WO2020059603A1 - Corps stratifié d'impression, procédé de fabrication d'un corps stratifié d'impression, procédé de formation de motif et kit - Google Patents

Corps stratifié d'impression, procédé de fabrication d'un corps stratifié d'impression, procédé de formation de motif et kit Download PDF

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Publication number
WO2020059603A1
WO2020059603A1 PCT/JP2019/035750 JP2019035750W WO2020059603A1 WO 2020059603 A1 WO2020059603 A1 WO 2020059603A1 JP 2019035750 W JP2019035750 W JP 2019035750W WO 2020059603 A1 WO2020059603 A1 WO 2020059603A1
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group
imprint
liquid film
film
photocurable composition
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PCT/JP2019/035750
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English (en)
Japanese (ja)
Inventor
直也 下重
旺弘 袴田
雄一郎 後藤
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富士フイルム株式会社
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Priority to JP2020548401A priority Critical patent/JPWO2020059603A1/ja
Publication of WO2020059603A1 publication Critical patent/WO2020059603A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/14—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of indefinite length
    • B29C39/20—Making multilayered or multicoloured articles
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/24—Layered products comprising a layer of synthetic resin characterised by the use of special additives using solvents or swelling agents
    • 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 a laminate for imprint. More specifically, the present invention relates to an imprint laminate used for forming a pattern by imprint. The present invention also relates to a method for producing a laminate for imprint, a method for forming a pattern, and a kit.
  • the imprint method is developed by embossing a well-known embossing technique in optical disk manufacturing, and pressing a mold prototype (generally called a mold, stamper, template, etc.) on a resist into a mechanical pattern.
  • a mold prototype generally called a mold, stamper, template, etc.
  • This is a technology for precisely transferring a fine pattern by deforming it.
  • Once a mold is made, it is economical because it can easily and repeatedly mold a fine structure such as a nanostructure.
  • it is a nano-processing technology that reduces harmful wastes and discharges. Application is expected.
  • the mold is peeled off to transfer a fine pattern to the photocured material. is there. Since this method enables imprinting at room temperature, it can be applied to the field of precision processing of ultra-fine patterns such as fabrication of semiconductor integrated circuits. Recently, new developments such as a nanocasting method combining these advantages and a reversal imprint method for producing a three-dimensional laminated structure have been reported.
  • the adhesion between the substrate and the photocurable composition for imprint has come to be viewed as a problem. That is, in the imprint method, after applying the photocurable composition for imprint to the surface of the substrate, and curing the photocurable composition for imprint by irradiating light with the mold in contact with the surface. When the mold is peeled off, the cured product may peel off from the substrate and adhere to the mold in the step of peeling off the mold. This is probably because the adhesion between the substrate and the cured product is lower than the adhesion between the mold and the cured product. Therefore, attempts have been made to form a lower layer film on a substrate and apply a photocurable composition for imprint thereon to improve the adhesion between the substrate and the cured product (see Patent Documents 1 and 2). ).
  • the cured product formed from the photocurable composition for imprints has good adhesion to the substrate, and the wettability of the photocurable composition for imprints is good. In recent years, it has been desired that these characteristics be compatible at a higher level.
  • the present invention provides the following. ⁇ 1> an underlayer film formed from an underlayer film forming composition containing a polymer having an aromatic ring and a polymerizable group; A liquid film provided on the surface of the lower film and containing a polymerizable compound that is liquid at 23 ° C. and 1 atm; Photocurable composition for imprint, provided on the surface of the liquid film, A laminate for imprinting, comprising: ⁇ 2> The imprint laminate according to ⁇ 1>, wherein the polymer includes a constituent unit including an aromatic ring and a polymerizable group.
  • R 12 may be the same, or different, may have two R 12 are bonded to each other to form a ring;
  • R 3 represents a hydrogen atom or a methyl group, and R 13 represents a substituent;
  • R 4 represents a hydrogen atom or a methyl group, and R 14 represents a substituent;
  • R 15 represents a substituent.
  • ⁇ 5> The imprinting laminate according to any one of ⁇ 1> to ⁇ 4>, wherein the polymerizable group of the polymer is at least one selected from a (meth) acryloyl group, an oxiranyl group, and an oxetanyl group. body.
  • ⁇ 6> The laminate for imprints according to any one of ⁇ 1> to ⁇ 5>, wherein the thickness of the liquid film is 10 nm or less.
  • ⁇ 7> The laminate for imprints according to any one of ⁇ 1> to ⁇ 6>, wherein the polymerizable compound contained in the liquid film is a polymerizable compound containing an aromatic ring.
  • ⁇ 8> The laminate for imprints according to any one of ⁇ 1> to ⁇ 7>, wherein the polymerizable compound contained in the liquid film is a polyfunctional polymerizable compound.
  • ⁇ 9> The imprint laminate according to any one of ⁇ 1> to ⁇ 8>, wherein the polymerizable compound contained in the liquid film is a radical polymerizable compound.
  • the photocurable composition for imprints includes a polymerizable compound and a photopolymerization initiator.
  • ⁇ 11> The imprint laminate according to ⁇ 10>, wherein the polymerizable compound contained in the photocurable composition for imprint is a polymerizable compound containing an aromatic ring.
  • ⁇ 12> The value of ⁇ HSP calculated by the following equation (H1) based on the Hansen solubility parameter of the liquid film and the Hansen solubility parameter of the photocurable composition for imprint is 10 or less, ⁇ 1> to ⁇ 11>.
  • ⁇ 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 photocurable composition for imprint and the dispersion term component of the Hansen solubility parameter vector of the liquid film
  • ⁇ P is the photocurable composition for imprint.
  • ⁇ H is the hydrogen bond term component of the Hansen solubility parameter vector of the photocurable composition for imprint.
  • a step of forming an underlayer film by applying a composition for forming an underlayer film containing a polymer having an aromatic ring and a polymerizable group on a substrate Forming a liquid film by applying a liquid film forming composition containing a polymerizable compound that is liquid at 23 ° C.
  • a step of applying the photocurable composition for imprint on the liquid film A method for producing a laminate for imprints comprising: ⁇ 14> a step of forming an underlayer film by applying a composition for forming an underlayer film containing a polymer having an aromatic ring and a polymerizable group on a substrate; Forming a liquid film by applying a liquid film forming composition containing a polymerizable compound that is liquid at 23 ° C.
  • a step of applying the photocurable composition for imprint on the liquid film Contacting a mold having a pattern with a photocurable composition for imprinting on a liquid film, A step of exposing the photocurable composition for imprint in a state where the mold is in contact with the mold, Step of peeling the mold from the exposed photocurable composition for imprint, A pattern forming method including: ⁇ 15> A kit used for the imprint laminate according to any one of ⁇ 1> to ⁇ 12>, An underlayer film forming composition containing a polymer having an aromatic ring and a polymerizable group, A liquid film-forming composition containing a polymerizable compound that is liquid at 23 ° C. and 1 atm; A photocurable composition for imprints.
  • (meth) acrylate represents acrylate and methacrylate.
  • imprint preferably refers to a pattern transfer having a size of 1 nm to 10 mm, and more preferably refers to a pattern transfer (nanoimprint) having a size of about 10 nm to 100 ⁇ m.
  • the notation of not indicating substituted or unsubstituted includes not only a group having no substituent but also a group having 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 having a wavelength in the ultraviolet, near-ultraviolet, far-ultraviolet, visible, and infrared regions, and electromagnetic waves, but also radiation. Radiation includes, for example, microwaves, electron beams, extreme ultraviolet (EUV), and X-rays. Alternatively, laser light such as a 248 nm excimer laser, a 193 nm excimer laser, or a 172 nm excimer laser can be used.
  • These lights may be monochrome light (single-wavelength light) that has passed through an optical filter, or may be light having different wavelengths (composite light).
  • the weight average molecular weight (Mw) in the present invention refers to a value measured by gel permeation chromatography (GPC) unless otherwise specified.
  • the temperature in the present invention is 23 ° C. unless otherwise specified.
  • the laminate for imprint of the present invention An underlayer film formed from an underlayer film forming composition containing a polymer having an aromatic ring and a polymerizable group, A liquid film provided on the surface of the lower film and containing a polymerizable compound that is liquid at 23 ° C. and 1 atm; Photocurable composition for imprint, provided on the surface of the liquid film, It is characterized by having.
