Curable composition for imprints, coating film, method for producing film, cured product, method for producing imprint pattern, and method for producing device

Abstract

To provide a cured composition for an imprint small in mold releasing force between an obtained cured material and a mold, a coated film of the composition, a manufacturing method of the film, a cured material of the composition, a manufacturing method of an imprint pattern using the composition, and, a manufacturing method of a device containing the manufacturing method of the imprint pattern.SOLUTION: Provided are a cured composition for imprints comprising organopolysiloxane having a radically polymerizable group, a radical generator, a monovalent hydrocarbon group having 4 to 11 carbon atoms, and a compound having a poly(oxyalkylene) group, wherein in the above monovalent hydrocarbon group, part or all of the hydrogen atoms may be substituted with halogen atoms, a coated film of the composition, a manufacturing method of the film, a cured material of the composition, a manufacturing method of an imprint pattern using the composition, and a manufacturing method of a device including the manufacturing of the imprint pattern.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a curable composition for imprinting, a coating film using the curable composition for imprinting, a method for producing a film, a cured product, a method for producing an imprint pattern, and a method for producing a device.

Background Art

[0002] The imprint method is a technique for transferring a fine pattern to a material by pressing a mold (generally called a mold or a stamper) on which a pattern is formed. Since it is possible to easily produce a precise fine pattern by using the imprint method, applications in various fields have been expected in recent years. In particular, nanoimprint technology for forming a fine pattern at the nano-order level has attracted attention.

[0003] Patent Document 1 describes a curable composition for photoimprinting containing a polymerizable compound (A) containing a silicon atom in the molecule, a photopolymerization initiator (B), and an additive (C), wherein the additive (C) is a compound having a specific structure. Patent Document 2 describes a curable composition for imprinting containing a monofunctional polymerizable compound having a specific structure, a photopolymerization initiator, and a release agent having a specific structure.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] As imprinting methods, methods called thermal imprinting method and curable imprinting method have been proposed based on their transfer methods. In the thermal imprinting method, a mold is pressed onto a thermoplastic resin heated above the glass transition temperature (hereinafter sometimes referred to as "Tg"), and after cooling, the mold is released to form a fine pattern. Although this method allows selection of various materials, it has problems such as the need for high pressure during pressing and difficulty in forming fine patterns due to a decrease in dimensional accuracy caused by thermal shrinkage, etc. On the other hand, in the curable imprinting method, for example, after photocuring or thermocuring in a state where a mold is pressed against a film formed from a curable composition for imprinting, the mold is released. Since imprinting is performed on an uncured material, some or all of the application of high pressure and high-temperature heating can be omitted, and it is possible to easily produce a fine pattern. Also, since the dimensional variation before and after curing is small, there is an advantage that a fine pattern can be formed with high accuracy. Recently, new developments such as a nanoimprinting method that combines the advantages of both the thermal imprinting method and the curable imprinting method, and a reversible imprinting method for producing a three-dimensional laminated structure have also been reported.

[0006] In the curable imprinting method, a curable composition for imprinting is applied onto a support (with an adhesion treatment performed on the surface if necessary) to form a film, and then a mold made of a light-transmissive material such as quartz is pressed against it. The curable composition for imprinting is cured by light irradiation or heating in a state where the mold is pressed against it, and then the mold is released to produce a cured product onto which the target pattern has been transferred. Examples of methods for applying a curable composition for imprinting onto a support include spin coating method and inkjet method. The spin coating method is an application method with excellent productivity in terms of high throughput. In addition, the method of performing microfabrication using the transferred imprint pattern as a mask is called nanoimprint lithography (NIL), and development is underway as a next-generation lithography technology to replace the current ArF immersion process. Therefore, the curable composition for imprint used in NIL, like EUV resists, must be able to resolve ultra-fine patterns of 20 nm or less and have high etching resistance as a mask when microfabricating the object to be processed. Specific examples of curable compositions for imprint assumed to be used as a mask include those described in Japanese Patent No. 5426814, JP-A-2015-009171, JP-A-2015-185798, JP-A-2015-070145, JP-A-2015-128134, and the like.

[0007] In the imprint method, for the purpose of suppressing deformation and breakage of the cured product and damage to the mold, it is required that the force (release force) necessary for peeling the mold from the cured product of the curable composition for imprint be small. An object of the present invention is to provide a curable composition for imprint in which the release force between the obtained cured product and the mold is small, a coating film of the curable composition for imprint, a method for producing the film, a cured product of the curable composition for imprint, a method for producing an imprint pattern using the curable composition for imprint, and a method for producing a device including the method for producing the imprint pattern.

Means for Solving the Problems

[0008] Typical embodiments of the present invention are shown below. <1> An organopolysiloxane having a radically polymerizable group, a radical generator, and a compound having a monovalent hydrocarbon group having 4 to 11 carbon atoms and a poly(oxyalkylene) group, wherein part or all of the hydrogen atoms of the monovalent hydrocarbon group may be substituted with halogen atoms, a curable composition for imprint. <2> The curable composition for imprinting according to <1>, wherein the repeating number of the oxyalkylene group in the poly(oxyalkylene) group is 4 to 20. <3> The curable composition for imprinting according to any one of <1> or <2>, wherein the number of carbon atoms of the oxyalkylene group in the poly(oxyalkylene) group is 2 or 3. <4> The curable composition for imprinting according to any one of <1> to <3>, wherein the monovalent hydrocarbon group is a linear alkyl group or a branched alkyl group. <5> The curable composition for imprinting according to any one of <1> to <4>, wherein the compound has two monovalent hydrocarbon groups. <6> The curable composition for imprinting according to any one of <1> to <5>, wherein the monovalent hydrocarbon group is directly bonded to the poly(oxyalkylene) group. <7> The curable composition for imprinting according to any one of <1> to <6>, wherein the monovalent hydrocarbon group is an unsubstituted hydrocarbon group. <8> The curable composition for imprinting according to any one of <1> to <7>, wherein the content of the poly(oxyalkylene) group in the compound is 30 to 90% by mass. <9> The curable composition for imprinting according to any one of <1> to <8>, wherein the compound is a compound represented by the following formula (C-1).

Chemical formula

Advantages of the Invention

[0009] According to the present invention, there are provided a curable composition for imprinting having a small release force between the obtained cured product and the mold, a coating film of the curable composition for imprinting, a method for manufacturing the film, a cured product of the curable composition for imprinting, a method for manufacturing an imprint pattern using the curable composition for imprinting, and a method for manufacturing a device including the method for manufacturing the imprint pattern.

Embodiments for Carrying Out the Invention

[0010] Hereinafter, the content of the present invention will be described in detail. In this specification, "~" is used to mean including the numerical values described before and after it as a lower limit value and an upper limit value. In this specification, "(meth)acrylate" represents acrylate and methacrylate, "(meth)acrylic" represents acrylic and methacrylic, and "(meth)acryloyl" represents acryloyl and methacryloyl. "(meth)acryloyloxy" represents acryloyloxy and methacryloyloxy. In this specification, "imprinting" preferably refers to pattern transfer of a size of 1 nm to 10 mm, and more preferably refers to pattern transfer of a size of approximately 10 nm to 100 μm (nanoimprinting). In the notation of groups (atomic groups) in this specification, notations without indicating substitution or non-substitution include both those without substituents and those with substituents. For example, the term "alkyl group" includes not only an alkyl group without substituents (unsubstituted alkyl group) but also an alkyl group with substituents (substituted alkyl group). In this specification, "light" includes not only light with wavelengths in the regions of ultraviolet, near-ultraviolet, far-ultraviolet, visible, infrared, etc., electromagnetic waves, but also radiation. Radiation includes, for example, microwaves, electron beams, extreme ultraviolet rays (EUV), and X-rays. Also, laser light such as 248 nm excimer laser, 193 nm excimer laser, 172 nm excimer laser, etc. can be used. These lights may be monochromatic light (single-wavelength light) passing through an optical filter, or light with different wavelengths (composite light). In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) are defined as polystyrene-converted values according to gel permeation chromatography (GPC measurement). In this specification, the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) can be determined, for example, by using HLC-8220 (manufactured by Tosoh Corporation) and using guard column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, or TSKgel Super HZ2000 (manufactured by Tosoh Corporation) as columns. Unless otherwise specified, the eluent is measured using THF (tetrahydrofuran). Also, unless otherwise specified, detection is performed using a detector with a UV wavelength of 254 nm. In this specification, unless otherwise specified, the temperature is 23 °C, the atmospheric pressure is 101325 Pa (1 atm), and the relative humidity is 50% RH. In this specification, the term "step" includes not only independent steps but also cases where it cannot be clearly distinguished from other steps, as long as the intended action of the step is achieved. In this specification, the total solid content refers to the total mass of the components obtained by removing the solvent from all the components of the composition. Also, in this specification, the solid content concentration is the mass percentage of the components other than the solvent with respect to the total mass of the composition. In this specification, a combination of preferred embodiments is a more preferred embodiment.

