は、インクジェット法により、前記下層膜の表面に適用する、請求項２３に記載の積層体の製造方法。 The method for producing a laminate according to claim 23, wherein the curable composition for imprints is applied to a surface of the lower layer film by an inkjet method.
  25. 　さらに、前記インプリント用下層膜形成組成物を基板上に層状に適用する工程を含み、前記層状に適用したインプリント用下層膜形成組成物を８０～２５０℃で、加熱することを含む、請求項２３または２４に記載の積層体の製造方法。 The method further comprises the step of applying the underprint film-forming composition for imprints in a layer form on a substrate, and heating the under-layer film formation composition for imprints applied to the layer form at 80 to 250 ° C. Item 25. The method for producing a laminate according to Item 23 or 24.
  26. 　請求項１９または２０に記載のキットを用いて硬化物パターンを製造する方法であって、基板上に、インプリント用下層膜形成組成物を適用して下層膜を形成する下層膜形成工程と、前記下層膜の表面に、インプリント用硬化性組成物を適用する適用工程と、前記インプリント用硬化性組成物と、パターン形状を転写するためのパターンを有するモールドとを接触させるモールド接触工程と、前記インプリント用硬化性組成物に光を照射して硬化物を形成する光照射工程と、前記硬化物と前記モールドとを引き離す離型工程と、を有する硬化物パターンの製造方法。 A method for producing a cured product pattern using the kit according to claim 19 or 20, wherein a lower film is formed on a substrate by applying a lower film forming composition for imprinting, An application step of applying an imprint curable composition to the surface of the lower layer film, a mold contact step of bringing the imprint curable composition into contact with a mold having a pattern for transferring a pattern shape; A method for producing a cured product pattern, comprising: a light irradiation step of irradiating light to the curable composition for imprints to form a cured product; and a releasing step of separating the cured product from the mold.
  27. 　請求項２６に記載の製造方法により硬化物パターンを得る工程を含む、回路基板の製造方法。 A method for producing a circuit board, comprising a step of obtaining a cured product pattern by the production method according to claim 26.
PCT/JP2019/008277 2018-03-07 2019-03-04 Underlayer film forming composition for imprinting, curable composition for imprinting, and kit WO2019172156A1 (en)

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WO2021125036A1 (en) * 2019-12-18 2021-06-24 日産化学株式会社 Composition for forming resist underlayer film for nanoimprinting

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