  • the laminate for imprints of the present invention has an underlayer film formed from a composition for forming an underlayer film containing a polymer having an aromatic ring and a polymerizable group. Since the polymer contained in the composition for forming an underlayer film contains an aromatic ring, it is considered that the aromatic ring contained in the polymer easily interacts with a substrate or the like. In addition, since this polymer also contains a polymerizable group, it is considered that an interaction between the substrate and the polymerizable group contained in the polymer can be obtained. Therefore, the adhesion between the substrate and the lower layer film can be further improved.
  • the laminate for imprints of the present invention has a liquid film containing a polymerizable compound that is liquid at 23 ° C. and 1 atm on the surface of the lower film.
  • the liquid film contains the above polymerizable compound, it is estimated that the polymerizable compound contained in the liquid film interacts with the lower layer film or the photocurable composition for imprint, and Adhesion with the lower layer film and adhesion between the liquid film and the cured product obtained from the photocurable composition for imprints formed thereon can be improved. Therefore, it is presumed that the laminate for imprints of the present invention can provide excellent adhesion of a cured product formed from the photocurable composition for imprints to a substrate or the like.
  • the liquid refers to a liquid having a viscosity at 23 ° C. of 100,000 mPa ⁇ s or less.
  • the imprint laminate of the present invention has the imprint photocurable composition on the liquid film, the imprint photocurable composition easily wets and spreads on the liquid film, and the imprint The photocurable composition for use has excellent wettability. Therefore, when the mold is brought into contact with the surface of the photocurable composition for imprints to form a pattern, excellent filling properties of the photocurable composition for imprints into the mold can be provided.
  • FIG. 1 a laminate 10 for imprint of the present invention is formed on a substrate 1. That is, in FIG. 1, the lower film 11 is formed on the substrate 1, and the liquid film 12 is formed on the lower film. Then, the photocurable composition for imprint 13 is disposed on the liquid film 12. The laminate of the lower layer film 11, the liquid film 12, and the photocurable composition for imprint 13 is the laminate for imprint 10 of the present invention.
  • the material of the substrate 1 on which the laminate for imprint is formed is not particularly specified, and is described in paragraph 0103 of JP-A-2010-109092 (the publication number of the corresponding US application is US2011 / 0183127). For reference, their contents are incorporated herein.
  • Specific examples of the substrate 1 include a silicon substrate, a glass substrate, a quartz substrate, a sapphire substrate, a silicon carbide (silicon carbide) substrate, a gallium nitride substrate, an aluminum substrate, an amorphous aluminum oxide substrate, a polycrystalline aluminum oxide substrate, and GaAsP.
  • a substrate having a carbon film on the surface as the substrate 1.
  • the carbon film is preferably provided on the outermost layer of the substrate.
  • the carbon film include an amorphous carbon film and a spin-on carbon film.
  • the spin-on carbon film reference can be made to the description in paragraph 0126 of JP-A-2011-164345, the contents of which are incorporated herein.
  • the contact angle of water on the substrate surface is preferably 1 ° or more, more preferably 20 ° or more, and even more preferably 40 ° or more. It is practical that the upper limit is 90 ° or less.
  • the thickness of the lower film 11 is preferably 2 nm or more, more preferably 3 nm or more, still more preferably 4 nm or more, and may be 5 nm or more, or may be 7 nm or more. It may be 10 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, and may be 15 nm or less. When the film thickness is equal to or more than the lower limit, the wettability of the photocurable composition for imprints can be increased. When the film thickness is equal to or less than the above upper limit, the remaining film after imprinting becomes thin, the thickness unevenness is less likely to occur, and the uniformity of the remaining film can be improved.
  • the surface free energy of the lower layer film 11 is preferably 30 mN / m or more, more preferably 40 mN / m or more, and further preferably 50 mN / m or more.
  • the upper limit is preferably 200 mN / m or less, more preferably 150 mN / m or less, and even more preferably 100 mN / m or less.
  • the surface free energy can be measured at 23 ° C. using a glass plate using a surface tensiometer “SURFACE TENS-IOMETER” CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd.
  • the underlayer film 11 is formed from a composition for forming an underlayer film containing a polymer having an aromatic ring and a polymerizable group. Details of the composition for forming the lower layer film will be described later.
  • the thickness of the liquid film 12 is preferably 20 nm or less, more preferably 15 nm or less, even more preferably 10 nm or less. Further, the thickness of the liquid film is preferably 2 nm or more. When the film thickness is equal to or more than the lower limit, the wettability of the photocurable composition for imprints can be increased. When the film thickness is equal to or less than the upper limit, occurrence of pattern collapse or the like can be suppressed.
  • the liquid film 12 contains a polymerizable compound that is liquid at 23 ° C. and 1 atm (hereinafter also referred to as polymerizable compound A).
  • the liquid film 12 preferably has a content of a non-volatile component (a component other than the solvent) of 0.01% by mass or more, more preferably 0.1% by mass or more.
  • the content of the polymerizable compound A in the liquid film 12 is preferably 50% by mass or more, and more preferably 80% by mass or more.
  • the liquid film 12 can be formed using a liquid film forming composition containing a polymerizable compound that is liquid at 23 ° C. and 1 atm. Details of the liquid film forming composition will be described later.
  • underlayer film forming composition >> Next, the composition for forming an underlayer film used for the imprint laminate of the present invention will be described.
  • the composition for forming a lower layer film includes a polymer having an aromatic ring and a polymerizable group (hereinafter, also referred to as a specific polymer).
  • the aromatic ring may be contained in the main chain of the constituent unit or may be contained in the side chain.
  • the polymerizable group may be contained in a constituent unit containing an aromatic ring, or may be contained in a constituent unit containing no aromatic ring.
  • the specific polymer may be a mixture of a polymer having an aromatic ring and having no polymerizable group and a polymer having a polymerizable group and having no aromatic ring. .
  • the aromatic ring contained in the specific polymer may be any of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, but is preferably an aromatic hydrocarbon ring.
  • the aromatic ring may be a single ring or a condensed ring, but is preferably a single ring. When it is a condensed ring, the number of rings is preferably two or three.
  • the ring is preferably a 3- to 8-membered ring, more preferably a 5- or 6-membered ring, and even more preferably a 6-membered ring.
  • aromatic hydrocarbon 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.
  • aromatic heterocyclic 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, 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 And a phenoxazine ring.
  • the aromatic ring contained in the specific polymer is
  • Examples of the polymerizable group contained in the specific polymer include a (meth) acryloyl group, an oxiranyl group, an oxetanyl group, a methylol group, a methylol ether group, a vinyl ether group, an isocyanate group, and an oxazoline group. And an oxetanyl group, and a (meth) acryloyl group is more preferable.
  • the ratio of the structural unit having a polymerizable group is preferably from 10 to 100% by mole, more preferably from 20 to 100% by mole, and more preferably from 30 to 100% by mole of all the structural units. Is more preferably, and particularly preferably 50 to 100 mol%.
  • the specific polymer may include only one type of structural unit having a polymerizable group, or may include two or more types of structural units. When two or more kinds are included, the total amount is preferably in the above range.
  • the specific polymer preferably contains at least one of the structural units represented by any of the following formulas (1) to (5).
  • R 11 represents a substituent
  • m1 represents an integer of 0 to 4. If m1 is 2 or more, plural R 11 may be the same, or different, may form two R 11 are bonded to each other ring.
  • R 2 represents a hydrogen atom or a methyl group
  • R 12 represents a substituent
  • m2 represents an integer of 0 to 5.
  • R 3 represents a hydrogen atom or a methyl group
  • R 13 represents a substituent.
  • R 4 represents a hydrogen atom or a methyl group
  • R 14 represents a substituent.
  • R 15 represents a substituent.
  • examples of the substituent represented by R 11 to R 15 include a substituent T described later and a group represented by the following formula (T1).
  • the substituent represented by R 13 to R 15 is preferably a group containing an aromatic ring, and more preferably a group represented by the formula (T1).
  • m1 represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and still more preferably 1 or 2.
  • m2 represents an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and still more preferably 1 or 2.
  • R 11 is preferably a group represented by the following formula (T1).
  • m1 is 2 or more, it is preferable that at least one of the plurality of R 11 is a group represented by the following formula (T1).
  • R 12 is preferably a group represented by the following formula (T1).
  • at least one of a plurality of R 12 is preferably a group represented by the following formula (T1).
  • L 1 and L 2 are each independently a linking group L described below, preferably a linking group Lh containing a hetero atom. However when n3 is 0, L 2 of the terminal is a substituent. La is a linking group containing an aromatic ring. However, when n2 is 0 and n3 is 0, La is a substituent containing an aromatic ring. P is a polymerizable group. n1 is 0 to 4. n2 is 0-4.