[0011] The curable composition for imprinting according to the first aspect of the present invention contains an organopolysiloxane having a radically polymerizable group, a radical generator, and a compound having a monovalent hydrocarbon group having 4 to 11 carbon atoms and a poly(oxyalkylene) group, and in the above monovalent hydrocarbon group, part or all of the hydrogen atoms may be substituted by halogen atoms. The curable composition for imprinting according to the second aspect of the present invention contains an organopolysiloxane having a radically polymerizable group, a radical generator, and a compound represented by the following formula (C-2). [Chemical formula] In formula (C-2), R 21 and R 22 are each independently a monovalent hydrocarbon group, and L 21 are each independently an alkylene group, and n2 represents an integer of 2 or more. Hereinafter, when simply described as "the composition of the present invention" or "the curable composition for imprinting of the present invention", it shall refer to both the curable composition for imprinting according to the first aspect of the present invention and the curable composition for imprinting according to the second aspect of the present invention. Also, the monovalent hydrocarbon group having 4 to 11 carbon atoms and the compound having a poly(oxyalkylene) group in the curable composition for imprinting according to the first aspect are also referred to as "specific compound 1". Furthermore, the compound represented by formula (C-2) in the curable composition for imprinting according to the second aspect is also referred to as "specific compound 2". Hereinafter, when simply described as "specific compound", it shall refer to both specific compound 1 and specific compound 2.

[0012] The curable composition for imprinting of the present invention has a small release force between the obtained cured product and the mold. Although the mechanism by which the above effect is obtained is unclear, it is presumed as follows. The curable composition for imprinting according to the first aspect of the present invention contains a specific compound 1. The curable composition for imprinting according to the second aspect of the present invention contains a specific compound 2. Here, since the poly(oxyalkylene) group contained in the specific compound 1 or the specific compound 2 is likely to adsorb to the mold, the above specific compound is unevenly distributed on the surface of the imprint pattern after curing. In particular, since the specific compound 1 has a monovalent hydrocarbon group having 4 to 11 carbon atoms and the specific compound 2 has two monovalent hydrocarbon groups, it is considered that the release agent is likely to segregate on the template surface due to the compatibility with the organopolysiloxane having a radical polymerizable group. As a result, the monovalent hydrocarbon group having 4 to 11 carbon atoms in the specific compound 1 or the R 21 and R 22 which is a monovalent hydrocarbon group in the specific compound 2 is also unevenly distributed on the surface of the imprint pattern. As a result, it is considered that the force required for releasing the mold and the imprint pattern can be reduced and the release force can be decreased due to reasons such as a decrease in the surface free energy of the imprint pattern. In addition, when the carbon number becomes 11 or more, the composition ratio of hydrocarbons increases, so the pattern becomes soft, and there are cases where pattern collapse or peeling is likely to occur. In addition, by containing the specific compound 1 or the specific compound 2, the composition ratio of hydrocarbons increases, so it is considered that the cleanability in SPM (sulfuric acid-hydrogen peroxide mixture) cleaning is improved. Hereinafter, the present invention will be described in detail.

[0013] <Organopolysiloxane having a radical polymerizable group> The curable composition for imprinting of the present invention contains an organopolysiloxane having a radical polymerizable group.

[0014] [Radical polymerizable group] As the radical polymerizable group in the organopolysiloxane having a radical polymerizable group, an ethylenically unsaturated bond-containing group is preferable, and examples thereof include a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinyl group, a vinyloxy group, an allyl group, a maleimide group, and a group in which a vinyl group is directly bonded to an aromatic ring (for example, a vinylphenyl group). A (meth)acrylamide group or a (meth)acryloxy group is more preferable, an acrylamide group or an acryloxy group is still more preferable, and an acryloxy group is particularly preferable.

[0015] If the radical polymerizable group value is at least the above lower limit, the elastic modulus at the time of curing is in an appropriate range, and it is considered that the releasability is excellent. On the other hand, if the polymerizable group value is at most the above upper limit, the crosslink density of the cured product pattern is in an appropriate range, and it is considered that the resolution of the transfer pattern is excellent.

[0016] [Organopolysiloxane] The organopolysiloxane refers to a compound containing a siloxane bond (-Si-O-Si-O-Si-) as a skeleton and having an organic group bonded to the silicon atom. In the above organic group, it is preferable that the atom bonded to the silicon atom is a carbon atom. To a part of the silicon atoms, atoms or groups other than organic groups (for example, a hydrogen atom, a hydroxy group, a hydrolyzable group, etc.) may be bonded. The hydrolyzable group is a group that can react with water to become a hydroxy group, and examples thereof include a halogen atom (such as a chlorine atom), an alkoxy group, an acyl group, and an amino group. As the organic group, a hydrocarbon group is preferable, and an aromatic hydrocarbon group or a saturated aliphatic hydrocarbon group is more preferable. The above hydrocarbon group, aromatic hydrocarbon group, and saturated aliphatic hydrocarbon group may each further have a substituent. Examples of the substituent include a halogen atom, an alkoxy group, an aryloxy group, and a group containing the above radical polymerizable group.

[0017] The organopolysiloxane having a radically polymerizable group is preferably a compound having at least one of the siloxane structure of the D unit represented by the following formula (S1) and the siloxane structure of the T unit represented by the formula (S2). [Chemical formula] In formula (S1) or formula (S2), R S1 ~R S3 each independently represents a hydrogen atom or a monovalent substituent, and * each independently represents a bonding site with another structure. R S1 ~R S3 are each independently preferably a monovalent substituent. Examples of the monovalent substituent include an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms) or an aliphatic hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms). Among them, a cyclic or chain (linear or branched) alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms) or a group containing a polymerizable group is preferable.

[0018]

[0019] [Chemical formula]

[0020] The organopolysiloxane having a radically polymerizable group is preferably a reaction product of a silicone resin and a compound having a polymerizable group. As the silicone resin, a reactive silicone resin is preferable. Examples of the reactive silicone resin include modified silicone resins having the silicone skeletons described above, such as monoamine-modified silicone resins, diamine-modified silicone resins, special amino-modified silicone resins, epoxy-modified silicone resins, alicyclic epoxy-modified silicone resins, carbinol-modified silicone resins, mercapto-modified silicone resins, carboxy-modified silicone resins, hydrogen-modified silicone resins, amino-polyether-modified silicone resins, epoxy-polyether-modified silicone resins, epoxy-aralkyl-modified silicone resins, and the like. As the compound having the polymerizable group, a compound having a polymerizable group and a group capable of reacting with an alkoxysilyl group or a silanol group is preferable, and a compound having a polymerizable group and a hydroxy group is more preferable. When the above-described modified silicone resin is used as the silicone resin, as the compound having the polymerizable group, a compound having a group that reacts with the polymerizable group and an amino group, an epoxy group, a mercapto group, a carboxy group, etc. contained in the above-described modified silicone resin may be used. Preferable embodiments of the polymerizable group in the compound having the polymerizable group are the same as the preferable embodiments of the polymerizable group in the above-described polymerizable compounds. Among these, as the compound having the polymerizable group, hydroxyalkyl (meth) acrylate is preferable, and 2-hydroxyethyl (meth) acrylate is more preferable. More specifically, it is preferably a reaction product of a compound having a polymerizable group and a group capable of reacting with an alkoxysilyl group or a silanol group (for example, a hydroxy group) and a silicone resin having an alkoxysilyl group or a silanol group.

[0021] The weight average molecular weight of the organopolysiloxane having a radical polymerizable group is preferably from 500 to 10,000, more preferably from 800 to 5,000, and still more preferably from 1,000 to 3,000.

[0022] In the organopolysiloxane having a radically polymerizable group, the number of radically polymerizable groups is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more per molecule. The upper limit is preferably 50 or less, more preferably 40 or less, even more preferably 30 or less, and still more preferably 20 or less.

[0023] The viscosity of the organopolysiloxane having a radically polymerizable group at 23°C is preferably 100 mPa·s or more, more preferably 120 mPa·s or more, and even more preferably 150 mPa·s or more. The upper limit of the viscosity is preferably 2,000 mPa·s or less, more preferably 1,500 mPa·s or less, even more preferably 1,200 mPa·s or less. In this specification, unless otherwise specified, the viscosity is the value measured using an E-type rotational viscometer RE85L manufactured by Toki Sangyo Co., Ltd., a standard cone and rotor (1°34’×R24), with the sample cup temperature adjusted to 23°C. Other details regarding the measurement comply with JIS Z8803:2011. Two samples are prepared for each level and measured three times each. The arithmetic mean value of a total of six measurements is adopted as the evaluation value.

[0024] 〔Other polymerizable compounds〕 The curable composition for imprinting of the present invention may further contain other polymerizable compounds different from the above-described organopolysiloxane having a radically polymerizable group. The other polymerizable compound is preferably a polyfunctional polymerizable compound having two or more polymerizable groups. The number of polymerizable groups of the other polymerizable compound is preferably 2 or more per molecule. The upper limit is preferably 4 or less, more preferably 3 or less, and even more preferably 2. The polymerizable group in the other polymerizable compound is not particularly limited, and examples thereof include a radically polymerizable group, a cyclic ether group (epoxy group, glycidyl group, oxetanyl group), etc., and a radically polymerizable group is preferred. The polymerizable group defined here is referred to as Qp. Preferred embodiments of the radically polymerizable group in other polymerizable compounds are the same as those of the radically polymerizable group in the organopolysiloxane having the above-described radically polymerizable group.

[0025] As an example of other polymerizable compounds, compounds represented by the following formula are exemplified.

Chemical formula

[0026] In the formula, R 21 is a q-valent organic group, R 22 is a hydrogen atom or a methyl group, and q is an integer of 2 or more. q is preferably an integer of 2 or more and 7 or less, more preferably an integer of 2 or more and 4 or less, still more preferably 2 or 3, and even more preferably 2. R 21 is preferably a 2- to 7-valent organic group, more preferably a 2- to 4-valent organic group, still more preferably a 2- or 3-valent organic group, and even more preferably a 2-valent organic group. R 21 is preferably a hydrocarbon group having at least one structure of linear, branched, and cyclic. The number of carbon atoms of the hydrocarbon group is preferably 2 to 20, and more preferably 2 to 10. R 21 When it is a divalent organic group, it is preferably an organic group represented by the following formula (1-2).