  • n4 is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 6, further preferably an integer of 1 to 4, and particularly preferably an integer of 1 to 3.
  • L 3 is a divalent linking group, and is preferably a linking group L described in detail below.
  • n5 is 0 or 1.
  • n11 an integer of 2 or more.
  • L 3 may be a trivalent or higher linking group, for example, a trivalent or higher alkane structure group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms). Preferred), an alkene structure group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, even more preferably 2 to 3), or an aryl structure group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms). (Preferably 6 to 10 is more preferable).
  • Examples of the linking group Lh containing a hetero atom include an oxygen atom, a sulfur atom, a carbonyl group, a thiocarbonyl group, a sulfonyl group, a sulfinyl group, an —NR N —, and an (oligo) alkyleneoxy group (an alkylene group in one structural unit).
  • the number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 3; the number of repetitions is preferably 1 to 50, more preferably 1 to 40, and still more preferably 1 to 30.
  • a linking group consisting of a combination is exemplified.
  • the number of atoms constituting the linking group Lh containing a hetero atom, excluding a hydrogen atom, is preferably 1 to 100, more preferably 1 to 70, and particularly preferably 1 to 50.
  • the number of connecting 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 may be an alkyleneoxy group or an oligoalkyleneoxy group.
  • the above (oligo) alkyleneoxy group and the like may be linear or cyclic, and may be linear or branched.
  • R N is a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and still more preferably having 1 to 3 carbon atoms), and is preferably a hydrogen atom, a methyl group, an ethyl group, or a propyl group.
  • L 1 and L 2 may each independently have a substituent T.
  • a hydroxyl group is substituted for the alkylene group of the alkyleneoxy group can be mentioned as a preferable example.
  • n3 is atom or group into the position of P when L 2 is a substituent in 0 may be of any, for example, a hydrogen atom, an alkyl group (having 1 to 12 carbon atoms are preferred, and 1-6 And more preferably 1 to 3.
  • Examples of the polymerizable group represented by P include the polymerizable groups described above, and are preferably (meth) acryloyl, oxiranyl, and oxetanyl, and more preferably (meth) acryloyl.
  • La is a linking group containing an aromatic ring.
  • La may be composed of only an aromatic ring, or may have a non-aromatic hydrocarbon linking group.
  • the non-aromatic hydrocarbon linking group include a non-aromatic hydrocarbon linking group among the linking groups L described in detail below, and an alkylene group (having 1 carbon atom) which may be linear or cyclic, linear or branched. To 24, more preferably 1 to 12, and still more preferably 1 to 6, an alkenylene group which may be linear or cyclic, linear or branched (preferably having 2 to 24 carbon atoms, and more preferably having 2 to 12 carbon atoms). , And 2 to 6 are more preferred).
  • the non-aromatic hydrocarbon linking group shown here is called a linking group Lt.
  • the aromatic ring La becomes a terminal substituent.
  • the terminal may be an arbitrary atom or atomic group, for example, a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, more preferably 1 to 3).
  • La may be a linking group having an aromatic ring, and may have a form in which the aromatic ring is not at the linking position. For example, a form in which an alkylene group is connected between L 21 and L 21 and an aromatic ring is substituted on the alkylene group may be used.
  • the formula weight of the group represented by the formula (T1) is preferably 80 or more, more preferably 100 or more, further preferably 130 or more, and particularly preferably 150 or more. It is practical that the upper limit is 500 or less.
  • 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), and an arylalkyl group (preferably having 7 to 21 carbon atoms, more preferably 7 to 15 carbon atoms). , 7 to 11 are more preferred), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms), and an alkynyl group (preferably having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms).
  • an amino group preferably having 0 to 24 carbon atoms, more preferably 0 to 12, and still more preferably 0 to 6
  • a thiol group e.g. A number of 6 to 22, preferably 6 to 18, more preferably 6 to 10
  • an alkoxyl group preferably 1 to 12 carbon atoms, more
  • an aryloyloxy group preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and still more preferably 7 to 11
  • a carbamoyl group preferably having 1 to 12 carbon atoms
  • a sulfamoyl group preferably having 0 to 12 carbon atoms, more preferably 0 to 6, and still more preferably 0 to 3).
  • a heterocyclic group preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 2 to 5 and preferably containing a 5- or 6-membered ring
  • R N is a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and still more preferably having 1 to 3 carbon atoms), and is preferably a hydrogen atom, a methyl group, an ethyl group, or a propyl group.
  • the alkyl, alkenyl, and alkynyl moieties contained in each substituent may be linear or cyclic, and may be linear or branched.
  • the substituent T is a group that can take a substituent, it may further have a substituent T.
  • the alkyl group may be a halogenated alkyl group, 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.
  • linking group L examples include an alkylene group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 1 to 6), and an alkenylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6; 2 to 3 are more preferable), alkynylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 and still more preferably 2 to 3), (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 still 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 an arylene group ( Preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, even more preferably 6 to 10), an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group
  • the particular polymer is a copolymer.
  • the copolymer component preferably contains at least one of the structural units represented by any of the following formulas (11) to (15) (hereinafter sometimes referred to as other structural units).
  • R 11a represents a substituent
  • m11 represents an integer of 1 to 4.
  • a plurality of R11a may be the same or different, and two R11a may combine with each other to form a ring.
  • at least one of m11 amino R 11a represents a group of formula (T2) to be described later.
  • R 2a represents a hydrogen atom or a methyl group
  • R 12a represents a substituent
  • m12 represents an integer of 1 to 5.
  • m12 is 2 or more, a plurality of R 12a may be the same or different, and two R 12a may be bonded to each other to form a ring.
  • Examples of the substituent represented by R 11a and R 12a include the substituent T described above and a group represented by the following formula (T2).
  • L 4 is the above-mentioned linking group L, and among these, an alkylene group, an arylene group, a (oligo) alkyleneoxy group, a carbonyl group, an oxygen atom, and a linking group related to a combination thereof are preferable.
  • n6 is 0 or 1, and 1 is preferred.
  • P has the same meaning as in formula (T1).
  • n7 is an integer of 1 to 6, preferably 1 or 2.
  • L 4 may be a trivalent or higher valent linking group, for example, a trivalent or higher alkane structure group (preferably having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms). More preferably, it is 1 to 3, more preferably, an alkene structure group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6, more preferably 2 to 3), or an aryl structure group (having 6 to 22 carbon atoms). Is preferable, 6 to 18 are more preferable, and 6 to 10 are more preferable.).
  • a trivalent or higher alkane structure group preferably having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms. More preferably, it is 1 to 3, more preferably, an alkene structure group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6, more preferably 2 to 3), or an aryl structure group (having 6 to 22 carbon atoms). Is preferable, 6 to 18 are more preferable, and 6 to 10 are more preferable.).
  • the formula weight of the group represented by the formula (T2) is preferably 80 or more, more preferably 100 or more, further preferably 130 or more, and particularly preferably 150 or more. It is practical that the upper limit is 500 or less.
  • the other structural unit is preferably a structural unit represented by the formula (11).
  • the formulas (2) to (5) preferably include the structural units represented by the formulas (12) to (15), respectively.
  • the specific polymer further includes a structural unit having no polymerizable group (sometimes referred to as “an additional structural unit”).
  • Still other structural units include structural units represented by formulas (21) to (25).
  • R 11b represents a substituent
  • m21 represents an integer of 1 to 4.
  • a plurality of R 11b may be the same or different, and two R 11b may be bonded to each other to form a ring.
  • at least one of m21 R 11b represents a group represented by the formula (T3).
  • R 2b represents a hydrogen atom or a methyl group
  • R 12b represents a substituent
  • m22 represents an integer of 1 to 5.
  • a plurality of R 12b may be the same or different, and two R 12b may be bonded to each other to form a ring.
  • R 12b represents a group represented by the formula (T3).
  • R 3b represents a hydrogen atom or a methyl group
  • R 13b represents a group represented by Formula (T3).
  • R 4b represents a hydrogen atom or a methyl group
  • R 14b represents a group represented by Formula (T3).
  • R 15b represents a group represented by Formula (T3).
  • Examples of the substituent represented by R 11b and R 12b include the substituent T described above and a group represented by the following formula (T3).
  • n8 is 0 or 1.
  • T 1 is the above substituent T. Among them, an alkyl group which may be substituted with a halogen atom, an aryl group which may be substituted with a halogen atom, and an arylalkyl group which may be substituted with a halogen atom. preferable.
  • n9 is an integer of 1 to 6, preferably 1 or 2.
  • L 5 may be a trivalent or more valent connecting group, for example, a trivalent or more alkane structure group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms). , 1 to 3 are more preferable), an alkene structure group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 is more preferable), or an aryl structure group (preferably having 6 to 22 carbon atoms). , 6 to 18 are more preferred, and 6 to 10 are even more preferred).
  • a trivalent or more alkane structure group preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms. , 1 to 3 are more preferable
  • an alkene structure group preferably having 2 to 12 carbon atoms, more preferably 2 to 6 is more preferable
  • an aryl structure group preferably having 6 to 22 carbon atoms.
  • 6 to 18 are more preferred, and 6 to 10 are even more preferred.
  • the structural unit represented by any of the formulas (1) to (5) may constitute all of the polymer (a homopolymer having a structural ratio of 100 mol%), Further, it may be a copolymer with other constituent units.
  • the constitutional ratio of the constitutional units represented by the formulas (1) to (5) / other constitutional units (constitutional units having a polymerizable group) / further constitutional units is based on a molar ratio, It is preferably from 10 to 100/0 to 80/0 to 50, more preferably from 30 to 100/0 to 70/0 to 30, and still more preferably from 50 to 100/0 to 50/0 to 10/0.
  • the ratio of the structural unit having a polymerizable group is preferably from 10 to 100% by mole, more preferably from 50 to 100% by mole of all the structural units.
  • the specific polymer contains only one kind of each of the structural units represented by the formulas (1) to (5), other structural units (structural units having a polymerizable group), and other structural units. Or two or more of them may be included. When two or more kinds are contained, it is preferable that the sum is the above ratio.
  • the weight average molecular weight of the specific polymer is preferably 4,000 or more, more preferably 5,000 or more, further preferably 7000 or more, and still more preferably 10,000 or more.
  • the upper limit is preferably 2,000,000 or less, more preferably 15,000,000 or less, and still more preferably 1,000,000 or less.
  • the method for measuring the weight average molecular weight is based on the method described in Examples described later.
  • the content of the specific polymer in the composition for forming an underlayer film is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 0.1% by mass or more. More preferred.
  • the upper limit is preferably 10% by mass or less, more preferably 7% by mass or less, still more preferably 5% by mass or less, even more preferably 4% by mass or less, and 3% by mass. %, Still more preferably 1% by mass or less, or 0.7% by mass or less.
  • the content of the specific polymer in the non-volatile components of the composition for forming a lower layer film is preferably 5% by mass or more, and more preferably 20% by mass or more.
  • the upper limit may be 100% by mass.
  • the amount is equal to or more than the above lower limit, the effect of blending the polymer can be suitably exhibited, and a uniform thin film can be easily prepared.
  • the content is not more than the above upper limit, the effect of using the solvent is suitably exhibited, and a uniform film can be easily formed over a wide area. Only one specific polymer may be used, or two or more specific polymers may be used. When two or more kinds are used, the total amount is preferably within the above range.
  • the composition for forming the lower layer film preferably contains a thermosetting accelerator. According to this aspect, it is easy to form a lower layer film having a high crosslinking density, and it is possible to effectively suppress diffusion of the liquid film provided on the lower layer film into the lower layer film.
  • thermosetting accelerator is preferably a compound that generates an acid or a cation at a temperature of 100 ° C. or higher (preferably 100 to 180 ° C., more preferably 120 to 180 ° C., and still more preferably 120 to 160 ° C.).
  • the thermosetting accelerator is preferably a compound that generates an acid having a pKa of 4 or less, more preferably a compound that generates an acid having a pKa of 3 or less, and most preferably a compound that generates an acid with a pKa of 2 or less.
  • pKa basically indicates pKa in water at 25 ° C. Those that cannot be measured in water refer to those measured after changing to a solvent suitable for measurement. Specifically, pKa described in a chemical handbook or the like can be referred to.
  • the acid having a pKa of 3 or less is preferably a sulfonic acid or a phosphonic acid, and more preferably a sulfonic acid.
  • thermosetting accelerator examples include compounds that generate a low nucleophilic acid such as sulfonic acid, carboxylic acid and disulfonylimide by heating.
  • the above-mentioned acid is preferably an acid having a pKa of 4 or less, more preferably an acid having a pKa of 3 or less, and still more preferably an acid having a pKa of 2 or less.
  • pKa basically indicates pKa in water at 25 ° C. Those that cannot be measured in water refer to those measured after changing to a solvent suitable for measurement.
  • thermosetting accelerator compounds described in paragraphs 0033 to 0047 of JP-A-2017-088866 can also be used as the thermosetting accelerator.
  • the content of the thermosetting accelerator in the composition for forming a lower layer film is preferably at least 0.0001% by mass, more preferably at least 0.001% by mass, and is at least 0.003% by mass. Is more preferable.
  • the upper limit is preferably 0.03% by mass or less, more preferably 0.02% by mass or less, and even more preferably 0.01% by mass or less.
  • the content of the thermosetting accelerator in the nonvolatile component of the composition for forming a lower layer film (refers to components other than the solvent in the composition, the same applies hereinafter) is preferably 0.1% by mass or more, and preferably 1% by mass. %, More preferably 3% by mass or more.
  • the upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less. Further, the content of the thermosetting accelerator is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the specific polymer described above.
  • the lower limit is preferably at least 0.5 part by mass, more preferably at least 1 part by mass, even more preferably at least 3 parts by mass.
  • the upper limit is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less.
  • the thermosetting accelerator may be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably within the above range.
  • the total amount is preferably in the above range.
  • the boiling point of the solvent for the lower layer film is preferably 230 ° C. or lower, more preferably 200 ° C. or lower, further preferably 180 ° C. or lower, further preferably 160 ° C. or lower, and more preferably 130 ° C. or lower. Is even more preferable.
  • the lower limit is practically 23 ° C., it is more practical that the lower limit is 60 ° C. or higher.
  • the solvent for the lower layer film is preferably an organic solvent.
  • the solvent is preferably a solvent having at least one of an ester group, a carbonyl group, a hydroxyl group and an ether group. Among them, it is preferable to use an aprotic polar solvent.
  • alkoxy alcohol propylene glycol monoalkyl ether carboxylate, propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate.
  • alkoxy alcohol examples include methoxyethanol, ethoxyethanol, methoxypropanol (eg, 1-methoxy-2-propanol), ethoxypropanol (eg, 1-ethoxy-2-propanol), and propoxypropanol (eg, 1-propoxy-2-propanol).
  • Propanol methoxybutanol (eg, 1-methoxy-2-butanol, 1-methoxy-3-butanol), ethoxybutanol (eg, 1-ethoxy-2-butanol, 1-ethoxy-3-butanol), methylpentanol (Eg, 4-methyl-2-pentanol).
  • 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, Acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthyl ketone or methyl amyl ketone is preferred.
  • cyclic ketone methylcyclohexanone, isophorone or cyclohexanone is preferable.
  • lactone ⁇ -butyrolactone ( ⁇ BL) is preferable.
  • alkylene carbonate propylene carbonate is preferred.
  • a solvent having a flash point (hereinafter, also referred to as a p component) of 30 ° C or higher.
  • Such components include propylene glycol monomethyl ether (p component: 47 ° C.), ethyl lactate (p component: 53 ° C.), ethyl 3-ethoxypropionate (p component: 49 ° C.), and methyl amyl ketone (p component: 42 ° C.), cyclohexanone (p component: 30 ° C.), pentyl acetate (p component: 45 ° C.), methyl 2-hydroxyisobutyrate (p component: 45 ° C.), ⁇ -butyrolactone (p component: 101 ° C.), or propylene carbonate (P component: 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 particularly preferred as the solvent for the lower layer film alkoxy alcohol, propylene glycol monoalkyl ether carboxylate, propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, chain ketone, cyclic ketone, lactone, and alkylene Carbonates.
  • Alkylene glycol compounds include polyethylene glycol, polypropylene glycol, their mono or dimethyl ether, mono or dioctyl ether, mono or dinonyl ether, mono or didecyl ether, monostearate, monooleate, monoadipate, and monosuccinate. Acid esters are exemplified, and polyethylene glycol and polypropylene glycol are preferred.
  • the surface tension at 23 ° C. of the alkylene glycol compound is preferably at least 38.0 mN / m, more preferably at least 40.0 mN / m. Although the upper limit of the surface tension is not particularly limited, it is, for example, 48.0 mN / m or less.
  • the wettability of the photocurable composition for imprints can be further improved.