Chemical formula

[0027] R 9is preferably a single bond, a linking group selected from the following formulas (9-1) to (9-10), or a combination thereof. Among them, it is preferably a linking group selected from formulas (9-1) to (9-3), (9-7), and (9-8).

[0028]

Chemical formula

[0029] R 101 ~R 117 is an arbitrary substituent. Among them, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms), an aralkyl group (preferably having 7 to 21 carbon atoms, more preferably 7 to 15 carbon atoms, and even more preferably 7 to 11 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms), a thienyl group, a furyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, a (meth)acryloyloxyalkyl group (the alkyl group preferably has 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms) are preferred. R 101 and R 102 、R 103 and R 104 、R 105 and R 106 、R 107 and R 108 、R 109 and R 110 、When there are multiple Rs 111 、When there are multiple Rs 112 、When there are multiple Rs 113 、When there are multiple Rs 114 、When there are multiple Rs 115 、When there are multiple Rs 116 、When there are multiple Rs 117 may combine with each other to form a ring. Ar is 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 specifically, a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, a fluorenediyl group can be mentioned. hCy 1is a heterocyclic group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 2 to 5 carbon atoms), and a 5-membered ring or 6-membered ring is more preferable. hCy 1 Specific examples of the heterocyclic ring constituting 1 include the aromatic heterocyclic ring hCy, pyrrolidone ring, tetrahydrofuran ring, tetrahydropyran ring, morpholine ring, etc. described below. Among them, thiophene ring, furan ring, and dibenzofuran ring are preferable. n and m are natural numbers of 100 or less, preferably 1 to 12, more preferably 1 to 6, still more preferably 1 to 3. p is 0 or more and an integer equal to or less than the maximum number substitutable for each ring. The upper limit value is preferably independently in each case equal to or less than half of the maximum number of substituents, more preferably 4 or less, still more preferably 2 or less.

[0030] Also, other polymerizable compounds preferably have a polymerizable group value of 150 or more as defined above, more preferably 160 or more, still more preferably 190 or more, and even more preferably 240 or more. The upper limit is preferably 2,500 or less, more preferably 1,800 or less, still more preferably 1,000 or less.

[0031] Other polymerizable compounds preferably have a cyclic structure. Examples of the cyclic structure include the aromatic hydrocarbon ring aCy, aromatic heterocyclic ring hCy, and alicyclic ring fCy described below.

[0032] In addition, examples of other polymerizable compounds include compounds containing a cyclic structure (ring-containing compounds), dendrimer-type compounds, etc.

[0033] <<<Ring-containing compound>>> Examples of the cyclic structure of the compound containing a ring (ring-containing compound) include an aromatic ring and an alicyclic ring. Examples of the aromatic ring include an aromatic hydrocarbon ring and an aromatic heterocyclic ring. As the aromatic hydrocarbon ring, those having 6 to 22 carbon atoms are preferred, 6 to 18 are more preferred, and 6 to 10 are even more preferred. Specific examples of the aromatic hydrocarbon ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, phenalene ring, fluorene ring, benzocyclooctene ring, acenaphthylene ring, biphenylene ring, indene ring, indane ring, triphenylene ring, pyrene ring, chrysene ring, perylene ring, tetrahydronaphthalene ring and the like. Among them, benzene ring or naphthalene ring is preferred, and benzene ring is more preferred. The aromatic ring may have a structure in which a plurality are linked, for example, biphenyl structure, diphenylalkane structure (for example, 2,2-diphenylpropane). (The aromatic hydrocarbon ring defined here is referred to as aCy) As the aromatic heterocyclic ring, those having 1 to 12 carbon atoms are preferred, 1 to 6 are more preferred, and 1 to 5 are even more preferred. Specific examples thereof include thiophene ring, furan ring, dibenzofuran ring, pyrrole ring, imidazole ring, benzimidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, thiadiazole ring, oxadiazole 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, phenoxathiin ring, phenoxazine ring and the like. (The aromatic heterocyclic ring defined here is referred to as hCy) The alicyclic ring preferably has 3 to 22 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. Specifically, examples of the aliphatic hydrocarbon ring include a cyclopropane ring, a cyclobutane ring, a cyclobutene ring, a cyclopentane ring, a cyclohexane ring, a cyclohexene ring, a cycloheptane ring, a cyclooctane ring, a dicyclopentadiene ring, a spirodecane ring, a spirononane ring, a tetrahydrodicyclopentadiene ring, an octahydronaphthalene ring, a decahydronaphthalene ring, a hexahydroindane ring, a bornane ring, a norbornane ring, a norbornene ring, an isobornane ring, a tricyclodecane ring, a tetracyclododecane ring, an adamantane ring, and the like. Examples of the aliphatic heterocyclic ring include a pyrrolidine ring, an imidazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring, an oxirane ring, an oxetane ring, an oxolane ring, an oxane ring, a dioxane ring, and the like. (The alicyclic ring defined herein is referred to as fCy.)

[0034] In the present invention, when the light-transmissive polymerizable compound is a ring-containing compound, it is preferably a compound containing an aromatic hydrocarbon ring, and more preferably a compound having a benzene ring. For example, a compound having the structure of the following formula C-1 can be mentioned.

[0035] [Chemical formula] In the formula, Ar represents the above aromatic hydrocarbon ring or aromatic heterocyclic ring. L 1 and L 2Each is independently a single bond or a linking group. Examples of the linking group include an oxygen atom (oxy group), a carbonyl group, an amino group, an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 3 carbon atoms), or a group combining these. Among them, a (poly)alkyleneoxy group is preferable. The (poly)alkyleneoxy group may be one alkyleneoxy group or a group in which a plurality of them are repeatedly linked. Also, the order of the alkylene group and the oxy group is not limited. The repeating number of the alkyleneoxy group is preferably 1 to 24, more preferably 1 to 12, even more preferably 1 to 6. Further, in the relationship of the connection between the (poly)alkyleneoxy group and the ring Ar or the polymerizable group Q serving as the parent nucleus, an alkylene group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 6 carbon atoms) may be interposed. Therefore, it may be a (poly)alkyleneoxy = alkylene group. R 3 is an arbitrary substituent, and examples thereof include an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, even more preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, even more preferably 6 to 10 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, even more preferably 7 to 11 carbon atoms), a hydroxy group, a carboxy group, an alkoxy group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 6 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, even more preferably 2 to 3 carbon atoms), and an aroyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, even more preferably 7 to 11 carbon atoms). L 3 is a single bond or a linking group. Examples of the linking group include the above L 1 , L 2 and the like. n3 is preferably 3 or less, more preferably 2 or less, even more preferably 1 or less, and particularly preferably 0. Q 1 and Q 2Each is independently a polymerizable group, and examples of the polymerizable group Qp are preferred. In the ring-containing compound, as the number of side chains having a polymerizable group increases, it becomes possible to form a strong crosslinked structure during curing, and the resolution tends to improve. From this viewpoint, nq is preferably 2 or more. As the upper limit, it is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. Similarly, from the viewpoint of easily forming a uniform crosslinked structure, when a group or substituent containing a polymerizable group is introduced into the cyclic structure, it is preferable that the substituents are arranged in series.

[0036] <<<Dendrimer-type compound>>> The light-transmissive polymerizable compound may be a dendrimer-type compound. A dendrimer means a dendritic polymer having a structure that branches regularly from the center. A dendrimer is composed of a central molecule (trunk) called a core and a side chain part (branch) called a dendron. Although a fan-shaped compound is general as a whole, a dendrimer in which the dendron spreads in a semi-circular or circular shape may also be used. A group having a polymerizable group can be introduced into the dendron part of this dendrimer (for example, the terminal part away from the core) to obtain a polymerizable compound. If a (meth)acryloyl group is used as the polymerizable group to be introduced, a dendrimer-type polyfunctional (meth)acrylate can be obtained. The preferable range of the number of polymerizable groups in the dendrimer-type compound has already been described. Regarding the dendrimer-type compound, for example, the matters disclosed in Japanese Patent No. 5512970 can be referred to, and the description is incorporated herein by reference.

[0037] Examples of other polymerizable compounds include the compounds described in paragraphs 0017 to 0024 and Examples of JP-A-2014-90133, the compounds described in paragraphs 0024 to 0089 of JP-A-2015-9171, the compounds described in paragraphs 0023 to 0037 of JP-A-2015-70145, and the compounds described in paragraphs 0012 to 0039 of WO16 / 152597, and these are incorporated herein by reference.

[0038] Other polymerizable compounds may be contained in the curable composition for imprinting in an amount of 10% by mass or more. In relation to the light-transmissive polymerizable compound, it is practical that the upper limit is less than 30% by mass. One or a plurality of other polymerizable compounds may be used. When a plurality of them are used, the total amount thereof falls within the above range.

[0039] <Radical generator> The curable composition for imprinting of the present invention contains a radical generator. The radical generator is preferably a thermal radical generator or a photo radical generator, and a photo radical generator is preferable from the viewpoint that it can be used in the photoimprint method. Any photo radical generator can be used as long as it generates an active species that polymerizes the above-mentioned polymerizable compound upon light irradiation. In the present invention, a plurality of types of photo radical generators may be used in combination.