  • the surface tension of the alkylene glycol compound is measured at 23 ° C. using a surface tension meter SURFACE TENS-IOMETER CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd. using a glass plate. The unit is indicated by mN / m. Two samples are prepared for each level, and each sample is measured three times. An arithmetic average value of a total of six times is adopted as the evaluation value.
  • the content of the alkylene glycol compound is preferably 40% by mass or less, more preferably 30% by mass or less, and more preferably 20% by mass or less of the nonvolatile component in the composition for forming an underlayer film. More preferably, it is particularly preferably at most 15% by mass.
  • the lower limit can be 0.5% by mass or more, and can be 1% by mass or more. Only one alkylene glycol compound may be used, or two or more alkylene glycol compounds may be used. When two or more kinds are used, the total amount is preferably within the above range.
  • a known compound can be arbitrarily used.
  • halogenated hydrocarbon derivatives for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
  • acylphosphine compounds for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
  • acylphosphine compounds for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
  • acylphosphine compounds for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
  • acylphosphine compounds for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a tri
  • the composition for forming a lower layer film may include one or more of a polymerization inhibitor, an antioxidant, a leveling agent, a thickener, a surfactant, and the like.
  • a polymerization inhibitor an antioxidant
  • a leveling agent e.g., a leveling agent
  • a thickener e.g., a surfactant
  • the viscosity of the composition for forming a liquid film is preferably 1,000 mPas or less, more preferably 800 mPas or less, further preferably 500 mPas or less, and more preferably 100 mPas or less. Is more preferred.
  • the lower limit of the viscosity is not particularly limited, but may be, for example, 1 mPa ⁇ s or more.
  • the viscosity is measured according to the following method. The viscosity is measured by adjusting the temperature of the sample cup to 23 ° C. using an E-type rotary viscometer RE85L manufactured by Toki Sangyo Co., Ltd. and a standard cone rotor (1 ° 34 ′ ⁇ R24).
  • the unit is mPa ⁇ s. Other details regarding the measurement conform to JISZ8803: 2011. Two samples are prepared for each level, and each sample is measured three times. An arithmetic average value of a total of six times is adopted as the evaluation value.
  • composition for forming a liquid film contains a polymerizable compound (polymerizable compound A) which is liquid at 23 ° C. and 1 atm.
  • the viscosity of the polymerizable compound A at 23 ° C. is preferably from 1 to 100,000 mPa ⁇ s.
  • the lower limit is preferably 5 mPa ⁇ s or more, and more preferably 11 mPa ⁇ s or more.
  • the upper limit is preferably 1,000 mPa ⁇ s or less, and more preferably 600 mPa ⁇ s or less.
  • the polymerizable compound A has an aromatic ring (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, still more preferably having 6 to 10 carbon atoms) and an alicyclic ring (having 3 to 24 carbon atoms, and preferably having 3 to 18 carbon atoms). (More preferably 3 to 6), and more preferably an aromatic ring.
  • the aromatic ring is preferably a benzene ring.
  • the molecular weight of the polymerizable compound A is preferably from 100 to 900.
  • Examples of the polymerizable group of the polymerizable compound A include a (meth) acryloyl group, an oxiranyl group, and an oxetanyl group, and a (meth) acryloyl group is preferable. Further, the polymerizable compound A is preferably a radical polymerizable compound.
  • the polymerizable compound A is also preferably a compound represented by the following formula (I-1).
  • L 20 is a 1 + q divalent linking group, for example, a 1 + q divalent alkane group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3), or an alkene structure group (Preferably having 2 to 12 carbon atoms, more preferably having 2 to 6 carbon atoms, and still more preferably having 2 to 3 carbon atoms), an aryl group (having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 10 carbon atoms) ), A group having a heteroaryl structure (preferably having 1 to 22 carbon atoms, more preferably having 1 to 18 carbon atoms, and still more preferably having 1 to 10 carbon atoms.
  • a 1 + q divalent alkane group preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3
  • an alkene structure group Preferably having 2 to 12 carbon atom
  • hetero atom examples include a nitrogen atom, a sulfur atom and an oxygen atom.
  • Examples of a group obtained by combining two aryl groups include groups having a structure such as biphenyl, diphenylalkane, biphenylene, and indene.
  • Examples of a combination of a group having a heteroaryl structure and a group having an aryl structure include groups having a structure such as indole, benzimidazole, quinoxaline, and carbazole.
  • L 20 is preferably a linking group containing at least one selected from an aryl group and a heteroaryl group, and more preferably a link group containing an aryl group.
  • R 21 and R 22 each independently represent a hydrogen atom or a methyl group.
  • Examples of the polymerizable compound A include compounds described in paragraphs 0017 to 0024 of JP-A-2014-090133 and the examples, compounds described in paragraphs 0024 to 0089 of JP-A-2005-009071, and JP-A-2015-070145.
  • the compounds described in paragraphs 0023 to 0037 of the publication and the compounds described in paragraphs 0012 to 0039 of WO 2016/152597 can also be used.
  • the content of the polymerizable compound A in the composition for forming a liquid film is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 0.1% by mass or more. Is more preferable.
  • the upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less.
  • the content of the polymerizable compound A in the non-volatile components of the composition for forming a liquid film (refer to components other than the solvent in the composition, the same applies hereinafter) is preferably 0.01% by mass or more. It is more preferably at least 05% by mass, even more preferably at least 0.1% by mass.
  • the upper limit may be 100% by mass.
  • the non-volatile component of the composition for forming a liquid film comprises substantially only the polymerizable compound A.
  • the case where the non-volatile component of the composition for forming a liquid film substantially consists only of the polymerizable compound A means that the content of the polymerizable compound A in the non-volatile component of the composition for forming a liquid film is 99.9% by mass. It is more preferably 99.99% by mass or more, more preferably only polymerizable compound A.
  • the composition for forming a liquid film preferably contains a solvent (hereinafter, sometimes referred to as a “solvent for a liquid film”).
  • the solvent for the liquid film include those described in the section of the solvent for the lower layer described above, and these can be used.
  • the composition for forming a liquid film preferably contains the solvent for a liquid film in an amount of 90% by mass or more, more preferably 99% by mass or more, and may be 99.99% by mass or more.
  • the boiling point of the liquid film solvent is preferably 230 ° C. or lower, more preferably 200 ° C. or lower, further preferably 180 ° C. or lower, still more preferably 160 ° C. or lower, and 130 ° C. or lower. Is even more preferable. Although the lower limit is practically 23 ° C., it is more practical that the lower limit is 60 ° C. or higher. By setting the boiling point within the above range, the solvent can be easily removed from the liquid film, which is preferable.
  • the composition for forming a liquid film may include a polymerization initiator.
  • the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator, and are preferably a photopolymerization initiator, and more preferably a photoradical polymerization initiator.
  • the polymerization initiator include those described in the section of the composition for forming an underlayer film described above, and these can be used.
  • the polymerization initiator When the polymerization initiator is contained, it is preferably 0.1 to 10% by mass, more preferably 1 to 8% by mass, and more preferably 2 to 5% by mass of the nonvolatile component of the liquid film forming composition. Is more preferable. When two or more polymerization initiators are used, the total amount is preferably within the above range.
  • composition for forming a liquid film may include one or more of a polymerization inhibitor, an antioxidant, a leveling agent, a thickener, a surfactant, and the like.
  • Photocurable composition for imprint >>> Next, the photocurable composition for imprints used in the laminate for imprints of the present invention will be described.
  • the photocurable composition for imprints is not particularly limited, and a known photocurable composition for imprints can be used.
  • the photocurable composition for imprints preferably contains at least a polymerizable compound.
  • the viscosity of the photocurable composition for imprints is preferably 20 mPa ⁇ s or less, more preferably 15 mPa ⁇ s or less, further preferably 11 mPa ⁇ s or less, and is 9 mPa ⁇ s or less. Is more preferred.
  • the lower limit of the viscosity is not particularly limited, but may be, for example, 5 mPa ⁇ s or more.
  • the viscosity is measured according to the following method. The viscosity is measured by adjusting the temperature of the sample cup to 23 ° C. using an E-type rotary viscometer RE85L manufactured by Toki Sangyo Co., Ltd. and a standard cone rotor (1 ° 34 ′ ⁇ R24).
  • the unit is mPa ⁇ s. Other details regarding the measurement conform to JISZ8803: 2011. Two samples are prepared for each level, and each sample is measured three times. An arithmetic average value of a total of six times is adopted as the evaluation value.