[0040] The content of the radical generator used in the present invention is, for example, 0.01 to 15% by mass, preferably 0.1 to 12% by mass, and more preferably 0.2 to 7% by mass with respect to the total solid content of the curable composition for imprinting. When two or more types of radical generators are used, it is preferable that the total amount thereof falls within the above range. When the content of the photo radical generator is 0.01% by mass or more, the sensitivity (rapid curability), resolution, line edge roughness, and film strength tend to improve, which is preferable. On the other hand, when the content of the radical generator is 15% by mass or less, the light transmittance, coloring property, handleability, etc. tend to improve, which is preferable.

[0041] Regarding the thermal radical generator, the components described in JP-A-2013-036027, JP-A-2014-090133, and JP-A-2013-189537 can be used. Regarding the content and the like, the descriptions in the above-mentioned publications can also be referred to.

[0042] As the photo radical generator used in the present invention, for example, commercially available initiators can be used. As examples thereof, for example, those described in paragraph number 0091 of JP-A-2008-105414 can be preferably employed. Among these, acetophenone-based compounds, phenylglyoxylate-based compounds, acylphosphine oxide-based compounds, and oxime ester-based compounds are preferable from the viewpoints of curing sensitivity and absorption characteristics. Preferable examples of the acetophenone-based compound include hydroxyacetophenone-based compounds, dialkoxyacetophenone-based compounds, and aminoacetophenone-based compounds. Preferable examples of the hydroxyacetophenone-based compound include Irgacure (registered trademark) 2959 (1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one), Irgacure (registered trademark) 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure (registered trademark) 500 (1-hydroxycyclohexyl phenyl ketone, benzophenone), and Darocure (registered trademark) 1173 (2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), which are available from BASF. Preferable examples of the dialkoxyacetophenone-based compound include Irgacure (registered trademark) 651 (2,2-dimethoxy-1,2-diphenylethane-1-one), which is available from BASF. Preferable examples of the aminoacetophenone-based compound include Irgacure (registered trademark) 369 (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one), Irgacure (registered trademark) 379 (EG) (2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)butan-1-one), and Irgacure (registered trademark) 907 (2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone), which are available from BASF. Preferable examples of the phenylglyoxylate-based compound include Irgacure (registered trademark) 754 and Darocure (registered trademark) MBF, which are available from BASF. As an acylphosphine oxide-based compound (a polymerization initiator having an acylphosphine oxide group in the molecule), preferably Irgacure® 819 (bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide), Irgacure® 1800 (bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide), which are available from BASF, Lucirin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide), and Lucirin TPO-L (2,4,6-trimethylbenzoylphenylethoxyphosphine oxide) are mentioned. As an oxime ester-based compound, preferably Irgacure® OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime)), Irgacure® OXE02 (ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime)), which are available from BASF, are mentioned.

[0043] <Specific compound> [Specific compound 1] The curable composition for imprinting according to the first aspect of the present invention contains Specific compound 1. Specific compound 1 has a monovalent hydrocarbon group having 4 to 11 carbon atoms and a poly(oxyalkylene) group.

[0044] -Poly(oxyalkylene) group- The poly(oxyalkylene) group in Specific compound 1 is a group in which two or more oxyalkylene groups are directly bonded. The repeating number of the oxyalkylene group in the above poly(oxyalkylene) group is preferably 4 to 40, more preferably 4 to 20, and still more preferably 4 to 15. Each oxyalkylene group contained in the poly(oxyalkylene) group may have the same or different structures. When the poly(oxyalkylene) group contains two or more oxyalkylene groups with different structures, for example, the poly(oxyalkylene) group may be a random combination of two or more oxyalkylene groups with different structures, or may contain a block formed by an oxyalkylene group of one structure and a block formed by an oxyalkylene group of another structure, and the arrangement of the oxyalkylene groups is not particularly limited. The number of carbon atoms of the alkylene group in the poly(oxyalkylene) group is preferably 2 to 10, more preferably 2 to 4, and even more preferably 2 or 3.

[0045] The poly(oxyalkylene) group preferably contains an oxyalkylene group represented by the following formula (OA-1), and more preferably is a group composed of the oxyalkylene group represented by the following formula (OA-1).

Chemical formula

[0046] The poly(oxyalkylene) group is preferably a poly(ethyleneoxy) group, a poly(ethyleneoxy-ran-propyleneoxy) group, or a poly(ethyleneoxy-block-propyleneoxy) group. Poly(A-ran-B) indicates that A and B are randomly bonded, and poly(A-block-B) indicates that a block formed by A and a block formed by B are bonded.

[0047] The content of the poly(oxyalkylene) group in the specific compound 1 is preferably 30 to 90% by mass, more preferably 40 to 85% by mass, and even more preferably 50 to 75% by mass.

[0048] -monovalent hydrocarbon group having 4 to 11 carbon atoms- The monovalent hydrocarbon group having 4 to 11 carbon atoms in Specific Compound 1 may be either an aromatic hydrocarbon group or an aliphatic hydrocarbon group, but is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group. Further, the above-mentioned aliphatic hydrocarbon group or alkyl group may be linear, branched, cyclic, or any structure represented by a combination thereof, but is preferably linear or branched. Among these, the monovalent hydrocarbon group is preferably a linear alkyl group or a branched alkyl group.

[0049] The number of carbon atoms of the above monovalent hydrocarbon group is 4 to 11, preferably 5 to 10, and more preferably 6 to 10.

[0050] Specific Compound 1 may have only one of the above monovalent hydrocarbon groups or may have two or more thereof. The number of the above monovalent hydrocarbon groups in Specific Compound 1 is preferably 1 or 2. Also, the embodiment having two of the above monovalent hydrocarbon groups is one of the preferred embodiments of the present invention. The above monovalent hydrocarbon group is preferably directly bonded to the above poly(oxyalkylene) group.

[0051] A part or all of the hydrogen atoms of the above monovalent hydrocarbon group may be substituted by a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., a fluorine atom or a chlorine atom is preferred, and a fluorine atom is more preferred. Also, the embodiment in which the above monovalent hydrocarbon group is an unsubstituted hydrocarbon group is one of the preferred embodiments of the present invention.

[0052] Specific examples of the above monovalent hydrocarbon group include, for example, the following groups, but are not limited thereto. For example, linear alkyl groups having 4 to 11 carbon atoms and branched alkyl groups having 4 to 11 carbon atoms other than those described below can also be used. In the following structures, * represents a bonding site with other structures.

Chemical formula

[0053] - the compound represented by formula (C-1)- Specific compound 1 is preferably a compound represented by the following formula (C-1).

Chemical formula

[0054] In formula (C-1), R 11 and R 12 each independently represents a hydrogen atom or a monovalent organic group, and at least one of R 11 and R 12 is a monovalent organic group having 4 to 11 carbon atoms. R 11 and R 12 The preferred embodiments of the monovalent hydrocarbon group having 4 to 11 carbon atoms in are the same as the preferred embodiments of the monovalent hydrocarbon group having 4 to 11 carbon atoms in the above-mentioned specific compound 1. R 11 and R 12 Examples of the monovalent organic group having 4 to 11 carbon atoms in include hydrocarbon groups having 1 to 3 carbon atoms and the like. R 11 and R 12 are preferably both monovalent hydrocarbon groups having 4 to 11 carbon atoms, or one is a monovalent hydrocarbon group having 4 to 11 carbon atoms and the other is a hydrogen atom.

[0055] In formula (C-1), L 11 is preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, and even more preferably an ethylene group or a propylene group. In formula (C-1), n1 is preferably 4 or more, more preferably 5 or more. Further, n1 is preferably 40 or less, and even more preferably 20 or less.

[0056] 〔Specific Compound 2〕 The curable composition for imprinting according to the second aspect of the present invention contains Specific Compound 2. Specific Compound 2 is a compound represented by the following formula (C-2).

Chemical formula

[0057] In formula (C-2), the monovalent hydrocarbon groups in R 21 and R 22 may each independently be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, but is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group. Further, the above aliphatic hydrocarbon group or alkyl group may have any of a linear, branched, cyclic, or a structure represented by a combination thereof, but is preferably linear or branched. Among these, the monovalent hydrocarbon group is preferably a linear alkyl group or a branched alkyl group.

[0058] R 21 and R 22 The number of carbon atoms of the monovalent hydrocarbon groups in is preferably 1 to 20, more preferably 4 to 11, still more preferably 5 to 10, and particularly preferably 6 to 10.

[0059] R 21 and R 22The monovalent hydrocarbon group in [compound] may have some or all of the hydrogen atoms substituted by halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., with a fluorine atom or a chlorine atom being preferred, and a fluorine atom being more preferred. In addition, the aspect where the monovalent hydrocarbon group is an unsubstituted hydrocarbon group is also one of the preferred aspects of the present invention.

[0060] Also, R 21 and R 22 The aspect where at least one of them is a monovalent hydrocarbon group having 4 to 11 carbon atoms is also preferred. The preferred aspects of the monovalent hydrocarbon group having 4 to 11 carbon atoms are the same as the preferred aspects of the monovalent hydrocarbon group having 4 to 11 carbon atoms in the above-mentioned specific compound 1. In formula (C-2), the preferred aspects of L 21 and n2 are the same as the preferred aspects of L 11 and n1 in formula (C-1), respectively.

[0061] 〔Specific Compound〕 The specific compound preferably has a weight average molecular weight of 300 to 1000, more preferably 350 to 900, and still more preferably 400 to 800.

[0062] The ClogP value of the specific compound is preferably 1 to 10, more preferably 2 to 8, and still more preferably 3 to 7. In addition, the absolute value of the difference between the CLogP value of the specific compound and the CLogP value of the organopolysiloxane having a radically polymerizable group is preferably 1 to 5, more preferably 1 to 4, and still more preferably 1 to 3. In this specification, "ClogP" means logP (log[water / octanol partition coefficient]) predicted by calculation from the chemical structure. The ClogP in this specification uses the value calculated by Chem Draw Pro 20.1.

[0063] The specific compound preferably has a hydroxy group. When the specific compound has a hydroxy group, the number of hydroxy groups in the specific compound is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 to 2.

[0064] The specific compound preferably does not have a radically polymerizable group so that it is likely to be unevenly distributed on the surface during curing. Examples of the radically polymerizable group include the same groups as those in the organopolysiloxane having the above-mentioned radically polymerizable group.

[0065] Specific examples of the specific compound include C-1 to C-20 and 22 in the examples described later, but are not limited thereto.

[0066] The content of the specific compound is preferably 0.5 to 10% by mass, more preferably 0.6 to 5% by mass, and even more preferably 0.7 to 3% by mass with respect to the total solid content of the composition. Also, the content of the specific compound with respect to the total mass of the above organopolysiloxane is preferably 0.5 to 10% by mass, more preferably 0.6 to 5% by mass, and even more preferably 0.7 to 3% by mass.

[0067] <Release agent> The curable composition for imprinting of the present invention may further contain a release agent. However, compounds corresponding to the above-mentioned specific compounds shall not correspond to the release agent. The content of the release agent is 0.1% by mass or more, preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and even more preferably 0.6% by mass or more with respect to the total solid content of the composition. The upper limit is less than 1.0% by mass, preferably 0.9% by mass or less, and more preferably 0.85% by mass or less. By setting the content of the release agent to the above lower limit or more, the releasability becomes good, and peeling of the cured film and mold damage during release can be prevented. Also, by setting it to the above upper limit or less, an excessive decrease in the pattern strength during curing due to the influence of the release agent can be avoided, and good resolution can be achieved. The release agent may be used alone or in combination of two or more. When using two or more, the total amount thereof shall be within the above range. The type of the release agent is not particularly limited, but preferably, it has a function of segregating at the interface with the mold and effectively promoting the release from the mold. In the present invention, it is preferable that the release agent substantially does not contain a fluorine atom and a silicon atom. Substantially not containing means that the total amount of the fluorine atom and the silicon atom is 1% by mass or less of the release agent, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and still more preferably 0.01% by mass or less. By using a release agent that substantially does not contain a fluorine atom and a silicon atom, from the viewpoint of making the curable composition for imprinting excellent in workability resistance to etching or the like while realizing high releasability of its film, it is preferable. Specifically, the release agent used in the present invention is preferably a surfactant. Alternatively, it is preferably an alcohol compound having at least one hydroxy group at the terminal or a compound having a (poly)alkylene glycol structure in which the hydroxy group is etherified ((poly)alkylene glycol compound). The surfactant and the (poly)alkylene glycol compound are preferably non-polymerizable compounds having no polymerizable group Qp. Note that (poly)alkylene glycol means that the alkylene glycol structure may be one or a plurality of them linked repeatedly.

[0068] <<Surfactant>> As the surfactant that can be used as the release agent in the present invention, a nonionic surfactant is preferable. A nonionic surfactant is a compound having at least one hydrophobic moiety and at least one nonionic hydrophilic moiety. The hydrophobic moiety and the hydrophilic moiety may be located at the ends or inside of the molecule, respectively. The hydrophobic moiety is composed of, for example, a hydrocarbon group, and the number of carbon atoms in the hydrophobic moiety is preferably 1 to 25, more preferably 2 to 15, still more preferably 4 to 10, and even more preferably 5 to 8. The nonionic hydrophilic moiety preferably has at least one group selected from the group consisting of an alcoholic hydroxyl group, a phenolic hydroxyl group, an ether group (preferably a (poly)alkyleneoxy group, a cyclic ether group), an amide group, an imide group, a ureido group, a urethane group, a cyano group, a sulfonamide group, a lactone group, a lactam group, and a cyclocarbonate group. Among them, a compound having an alcoholic hydroxyl group or an ether group (preferably a (poly)alkyleneoxy group, a cyclic ether group) is more preferable.

[0069] <<Alcohol compound, (poly)alkylene glycol compound>> As a preferable release agent used in the curable composition for imprinting of the present invention, as described above, an alcohol compound having at least one hydroxy group at the end or a (poly)alkylene glycol compound in which the hydroxy group is etherified can be mentioned.

[0070] (Poly)alkylene glycol compounds preferably have an alkyleneoxy group or a polyalkyleneoxy group, and more preferably have a (poly)alkyleneoxy group containing an alkylene group having 1 to 6 carbon atoms. Specifically, it preferably has a (poly)ethyleneoxy group, a (poly)propyleneoxy group, a (poly)butyleneoxy group, or a mixed structure thereof, more preferably has a (poly)ethyleneoxy group, a (poly)propyleneoxy group, or a mixed structure thereof, and even more preferably has a (poly)propyleneoxy group. The (poly)alkylene glycol compound may be substantially composed of only the (poly)alkyleneoxy group except for the terminal substituents. Here, "substantially" means that the components other than the (poly)alkyleneoxy group are 5% by mass or less of the whole, preferably 1% by mass or less. In particular, it is particularly preferable to include a compound substantially composed of only the (poly)propyleneoxy group as the (poly)alkylene glycol compound.

[0071] In the (poly)alkylene glycol compound, the repeating number of the alkyleneoxy group is preferably 3 to 100, more preferably 4 to 50, even more preferably 5 to 30, and still more preferably 6 to 20.

[0072] In the (poly)alkylene glycol compound, if the terminal hydroxy group is etherified, the remaining terminal may be a hydroxy group, or the hydrogen atom of the terminal hydroxy group may be substituted. Preferred groups in which the hydrogen atom of the terminal hydroxy group may be substituted include an alkyl group (i.e., (poly)alkylene glycol alkyl ether) and an acyl group (i.e., (poly)alkylene glycol ester). Compounds having a plurality (preferably 2 or 3) of (poly)alkylene glycol chains via a linking group can also be preferably used.

[0073] Preferred specific examples of the (poly)alkylene glycol compound include polyethylene glycol, polypropylene glycol (e.g., manufactured by Wako Pure Chemical Industries, Ltd.), mono- or dimethyl ethers thereof, mono- or dicetyl ethers thereof, monostearic acid esters thereof, monooleic acid esters thereof, polyoxyethylene glyceryl ethers, polyoxypropylene glyceryl ethers, polyoxyethylene lauryl ethers, and trimethyl ethers thereof.

[0074] The (poly)alkylene glycol compound is preferably a compound represented by the following formula (P1) or (P2).

Chemical formula

[0075] The weight average molecular weight of the alcohol compound or (poly)alkylene glycol compound used as the release agent is preferably from 150 to 6000, more preferably from 200 to 3000, still more preferably from 250 to 2000, and even more preferably from 300 to 1200. Moreover, examples of commercially available products of the (poly)alkylene glycol compound that can be used in the present invention include Orphen E1010 (manufactured by Nisshin Chemical Industry Co., Ltd.), Brij 35 (manufactured by Kishida Chemical Co., Ltd.), and the like.

[0076] <Polymerization inhibitor> The curable composition for imprinting of the present invention may contain at least one kind of polymerization inhibitor. The polymerization inhibitor has a function of quenching (deactivating) reactive substances such as radicals generated from the photoinitiator, and plays a role of suppressing the reaction at a low exposure amount of the curable composition for imprinting. In particular, when other polymerizable compounds are contained, it becomes possible to sufficiently dissolve the polymerization inhibitor, and the above effects are likely to be exhibited. Examples of polymerization inhibitors include hydroquinone, 4-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, etc. These are preferably used. In addition, the polymerization inhibitors described in paragraph 0060 of JP-A-2015-127817 and the compounds described in paragraphs 0031 to 0046 of WO2015 / 125469 can also be used. Specific examples of commercially available polymerization inhibitors include Q-1300, Q-1301, TBHQ (manufactured by Wako Pure Chemical Industries, Ltd.), and the Quinopower series (manufactured by Kawasaki Chemical Industry Co., Ltd.). In addition, the following compounds can also be used (Me represents a methyl group).