  • the surface tension of the photocurable composition for imprints is preferably at least 28 mN / m, more preferably at least 30 mN / m, even more preferably at least 32 mN / m.
  • the upper limit of the surface tension is not particularly limited, but is preferably 40 mN / m or less, more preferably 38 mN / m or less, and more preferably 36 mN / m, from the viewpoint of imparting inkjet suitability. m or less.
  • the surface tension of the photocurable composition for imprints is measured according to the following method.
  • the surface tension was measured at 23 ° C. using a glass plate using a surface tension meter SURFACE TENS-IOMETER CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd.
  • the unit is shown in mN / m. Two samples were prepared for each level, and each was measured three times. An arithmetic average value of a total of six times is adopted as the evaluation value.
  • the Onishi parameter of the photocurable composition for imprints is preferably 5 or less, more preferably 4 or less, and even more preferably 3.7 or less.
  • the lower limit value of the Onishi parameter of the photocurable composition for imprinting is not particularly limited, but may be, for example, 1 or more, or 2 or more.
  • the photocurable composition for imprints used in the present invention has a value of ⁇ HSP calculated by the following formula (H1) based on the Hansen solubility parameter of the liquid film and the Hansen solubility parameter of the photocurable composition for imprint. It is preferably 10 or less, more preferably 5 or less, and still more preferably 3 or less. The lower limit may be zero. When the value of ⁇ HSP is 10 or less, the effect of the photocurable composition 13 for imprints on droplet expandability can be expected.
  • ⁇ 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 photocurable composition for imprinting and the dispersion term component of the Hansen solubility parameter vector of the liquid film
  • ⁇ P is the photocurable composition for imprinting.
  • the difference between the polarity term component of the Hansen solubility parameter vector and the polarity term component of the Hansen solubility parameter vector of the liquid film, ⁇ H is the hydrogen bond term component of the Hansen solubility parameter vector of the photocurable composition for imprinting, The difference in the hydrogen bond term component of the Hansen solubility parameter vector of the film.
  • the dispersion term component of the Hansen solubility parameter vector of the photocurable composition for imprinting is preferably from 8 to 25, more preferably from 10 to 20, and even more preferably from 14 to 18.
  • the polarity term component of the Hansen solubility parameter vector of the photocurable composition for imprint is preferably 1 to 10, more preferably 2 to 8, and even more preferably 3 to 5.
  • the hydrogen bond term component of the Hansen solubility parameter vector of the photocurable composition for imprint is preferably from 1 to 15, more preferably from 3 to 10, and even more preferably from 3 to 8.
  • the dispersion term component, the polar term component, and the hydrogen bond term component of the Hansen solubility parameter vector of the liquid film and the photocurable composition for imprinting are respectively set by the methods described in Examples described later. Further, in the present invention, the dispersion term component, the polar term component, and the hydrogen bond term component of the Hansen solubility parameter vector of the liquid film are the dispersion of the Hansen solubility parameter of the non-volatile component (the component other than the solvent) of the liquid film forming composition. The values of the term component, the polar term component, and the hydrogen bond term component are used.
  • the polymerizable compound may be a monofunctional polymerizable compound having only one polymerizable group in one molecule, or a polyfunctional polymerizable compound having two or more polymerizable groups in one molecule. Is also good. A monofunctional polymerizable compound and a polyfunctional polymerizable compound may be used in combination.
  • the polymerizable compound contained in the photocurable composition for imprint preferably contains a polyfunctional polymerizable compound, and more preferably contains a polymerizable compound containing 2 to 5 polymerizable groups in one molecule. More preferably, a polymerizable compound having two to four polymerizable groups is contained in one molecule, and particularly preferably, a polymerizable compound having two polymerizable groups is contained in one molecule.
  • At least one of the above polymerizable compounds is a compound represented by the following formula (I-1).
  • L 20 is a 1 + q divalent linking group, for example, a 1 + q divalent alkane group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3), or an alkene structure group (Preferably having 2 to 12 carbon atoms, more preferably having 2 to 6 carbon atoms, and still more preferably having 2 to 3 carbon atoms), an aryl group (having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 10 carbon atoms) ), A group having a heteroaryl structure (preferably having 1 to 22 carbon atoms, more preferably having 1 to 18 carbon atoms, and still more preferably having 1 to 10 carbon atoms.
  • a 1 + q divalent alkane group preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3
  • an alkene structure group Preferably having 2 to 12 carbon atom
  • L 21 and L 22 each independently represent a single bond or the above-mentioned linking group L, and is preferably a single bond or an alkylene group.
  • L 20 and L 21 or L 22 may form a ring without intervention or through a linking group L.
  • L 20 , L 21 and L 22 may have the substituent T described above.
  • a plurality of substituents T may combine to form a ring. When there are a plurality of substituents T, they may be the same or different.
  • q2 is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, still more preferably 0 or 1, and particularly preferably 1.
  • Examples of the polymerizable compound include compounds used in Examples described later, paragraphs 0017 to 0024 of JP-A-2014-133 and compounds described in Examples, and paragraphs 0024 to 0089 of JP-A-2005-009071.
  • the compounds described in paragraphs 0023 to 0037 of JP-A-2015-070145 and the compounds described in paragraphs 0012 to 0039 of WO2016 / 152597 can be exemplified, but the present invention is not limited thereto. Is not to be interpreted.
  • the polymerizable compound is preferably contained in the photocurable composition for imprints in an amount of 30% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, even more preferably 55% by mass or more. It may be at least 70 mass%, and may be at least 70 mass%. Further, the upper limit is preferably less than 99% by mass, more preferably 98% by mass or less, and can be 97% by mass or less.
  • a known compound can be arbitrarily used.
  • halogenated hydrocarbon derivatives eg, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
  • acylphosphine compounds eg, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
  • acylphosphine compounds eg, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
  • acylphosphine compounds eg, acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides Thio compounds, ketone compounds, aromatic onium salts, acetophenone compounds, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron
  • the photopolymerization initiator is preferably contained in the photocurable composition for imprints in an amount of 0.01 to 15% by mass, more preferably 0.1 to 12% by mass, and still more preferably 0.2 to 7% by mass. % By mass.
  • the photocurable composition for imprints may further contain a surfactant, a sensitizer, a release agent, an antioxidant, a polymerization inhibitor, and the like.
  • Specific examples of the photocurable composition for imprints that can be used in the present invention include compositions described in JP-A-2013-036027, JP-A-2014-090133, and JP-A-2013-189537. Illustrated, and their contents are incorporated herein. The description of the above publication can also be referred to for the method of preparing the photocurable composition for imprints, and the contents thereof are incorporated in the present specification.
  • the content of the solvent in the photocurable composition for imprints is preferably 5% by mass or less, more preferably 3% by mass or less, and more preferably 1% by mass or less of the photocurable composition for imprints. It is more preferred that there be.
  • the photocurable composition for imprinting is preferably a polymer (preferably having a weight average molecular weight of more than 1,000, more preferably having a weight average molecular weight of more than 2,000, even more preferably having a weight average molecular weight of 10,000 or more. (Polymer) is not substantially contained.
  • the phrase "contains substantially no polymer” means, for example, that the content of the polymer is 0.01% by mass or less of the photocurable composition for imprint, preferably 0.005% by mass or less, and is not contained at all. Is more preferable.
  • the kit of the present invention is a kit used for the above-described imprint laminate of the present invention, which comprises a composition for forming an underlayer film containing a polymer having an aromatic ring and a polymerizable group, at 23 ° C. and 1 atm. And a liquid film-forming composition containing a polymerizable compound that is liquid in the above, and a photocurable composition for imprint.
  • the composition for forming a lower layer film, the composition for forming a liquid film, and the photocurable composition for imprinting include those described above, and the preferred ranges are also the same.
  • the method for producing a laminate for imprinting of the present invention includes a step of forming an underlayer film by applying an underlayer film forming composition containing a polymer having an aromatic ring and a polymerizable group on a substrate, Forming a liquid film by applying a liquid film forming composition containing a polymerizable compound that is liquid at 23 ° C. and 1 atm on the lower layer film; Applying the photocurable composition for imprints on the liquid film.
  • each step will be described.
  • the underlayer film is formed by applying a composition for forming an underlayer film containing a polymer having an aromatic ring and a polymerizable group on a substrate.
  • the substrate to which the composition for forming an underlayer film is applied is not particularly limited.
  • the one described in the section of the imprint laminate described above is used.
  • the composition for forming an underlayer film those described in the section of the laminate for imprint described above are used.