Chemical formula

[0077] <Solvent> The above-mentioned curable composition for imprinting may contain a solvent. The solvent refers to a compound that is liquid at 23°C and has a boiling point of 250°C or lower. When containing a solvent, its content is preferably, for example, 1% by mass or more, more preferably 10% by mass or more, and even more preferably 30% by mass or more. The content is also preferably, for example, 99.5% by mass or less, more preferably 99% by mass or less, and even more preferably 98% by mass or less. Also, the content of the solvent being 90 to 99% by mass based on the total mass of the composition is also one of the preferred embodiments of the present invention. In the above embodiment, the content of the solvent is preferably 92 to 99% by mass, and also preferably 94 to 99% by mass. The solvent may contain only one type or two or more types. When two or more types are contained, the total amount is preferably within the above range. In the present invention, the boiling point of the component having the highest content among the solvents is preferably 200°C or lower, and more preferably 160°C or lower. By setting the boiling point of the solvent to the above temperature or lower, it becomes possible to remove the solvent in the curable composition for imprinting by baking. The lower limit value of the boiling point of the solvent is not particularly limited, but 60°C or higher is practical, and it may be 80°C or higher, or even 100°C or higher. The solvent is preferably an organic solvent. The solvent is preferably a solvent having at least one of an ester group, a carbonyl group, an alkoxy group, a hydroxyl group, and an ether group. Specific examples of the solvent include 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. Examples of the alkoxy alcohol include methoxyethanol, ethoxyethanol, methoxypropanol (e.g., 1-methoxy-2-propanol), ethoxypropanol (e.g., 1-ethoxy-2-propanol), propoxypropanol (e.g., 1-propoxy-2-propanol), methoxybutanol (e.g., 1-methoxy-2-butanol, 1-methoxy-3-butanol), ethoxybutanol (e.g., 1-ethoxy-2-butanol, 1-ethoxy-3-butanol), methylpentanol (e.g., 4-methyl-2-pentanol), and the like. As the propylene glycol monoalkyl ether carboxylate, at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate is preferable, and propylene glycol monomethyl ether acetate is particularly preferable. Moreover, as the propylene glycol monoalkyl ether, propylene glycol monomethyl ether or propylene glycol monoethyl ether is preferable. As the lactate ester, ethyl lactate, butyl lactate, or propyl lactate is preferable. As the acetate ester, 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 preferable. As the alkoxypropionate ester, methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferable. Examples of the chain ketone include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, or methyl amyl ketone. As the cyclic ketone, methylcyclohexanone, isophorone or cyclohexanone is preferred. As the lactone, γ-butyrolactone (γ-BL) is preferred. As the alkylene carbonate, propylene carbonate is preferred. In addition to the above components, it is preferable to use an ester solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, still more preferably 7 to 10) and 2 or less heteroatoms. Preferable examples of the ester solvent having 7 or more carbon atoms and 2 or less heteroatoms include amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, butyl propionate, isobutyl isobutyrate, heptyl propionate, butyl butanoate, etc., and it is particularly preferable to use isoamyl acetate. Also, it is preferable to use those having a flash point (hereinafter also referred to as fp) of 30°C or higher. As such a component (M2), 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. Among these, propylene glycol monoethyl ether, ethyl lactate (EL), pentyl acetate or cyclohexanone is more preferred, and propylene glycol monoethyl ether or ethyl lactate is particularly preferred. Here, the "flash point" means the value described in the reagent catalog of Tokyo Chemical Industry Co., Ltd. or Sigma-Aldrich Co., LLC. More preferable solvents include at least one selected from the group consisting of water, propylene glycol monomethyl ether acetate (PGMEA), ethoxyethyl propionate, cyclohexanone, 2-heptanone, γ-butyrolactone, butyl acetate, propylene glycol monomethyl ether (PGME), ethyl lactate, and 4-methyl-2-pentanol, and at least one selected from the group consisting of PGMEA and PGME is more preferable.

[0078] <Ultraviolet absorber> The curable composition for imprinting of the present invention may contain an ultraviolet absorber. The ultraviolet absorber absorbs leakage light (flare light) generated during exposure to suppress the reaction light from reaching the photoinitiator, and plays a role in suppressing the reaction of the curable composition for imprinting at a low exposure amount. Examples of the type of ultraviolet absorber include benzotriazole-based, triazine-based, cyanoacrylate-based, benzophenone-based, and benzoate-based ones. The content of the ultraviolet absorber is preferably 0.01 to 5% by mass, and more preferably 0.02 to 3% by mass. The ultraviolet absorber may be used alone or in combination of a plurality. When using a plurality, it is preferable that the total amount is within the above range.

[0079] <Other components> Other components can also be used in the curable composition for imprinting of the present invention. For example, it may contain a sensitizer, an antioxidant, etc. The content is not particularly limited, but about 0.01 to 20% by mass may be appropriately blended in the total solid content of the composition. Specific examples of other components contained in the curable composition for imprinting of the present invention include additives contained in the compositions described in JP-A-2013-036027, JP-A-2014-090133, and JP-A-2013-189537, and the contents of these are incorporated herein. Also, regarding the preparation of the composition and the method for manufacturing an imprint pattern, the descriptions in the above publications can be referred to, and the contents of these are incorporated herein.

[0080] <Physical properties> In the present invention, the curable composition for imprinting is formed into a film shape and irradiated with an exposure amount of 300 mJ / cm 2 The elastic modulus calculated by the Oliver-Pharr method of the cured film having a thickness of 300 nm formed by irradiation is preferably 1.5 GPa or more, more preferably 1.8 GPa or more, and even more preferably 2.0 GPa or more. As the upper limit, it is practical that it is 4.0 GPa or less. When the elastic modulus of the cured film of the curable composition for imprinting is equal to or higher than the above lower limit value, it becomes possible to impart sufficient strength to the imprint pattern and the resolution is improved. On the other hand, by setting it to be equal to or lower than the upper limit value, the releasability from the mold is improved and defects are reduced.

[0081] In the curable composition for imprinting of the present invention, the difference between the surface tension of the total solid content and the surface tension of the components obtained by removing the release agent from the total solid content of the curable composition for imprinting is preferably 1.5 mN / m or less, more preferably 1.0 mN / m or less, and even more preferably 0.8 mN / m or less. As the lower limit value, for example, it is practical that it is 0.01 mN / m or more, and further 0.1 mN / m or more. The smaller this difference is, the more the compatibility of the release agent in the curable composition for imprinting is improved, and it becomes possible to form a homogeneous cured film.

[0082] <Storage container> As the storage container for the curable composition for imprinting used in the present invention, a conventionally known storage container can be used. Further, as the storage container, for the purpose of suppressing the mixing of impurities into the raw materials and the composition, it is also preferable to use a multilayer bottle in which the inner wall of the container is composed of 6 types of resins in 6 layers, or a bottle in which 6 types of resins are in a 7-layer structure. Examples of such containers include the containers described in JP-A-2015-123351.

[0083] <Coating film and method for producing the same> The film of the present invention is a coating film of the curable composition for imprinting of the present invention. When the curable composition for imprinting of the present invention contains a solvent, the solvent may be removed by drying in the coating film of the present invention. That is, the film of the present invention contains an organopolysiloxane having a radically polymerizable group, a radical generator, a specific compound, and, if necessary, components other than the above contained in the curable composition for imprinting of the present invention, and may contain a solvent or may be a film substantially free of a solvent. The content of the solvent in the film of the present invention is preferably 3% by mass or less, more preferably 1% by mass or less, and still more preferably 0.1% by mass or less based on the total mass of the film. The lower limit of the above content is not particularly limited and may be 0% by mass. The film of the present invention is preferably formed, for example, by applying the curable composition for imprinting of the present invention onto a support or a mold.

[0084] The method for producing the film of the present invention includes a step of applying the curable composition for imprinting of the present invention onto a support or a mold. When the curable composition for imprinting of the present invention contains a solvent, the method for producing the film of the present invention preferably includes a step of applying the curable composition for imprinting of the present invention onto a support or a mold, and a drying step of drying the applied curable composition for imprinting. Details of the above application step and drying step are the same as those of the application step and drying step in the method for producing a pattern described later.

[0085] (Method for producing a cured product and an imprint pattern) The cured product of the present invention is a cured product obtained by curing the curable composition for imprinting of the present invention. The cured product of the present invention is preferably a patterned cured product (imprint pattern). Hereinafter, a method for producing an imprint pattern will be described.

[0086] <Method for producing an imprint pattern> The method for producing an imprint pattern of the present invention includes an application step of applying the curable composition for imprinting of the present invention to an applied member selected from the group consisting of a support and a mold, a contact step of bringing a member not selected as the applied member from the group consisting of the support and the mold into contact with the curable composition for imprinting as a contact member, a curing step of curing the curable composition for imprinting into a cured product, and a peeling step of peeling the mold and the cured product.

[0087] 〔Application step〕 The method for producing an imprint pattern of the present invention includes an application step of applying the curable composition for imprinting of the present invention to an applied member selected from the group consisting of a support and a mold. In the application step, one member selected from the group consisting of a support and a mold is selected as the applied member, and the curable composition for imprinting of the present invention is applied onto the selected applied member. Of the support and the mold, one selected is the applied member, and the other becomes the contact member. That is, in the application step, after applying the curable composition for imprinting of the present invention to the support, it may be brought into contact with the mold, or after applying it to the mold, it may be brought into contact with the support (which may have an adhesion layer or the like described later).

[0088] - Support - As the support, the description in paragraph 0103 of JP-A-2010-109092 (the corresponding US application is US Patent Application Publication No. 2011 / 0199592) can be referred to, and these contents are incorporated herein. Specifically, examples include a silicon substrate, a glass substrate, a sapphire substrate, a silicon carbide substrate, a gallium nitride substrate, a metal aluminum substrate, an amorphous aluminum oxide substrate, a polycrystalline aluminum oxide substrate, GaAsP, GaP, AlGaAs, InGaN, GaN, AlGaN, ZnSe, AlGaInP, or a substrate composed of ZnO. Specific examples of the glass substrate include aluminosilicate glass, aluminoborosilicate glass, and barium borosilicate glass. In the present invention, a silicon substrate is preferable as the substrate.

[0089] The support is preferably a member provided with an adhesion layer on the surface to which the curable composition for imprinting is applied. The adhesion layer is preferably an adhesion layer formed by applying a composition for forming an adhesion layer described later to the support. Further, the support may further include a liquid film described later on the surface opposite to the side in contact with the support of the adhesion layer. The liquid film is preferably a liquid film formed by applying a composition for forming a liquid film described later on the adhesion layer.

[0090] As the adhesion layer, for example, those described in paragraphs 0017 to 0068 of JP-A-2014-024322, paragraphs 0016 to 0044 of JP-A-2013-093552, the adhesion layer described in JP-A-2014-093385, the adhesion layer described in JP-A-2013-202982, etc. can be used, and these contents are incorporated herein.

[0091] -Mold- In the present invention, the mold is not particularly limited. Regarding the mold, the descriptions in paragraphs 0105 to 0109 of JP-A-2010-109092 (the corresponding US application is US Patent Application Publication No. 2011 / 0199592) can be referred to, and these contents are incorporated herein. As the mold used in the present invention, a quartz mold is preferable. The pattern (line width) of the mold used in the present invention is preferably 50 nm or less in size. The pattern of the mold can be formed, for example, by photolithography, electron beam drawing method, etc., according to the desired processing accuracy. However, in the present invention, the method for manufacturing the mold pattern is not particularly limited. Further, as the imprint pattern, a mold in which an imprint pattern including any one of the shapes of a line, a hole, and a pillar is formed is preferable. Among them, a mold in which an imprint pattern including any one of the shapes of a line, a hole, and a pillar with a size of 100 nm or less is formed is preferable.

[0092] - Application method - The method for applying the curable composition for imprinting of the present invention to the member to be applied is not particularly defined, and generally well-known application methods can be adopted. 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 scan method, inkjet method are exemplified. Among these, the inkjet method and the spin coating method are preferably mentioned. Further, the curable composition for imprinting may be applied by multiple coating. In the method of arranging droplets by the inkjet method, the volume of the droplets is preferably about 1 to 20 pL, and it is preferable to arrange them on the surface of the support with an interval between the droplets. The interval between the droplets may be appropriately set according to the volume of the droplets, but an interval of 10 to 1000 μm is preferable. The interval between the droplets is the arrangement interval of the nozzles of the inkjet in the case of the inkjet method. The inkjet method has an advantage that the loss of the curable composition for imprinting is small. As a specific example of the method for applying a curable composition for imprinting by an inkjet method, the methods described in JP-A-2015-179807, International Publication No. 2016 / 152597, etc. can be mentioned, and the methods described in these documents can also be preferably used in the present invention. On the other hand, the spin coating method has the advantages that the stability of the coating process is high and the options of materials that can be used are widened. As a specific example of the method for applying a curable composition for imprinting by the spin coating method, the methods described in JP-A-2013-095833, JP-A-2015-071741, etc. can be mentioned, and the methods described in these documents can also be preferably used in the present invention.

[0093] - Drying step - Further, the method for producing an imprint pattern of the present invention may further include a drying step of drying the curable composition for imprinting of the present invention applied in the application step. In particular, when a composition containing a solvent is used as the curable composition for imprinting of the present invention, it is preferable that the method for producing an imprint pattern of the present invention includes a drying step. In the drying step, at least a part of the solvent contained in the applied curable composition for imprinting of the present invention is removed. The drying method is not particularly limited, and drying by heating, drying by blowing air, etc. can be used without particular limitation, but drying by heating is preferably performed. The heating means is not particularly limited, and known hot plates, ovens, infrared heaters, etc. can be used. In the present invention, a layer formed from the curable composition for imprinting after the application step and, if necessary, the drying step is also referred to as a "curable film" before the contact step.

[0094] 〔Contact step〕 The method for producing an imprint pattern of the present invention includes a contact step of bringing a member not selected as the above-described applied member into contact with the curable composition for imprinting (curable film) as a contact member from the group consisting of the above-described support and the above-described mold. When the support is selected as the member to be applied in the above application step, in the contact step, the mold as the contact member is brought into contact with the surface of the support to which the curable composition for imprinting of the present invention is applied (the surface on which the curable film is formed). When the mold is selected as the member to be applied in the above application step, in the contact step, the support as the contact member is brought into contact with the surface of the mold to which the curable composition for imprinting of the present invention is applied (the surface on which the curable film is formed). That is, in the contact step, the curable composition for imprinting of the present invention comes to exist between the member to be applied and the contact member. Details of the support and the mold are as described above.

[0095] When bringing the curable composition for imprinting of the present invention (curable film) applied on the member to be applied into contact with the contact member, the pressing pressure is preferably 1 MPa or less. By setting the pressing pressure to 1 MPa or less, the support and the mold are less likely to deform, and the pattern accuracy tends to improve. Also, it is preferable in that the apparatus can be miniaturized because the pressing force is low. Also, it is preferable to perform the contact between the curable film and the contact member in an atmosphere containing helium gas or condensable gas, or both helium gas and condensable gas.

[0096] 〔Curing step〕 The method for producing an imprint pattern of the present invention includes a curing step of converting the curable composition for imprinting into a cured product. The curing step is performed after the contact step and before the peeling step. The method for producing a cured product of the present invention includes a step of curing the curable composition for imprinting obtained by the method for producing the curable composition for imprinting of the present invention. The above curing step can be performed in the same manner as the curing step in the method for producing an imprint pattern of the present invention. Also, the above cured product is preferably a cured product in a state where the mold is peeled off by the peeling step described later. Examples of the curing method include curing by heating, curing by exposure, etc., and it may be determined according to the type of polymerization initiator contained in the curable composition for imprinting. However, curing by exposure is preferred. For example, when the polymerization initiator is a photoinitiator, the curable composition for imprinting can be cured by performing exposure in the curing step.

[0097] The exposure wavelength is not particularly limited and may be determined according to the polymerization initiator. For example, ultraviolet light or the like can be used. The exposure light source may be determined according to the exposure wavelength. Examples include g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broadband light (light containing at least two wavelengths selected from the group consisting of the three wavelengths of g, h, and i lines and light having a wavelength shorter than the i-line. For example, a high-pressure mercury lamp when an optical filter is not used, etc.), semiconductor lasers (wavelengths 830 nm, 532 nm, 488 nm, 405 nm, etc.), metal halide lamps, excimer lasers, KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), F2 excimer lasers (wavelength 157 nm), extreme ultraviolet light; EUV (wavelength 13.6 nm), electron beams, etc. Among these, exposure using i-line or broadband light is preferably mentioned.

[0098] The irradiation amount (exposure amount) during exposure only needs to be sufficiently larger than the minimum irradiation amount required for curing the curable composition for imprinting. The irradiation amount required for curing the curable composition for imprinting can be appropriately determined by examining the consumption amount of unsaturated bonds in the curable composition for imprinting, etc. The exposure amount is preferably in the range of, for example, 5 to 1,000 mJ / cm 2 and more preferably in the range of 10 to 500 mJ / cm 2 The exposure illuminance is not particularly limited and may be selected according to the relationship with the light source. However, it is preferably in the range of 1 to 500 mW / cm and more preferably in the range of 10 to 400 mW / cm 2 ​2 It is more preferable to be within the range of. The exposure time is not particularly limited and may be determined in consideration of the exposure illuminance according to the exposure amount, but it is preferably 0.01 to 10 seconds, and more preferably 0.5 to 1 second. The temperature of the support during exposure is usually room temperature, but exposure may be performed while heating to enhance reactivity. As a pre-exposure step, putting it in a vacuum state is effective for preventing bubble mixing, suppressing a decrease in reactivity due to oxygen mixing, and improving the adhesion between the mold and the imprint curable composition, so light irradiation may be performed in a vacuum state. Also, the preferable degree of vacuum during exposure is in the range of 10 -1 Pa to atmospheric pressure.

[0099] After exposure, if necessary, the imprint curable composition after exposure may be heated. The heating temperature is preferably 150 to 280°C, and more preferably 200 to 250°C. Also, the heating time is preferably 5 to 60 minutes, and even more preferably 15 to 45 minutes. Also, in the curing step, only the heating step may be performed without exposure. For example, when the above polymerization initiator is a thermal polymerization initiator, the imprint curable composition can be cured by heating in the curing step. The preferable modes of the heating temperature and heating time in that case are the same as those of the heating temperature and heating time when heating is performed after the above exposure. The heating means is not particularly limited, and examples include the same heating means as the heating in the above drying step.

[0100] 〔Peeling step〕 The method for producing an imprint pattern of the present invention includes a peeling step of peeling the above mold and the above cured product. In the peeling step, the cured product obtained in the curing step is peeled from the mold, and a patterned cured product (also referred to as a "cured product pattern") with the pattern of the mold transferred thereto is obtained. The obtained cured product pattern can be used for various applications as described later. In the present invention, particularly, a fine cured product pattern on the nano-order can be formed, and further, a cured product pattern with a size of 50 nm or less, particularly 30 nm or less, can be formed, which is beneficial. The lower limit value of the size of the cured product pattern is not particularly defined, but for example, it can be 1 nm or more. The peeling method is not particularly limited, and for example, it can be carried out using a mechanical peeling device or the like known in the imprint pattern manufacturing method.