  • the lower layer film is preferably formed by applying the composition for forming a lower layer film on a substrate in a layered manner. An adhesive film may be provided on the surface of the substrate below the lower film.
  • a liquid film forming composition containing a polymerizable compound that is liquid at 23 ° C. and 1 atm is applied on the lower film to form a liquid film.
  • the liquid film is preferably formed by applying the composition for forming a liquid film on the lower film in a layered manner.
  • the composition for forming a liquid film those described in the section of the laminate for imprint described above are used.
  • the method for applying the composition for forming a liquid film is not particularly limited, and a generally well-known application method can be employed. For example, a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spin coating method, a slit scanning method, and an ink jet method are exemplified, and a spin coating method is preferable.
  • the solvent is preferably volatilized (dried) by heat to form a liquid film.
  • the heating temperature is preferably from 80 to 200 ° C, more preferably from 80 to 180 ° C, even more preferably from 80 to 150 ° C.
  • the heating temperature is preferably lower than the temperature at which the polymerizable compound contained in the composition for forming a liquid film reacts and cures.
  • the heating time is preferably 30 seconds to 5 minutes.
  • the photocurable composition for imprint on the liquid film.
  • the photocurable composition for imprint those described in the section of the laminate for imprint described above are used.
  • the method of applying the photocurable composition for imprinting is not particularly limited, and the description in paragraph 0102 of JP2010-109092A (the publication number of the corresponding US application is US2011 / 0183127) can be referred to. The contents are incorporated herein.
  • the photocurable composition for imprinting is preferably applied to the surface of a liquid film by an inkjet method. Further, the photocurable composition for imprints may be applied by multiple coating.
  • the amount of the droplets is preferably about 1 to 20 pL, and it is preferable to arrange the droplets on the liquid film surface at intervals.
  • the interval between droplets is preferably 10 to 1000 ⁇ m.
  • the interval between the droplets is the interval between the nozzles of the inkjet.
  • the imprint laminate of the present invention can be manufactured.
  • the pattern forming method of the present invention is a step of forming an underlayer film by applying an underlayer film forming composition containing a polymer having an aromatic ring and a polymerizable group on a substrate, Forming a liquid film by applying a liquid film forming composition containing a polymerizable compound that is liquid at 23 ° C.
  • a step of applying the photocurable composition for imprint on the liquid film Contacting a mold having a pattern with a photocurable composition for imprinting on a liquid film, Step of exposing the photocurable composition for imprints in a state where the mold is in contact with the A step of peeling the mold from the exposed photocurable composition for imprint, including.
  • a desired cured product pattern imprint pattern
  • the step of forming the lower layer film, the step of forming the liquid film, and the step of applying the photocurable composition for imprint are the same as those described in the section of the method for producing a laminate for imprint described above.
  • the imprint laminate shown in FIG. 1 is formed.
  • the photocurable composition for imprint 13 on the liquid film 12 is brought into contact with the mold 20 having a pattern. Specifically, the mold 20 is pressed against the surface of the photocurable composition 13 for imprints.
  • a mold that can be used in the present invention is a mold having a pattern to be transferred.
  • the pattern of the mold can be formed according to a desired processing accuracy by, for example, photolithography or electron beam lithography, but the method of manufacturing a mold pattern is not particularly limited in the present invention. Further, a pattern formed by the method for producing a cured product pattern according to a preferred embodiment of the present invention can be used as a mold.
  • the material constituting the light-transmitting mold used in the present invention is not particularly limited, but may be a light-transmitting resin such as glass, quartz, polymethyl methacrylate (PMMA), or a polycarbonate resin, a transparent metal vapor-deposited film, or polydimethylsiloxane.
  • Examples thereof include a flexible film, a photocurable film, and a metal film, and quartz is preferable.
  • the non-light-transmitting mold material used when a light-transmitting substrate is used in the present invention is not particularly limited, but may be any material having a predetermined strength. Specific examples include ceramic materials, vapor-deposited films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, and substrates such as SiC, silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon. And are not specifically restricted.
  • the mold pressure is preferably set to 10 atm or less.
  • the mold pressure is preferably set to 10 atm or less.
  • the mold 20 and the substrate 1 are less likely to be deformed, and the pattern accuracy tends to be improved. It is also preferable because the pressure is low and the device tends to be reduced in size.
  • the contact between the photocurable composition for imprint 13 and the mold 20 is performed in an atmosphere containing a helium gas, a condensable gas, or both a helium gas and a condensable gas.
  • the photocurable composition for imprint 13 is exposed while the mold 20 is in contact with the photocurable composition for imprint 13.
  • the irradiation amount at the time of exposure may be sufficiently larger than the minimum irradiation amount necessary for curing the photocurable composition 13 for imprints.
  • the irradiation amount required for curing the photocurable composition for imprint 13 is determined as appropriate by examining the consumption of unsaturated bonds of the photocurable composition for imprint 13 and the like.
  • the type of light used for the exposure is not particularly limited, but ultraviolet light is exemplified.
  • the substrate temperature during the exposure is usually room temperature, but the exposure may be performed while heating to increase the reactivity.
  • a vacuum state is set as a pre-exposure stage, it is effective in preventing air bubbles from being mixed, suppressing a decrease in reactivity due to oxygen being mixed, and improving the adhesion between the mold 20 and the photocurable composition 13 for imprint.
  • Light irradiation may be performed in the state.
  • the preferable degree of vacuum at the time of exposure 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.
  • a step of applying heat to the photocurable composition for imprint 13 after the exposure to further cure the composition may be included.
  • the heating temperature is preferably from 150 to 280 ° C, more preferably from 200 to 250 ° C.
  • the heating time is preferably from 5 to 60 minutes, more preferably from 15 to 45 minutes.
  • the mold 20 is peeled off from the exposed photocurable composition for imprints (FIG. 3).
  • a pattern having a shape following the pattern of the mold 20 (hereinafter, also referred to as a cured product pattern) is formed.
  • the obtained cured product pattern can be used for various applications as described below.
  • the present invention is particularly advantageous in that a fine pattern on the order of nanometers 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 method for producing a cured product pattern is not particularly limited, but may be, for example, 1 nm or more.
  • the pattern (cured product pattern) formed by the pattern forming method of the present invention can be used as a permanent film used for a liquid crystal display (LCD) or the like, or as an etching resist (lithographic mask) for manufacturing a semiconductor element.
  • the present invention discloses a circuit board manufacturing method including a step of obtaining a pattern (cured product pattern) by a pattern forming method according to a preferred embodiment of the present invention.
  • a polarizing plate having a large screen size for example, more than 55 inches or more than 60 inches
  • a polarizing plate described in JP-A-2015-132825 or WO2011 / 132649 can be manufactured.
  • One inch is 25.4 mm.
  • the pattern (cured product pattern) formed by the pattern forming method of the present invention is also useful as an etching resist (lithographic mask).
  • a cured product pattern is used as an etching resist
  • a pattern (cured product pattern) is formed on a substrate by applying the pattern forming method of the present invention, and the obtained cured product pattern is used as an etching mask.
  • an etching gas such as hydrogen fluoride in the case of wet etching or CF 4 in the case of dry etching, a pattern can be formed on the substrate according to a desired cured product pattern. it can.
  • the pattern (cured product pattern) formed by the pattern forming method of the present invention includes a recording medium such as a magnetic disk, a light receiving element such as a solid-state imaging device, an LED (light emitting diode), an organic EL (organic electroluminescence), and the like.
  • Light emitting devices such as liquid crystal display devices (LCD), diffraction gratings, relief holograms, optical waveguides, optical filters, optical components such as microlens arrays, thin film transistors, organic transistors, color filters, antireflection films, polarizing plates, Flat panel display members such as polarizing elements, optical films, pillars, etc., nanobiodevices, immunoassay chips, deoxyribonucleic acid (DNA) separation chips, microreactors, photonic liquid crystals, and micropatterns using self-assembly of block copolymers (Directed self-assembly, DSA) can also be preferably used in the preparation of the guide patterns, etc. for.
  • LCD liquid crystal display devices
  • DSA directed self-assembly
  • the weight average molecular weight (Mw) of the polymer was defined as a value in terms of polystyrene according to gel permeation chromatography (GPC measurement).
  • the apparatus used was HLC-8220 (manufactured by Tosoh Corporation), and the columns used were a guard column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by Tosoh Corporation).
  • the eluent used was THF (tetrahydrofuran).
  • an RI (Refractive Index) detector was used.
  • the Hansen solubility parameters of the liquid film and the photocurable composition for imprints were calculated using HSP calculation software HSPiP. Specifically, by inputting the structural formula of each compound contained in the liquid film and the photocurable composition for imprints into the software in the SMILES format, the Hansen of the liquid film and the photocurable composition for imprints is input.
  • the variance term component hereinafter also referred to as D component
  • the polar term component hereinafter also referred to as P component
  • H component hydrogen bond term component
  • ⁇ HSP Hansen solubility parameters
  • the obtained mixture was added dropwise over 2 hours at a temperature at which the internal temperature of the flask did not exceed 95 ° C, and aging was performed at 90 ° C for 4 hours. 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 solution in the flask was added dropwise at a temperature not exceeding 5 ° C. over 30 minutes, followed by stirring for 1 hour. Thereafter, the mixture was stopped for 1 hour and filtered under reduced pressure.
  • the target compound (intermediate P-1B) was synthesized by drying the obtained powder under reduced pressure.
  • composition for forming lower layer film Each of the compounds shown in the following table was mixed, and subjected to two-stage filtration with a polytetrafluoroethylene (PTFE) filter having a pore size of 0.1 ⁇ m and a PTFE filter having a pore size of 0.003 ⁇ m to obtain a composition X-1 for forming an underlayer film.
  • PTFE polytetrafluoroethylene
  • T-1 IRGACURE OXE01 (manufactured by BASF)
  • T-2 Omnirad TPO H (manufactured by IGM Resins BV)
  • T-3 Sun-Aid SI-150L (manufactured by Sanshin Chemical Industry Co., Ltd.)
  • composition for forming liquid film Each compound shown in the following table was mixed, and subjected to two-stage filtration with a polytetrafluoroethylene (PTFE) filter having a pore size of 0.1 ⁇ m and a PTFE filter having a pore size of 0.003 ⁇ m to obtain a composition W-1 for forming a liquid film.
  • PTFE polytetrafluoroethylene
  • ⁇ W-29 was prepared.
  • the Hansen solubility parameters of the nonvolatile components of the composition for forming a liquid film are shown in the following table.
  • J-1 to J-24 Compounds having the following structures (polymerizable compounds that are liquid at 23 ° C. and 1 atm)
  • T-2 Omnirad TPO H (manufactured by IGM Resins BV)
  • T-3 Sun-Aid SI-150L (manufactured by Sanshin Chemical Industry Co., Ltd.)
  • T-4 Omnirad 184 (manufactured by IGM Resins BV)
  • T-5 BLAUNON SR-705 (manufactured by Aoki Yushi Kogyo Co., Ltd., polyoxyethylene stearyl ether)
  • the Hansen solubility parameters of the photocurable composition for imprints are as follows.
  • ⁇ Calculation of ⁇ HSP value of Hansen solubility parameter of liquid film and Hansen solubility parameter of photocurable composition for imprint> The Hansen solubility parameters of the liquid film and the photocurable composition for imprints were calculated using HSP calculation software HSPiP. Specifically, by inputting the structural formula of each compound contained in the liquid film and the photocurable composition for imprints into the software in the SMILES format, the Hansen of the liquid film and the photocurable composition for imprints is input. Each component ( ⁇ D, ⁇ P, ⁇ H) of the solubility parameter was calculated.
  • a Hansen solubility parameter of the liquid film As the Hansen solubility parameter of the liquid film, a Hansen solubility parameter of a non-volatile component (a component other than the solvent) of the composition for forming a liquid film was used.
  • the ⁇ HSP value of the Hansen solubility parameter of the liquid film and the Hansen solubility parameter of the photocurable composition for imprint was calculated by applying the calculated Hansen solubility parameter to the following equation.
  • ⁇ HSP (4.0 ⁇ ⁇ D 2 + ⁇ P 2 + ⁇ H 2 ) 0.5
  • a composition for forming an underlayer film shown in the following table was spin-coated on a silicon wafer, heated for 1 minute using a hot plate at 220 ° C., and the solvent was dried to form an underlayer film having a thickness of 5 nm.
  • the surface of the lower layer film was spin-coated with a liquid film forming composition shown in the following table, heated for 1 minute using a hot plate at 100 ° C., and the solvent was dried to obtain a liquid having a film thickness shown in the following table.
  • a film was formed. The thicknesses of the lower layer film and the liquid film were measured by an ellipsometer and an atomic force microscope.
  • a photocurable composition for imprints temperature-controlled to 25 ° C., as shown in the following table, was applied at 1 pL / nozzle using an inkjet printer DMP-2831, manufactured by FUJIFILM Dymatics. And the droplets were applied to the surface of the liquid film so that the droplets were arranged in a square array at intervals of about 100 ⁇ m.
  • a quartz mold (rectangular line / space pattern (1/1), line width 60 nm, groove depth 100 nm, line edge roughness 3.5 nm) is pressed into contact with the photocurable composition for imprint on the liquid film. The mold was filled with the photocurable composition for imprinting.
  • the pattern was transferred to the photocurable composition for imprints by removing the mold.
  • the pattern transferred to the photocurable composition for imprinting was observed using an optical microscope (manufactured by Olympus, STM6-LM), and the peeling failure of the pattern was evaluated based on the following criteria.
  • a composition for forming an underlayer film shown in the following table was spin-coated on a silicon wafer, heated for 1 minute using a hot plate at 220 ° C., and the solvent was dried to form an underlayer film having a thickness of 5 nm.
  • the surface of the lower layer film was spin-coated with a liquid film forming composition shown in the following table, heated for 1 minute using a hot plate at 100 ° C., and the solvent was dried to obtain a liquid having a film thickness shown in the following table.
  • a film was formed. The thicknesses of the lower layer film and the liquid film were measured by an ellipsometer and an atomic force microscope.
  • a solid film was formed in Comparative Example 4 using the liquid film forming composition W-2.
  • a photocurable composition for imprints temperature-controlled to 25 ° C., as shown in the following table, was applied at 1 pL / nozzle using an inkjet printer DMP-2831, manufactured by FUJIFILM Dymatics. And the droplets were applied to the surface of the liquid film so that the droplets were arranged in a square array at intervals of about 100 ⁇ m.
  • a quartz substrate was pressed against the photocurable composition for imprint on the liquid film to flatten the photocurable composition for imprint.
  • the quartz substrate was peeled off to obtain a flat film.
  • the flat film surface was observed using an optical microscope (Olympus STM6-LM), and the wettability was evaluated according to the following criteria.
  • C Unfilling at the boundary of the inkjet droplet was confirmed over the entire surface of the imprint area.
  • D An area where a flat film was not formed because the ink-jet droplets were not connected to each other was confirmed.
  • Comparative Example 1 in which a polymer containing no aromatic ring was used as the underlayer film-forming composition and Comparative Example 2 in which a polymer containing no polymerizable group was used as the underlayer film-forming composition had insufficient adhesion. there were.
  • Comparative Example 3 in which no liquid film was provided, the wettability was insufficient.
  • Comparative Example 4 in which a solid film was formed instead of the liquid film, had insufficient wettability.
  • Comparative Example 5 using the liquid film forming composition containing no polymerizable compound had insufficient adhesion.
  • ⁇ HSP Hansen solubility parameters
  • substrate 10 laminate for imprint 11: lower film 12: liquid film 13: photocurable composition for imprint 20: mold

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  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)
  • Laminated Bodies (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)

Abstract

La présente invention concerne un corps stratifié d'impression 10 ayant : un film de sous-couche 11 qui est formé à partir d'une composition de formation de film de sous-couche, qui contient un polymère ayant un cycle aromatique et un groupe polymérisable ; un film liquide qui est disposé sur la surface du film de sous-couche et contient un composé polymérisable qui est un liquide à 23 °C et 1 atm ; et une composition de photodurcissement d'impression qui est disposée sur la surface du film liquide 12. La présente invention concerne également un procédé de fabrication d'un corps stratifié d'impression, un procédé de formation d'un motif, et un kit.
PCT/JP2019/035750 2018-09-18 2019-09-11 Corps stratifié d'impression, procédé de fabrication d'un corps stratifié d'impression, procédé de formation de motif et kit WO2020059603A1 (fr)

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WO2022259748A1 (fr) * 2021-06-09 2022-12-15 キヤノン株式会社 Composition durcissable, procédé de formation de film et procédé de fabrication d'article
JP7408821B2 (ja) 2020-08-28 2024-01-05 富士フイルム株式会社 下層膜形成用組成物、カラーフィルタ、カラーフィルタの製造方法、固体撮像素子および画像表示装置

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