[0101] (Device, method for manufacturing a device, application of a cured product pattern) The device of the present invention contains the cured product of the present invention. Further, the device of the present invention can be obtained, for example, by the following method for manufacturing a device of the present invention. The method for manufacturing a device of the present invention includes the method for manufacturing an imprint pattern of the present invention. Specifically, there can be mentioned a method for manufacturing a device in which a pattern (cured product pattern) formed by the method for manufacturing an imprint pattern of the present invention is used as a permanent film used in a liquid crystal display device (LCD) or the like, or an etching resist (mask for lithography) for manufacturing a semiconductor element. In particular, the present invention discloses a method for manufacturing a circuit board, which includes a step of obtaining a pattern (cured product pattern) by the method for manufacturing an imprint pattern of the present invention, and a method for manufacturing a device including the circuit board. Further, in the method for manufacturing a circuit board according to a preferred embodiment of the present invention, the method may include a step of etching or ion implanting a substrate using the pattern (cured product pattern) obtained by the method for forming the pattern as a mask, and a step of forming an electronic component. The circuit board is preferably a semiconductor element. That is, the present invention discloses a method for manufacturing a semiconductor device including the method for manufacturing an imprint pattern of the present invention. Further, the present invention discloses a method for manufacturing a device, which includes a step of obtaining a circuit board by the method for manufacturing the circuit board, and a step of connecting the circuit board and a control mechanism for controlling the circuit board. Also, by forming a grid pattern on a glass substrate of a liquid crystal display device using the method for manufacturing an imprint pattern of the present invention, a polarizing plate with less reflection and absorption and a large screen size (for example, over 55 inches, 60 inches) can be manufactured at low cost. That is, the present invention discloses a method for manufacturing a polarizing plate including the method for manufacturing an imprint pattern of the present invention and a method for manufacturing a device including the polarizing plate. For example, a polarizing plate described in JP-A-2015-132825 or WO 2011 / 132649 can be manufactured. Note that 1 inch is 25.4 mm.

[0102] The pattern (cured product pattern) manufactured by the method for manufacturing an imprint pattern of the present invention is also useful as an etching resist (mask for lithography). That is, the present invention discloses a method for manufacturing a device, which includes the method for manufacturing an imprint pattern of the present invention and uses the obtained cured product pattern as an etching resist. When using the cured product pattern as an etching resist, first, the method for manufacturing the imprint pattern of the present invention is applied onto a support to form a pattern (cured product pattern), and an embodiment is provided in which the support is etched using the obtained cured product pattern as an etching mask. In the case of wet etching, etching is performed using an etching gas such as hydrogen fluoride, and in the case of dry etching, etching is performed using an etching gas such as CF4, whereby a pattern can be formed on the support along the shape of the desired cured product pattern.

[0103] In addition, the pattern (cured product pattern) produced by the method for manufacturing the imprint pattern of the present invention can be preferably used for the production of recording media such as magnetic disks, light receiving elements such as solid-state imaging devices, light emitting elements such as LEDs (light emitting diodes) and organic ELs (organic electroluminescence), optical devices such as liquid crystal display devices (LCDs), 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, polarizing elements, optical films, flat panel display members such as columnar materials, nanobiodevices, immunoassay chips, deoxyribonucleic acid (DNA) separation chips, microreactors, photonic liquid crystals, and guide patterns for fine pattern formation (directed self-assembly, DSA) using self-organization of block copolymers. That is, in the present invention, a method for manufacturing these devices including the method for manufacturing the imprint pattern of the present invention is disclosed.

[0104] <Composition for forming an adhesion layer> As described above, by providing an adhesion layer between the support and the curable composition for imprinting, effects such as improved adhesion between the support and the curable composition layer for imprinting can be obtained. In the present invention, the adhesion layer is obtained by applying a composition for forming an adhesion layer onto a support by the same method as the curable composition for imprinting, and then curing the composition. Hereinafter, each component of the composition for forming an adhesion layer will be described.

[0105] The composition for forming an adhesion layer contains a curable component. The curable component is a component that constitutes the adhesion layer and may be either a polymer component (e.g., having a molecular weight exceeding 1000) or a low-molecular component (e.g., having a molecular weight less than 1000). Specifically, resins and crosslinking agents are exemplified. Each of these may be used alone or in combination of two or more.

[0106] The total content of the curable component in the composition for forming an adhesion layer is not particularly limited, but is preferably 50% by mass or more in the total solid content, more preferably 70% by mass or more in the total solid content, and even more preferably 80% by mass or more in the total solid content. The upper limit is not particularly restricted, but is preferably 99.9% by mass or less.

[0107] The concentration of the curable component in the composition for forming an adhesion layer (including the solvent) is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more. As the upper limit, it is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less, and still more preferably less than 1% by mass.

[0108] [Resin] Known resins can be widely used as the resin in the composition for forming an adhesion layer. The resin used in the present invention preferably has at least one of a radical polymerizable group and a polar group, and more preferably has both a radical polymerizable group and a polar group.

[0109] By having a radical polymerizable group, an adhesion layer excellent in strength can be obtained. Also, by having a polar group, the adhesion to the support is improved. Further, when a crosslinking agent is blended, the crosslinked structure formed after curing becomes stronger, and the strength of the obtained adhesion layer can be improved.

[0110] The radically polymerizable group preferably contains an ethylenically unsaturated bond-containing group. Examples of the ethylenically unsaturated bond-containing group include (meth)acryloyl groups (preferably (meth)acryloyloxy groups, (meth)acryloylamino groups), vinyl groups, vinyloxy groups, allyl groups, methylallyl groups, propenyl groups, butenyl groups, vinylphenyl groups, cyclohexenyl groups, with (meth)acryloyl groups and vinyl groups being preferred, (meth)acryloyl groups being more preferred, and (meth)acryloyloxy groups being even more preferred. The ethylenically unsaturated bond-containing group defined herein is referred to as Et.

[0111] Further, the polar group is preferably at least one of an acyloxy group, a carbamoyloxy group, a sulfonyloxy group, an acyl group, an alkoxycarbonyl group, an acylamino group, a carbamoyl group, an alkoxycarbonylamino group, a sulfonamide group, a phosphoric acid group, a carboxy group, and a hydroxy group, more preferably at least one of an alcoholic hydroxy group, a phenolic hydroxy group, and a carboxy group, and even more preferably an alcoholic hydroxy group or a carboxy group. The polar group defined herein is referred to as polar group Po. The polar group is preferably a nonionic group.

[0112] The resin in the composition for forming the adhesion layer may further contain a cyclic ether group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group, with the epoxy group being preferred. The cyclic ether group defined herein is referred to as cyclic ether group Cyt.

[0113] Examples of the above resin include (meth)acrylic resins, vinyl resins, novolak resins, phenol resins, melamine resins, urea resins, epoxy resins, and polyimide resins, and it is preferably at least one of (meth)acrylic resins, vinyl resins, and novolak resins.

[0114] The weight average molecular weight of the above resin is preferably 4000 or more, more preferably 6000 or more, and even more preferably 8000 or more. As the upper limit, it is preferably 1000000 or less, and may be 500000 or less.

[0115] The above resin preferably has at least one structural unit of the following formulas (1) to (3).

[0116]

Chemical formula

[0117] In the formula, R 1 and R 2 are each independently a hydrogen atom or a methyl group. R 21 and R 3 are each independently a substituent. L 1 , L 2 and L 3 are each independently a single bond or a linking group. n2 is an integer from 0 to 4. n3 is an integer from 0 to 3. Q 1 is an ethylenically unsaturated bond-containing group or a cyclic ether group. Q 2 is an ethylenically unsaturated bond-containing group, a cyclic ether group or a polar group.

[0118] R 1 and R 2 are preferably methyl groups.

[0119] R 21 and R 3 are each independently preferably the above substituents.

[0120] R 21When there are a plurality of them, they may be connected to each other to form a cyclic structure. In this specification, "connection" means not only a mode of bonding and continuity but also a mode of condensation (ring contraction) with the loss of some atoms. Also, unless otherwise specified, the cyclic structure formed may contain an oxygen atom, a sulfur atom, or a nitrogen atom (amino group). Examples of the cyclic structure formed include an aliphatic hydrocarbon ring (hereinafter, those exemplified below are referred to as ring Cf) (for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, etc.), an aromatic hydrocarbon ring (hereinafter, those exemplified below are referred to as ring Cr) (benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, etc.), a nitrogen-containing heterocyclic ring (hereinafter, those exemplified below are referred to as ring Cn) (for example, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrroline ring, pyrrolidine ring, imidazolidine ring, pyrazolidine ring, piperidine ring, piperazine ring, morpholine ring, etc.), an oxygen-containing heterocyclic ring (hereinafter, those exemplified below are referred to as ring Co) (furan ring, pyran ring, oxirane ring, oxetane ring, tetrahydrofuran ring, tetrahydropyran ring, dioxane ring, etc.), a sulfur-containing heterocyclic ring (hereinafter, those exemplified below are referred to as ring Cs) (thiophene ring, thiirane ring, thietane ring, tetrahydrothiophene ring, tetrahydrothiopyran ring, etc.), and the like.

[0121] R 3 When there are a plurality of them, they may be connected to each other to form a cyclic structure. Examples of the cyclic structure formed include Cf, ring Cr, ring Cn, ring Co, ring Cs, and the like.

[0122] L 1 、L 2 、L 3is preferably a single bond or a linking group L described below, independently of each other. Among them, a single bond, an alkylene group or an (oligo)alkyleneoxy group defined by the linking group L is preferable, and an alkylene group is more preferable. The linking group L preferably has a polar group Po as a substituent. Also, an embodiment in which the alkylene group has a hydroxy group as a substituent is preferable. In the present specification, the "(oligo)alkyleneoxy group" means a divalent linking group having one or more "alkyleneoxy" as a structural unit. The number of carbon atoms in the alkylene chain in the structural unit may be the same or different for each structural unit.

[0123] n2 is preferably 0 or 1, and more preferably 0. n3 is preferably 0 or 1, and more preferably 0.

[0124] Q 1 is preferably an ethylenically unsaturated bond-containing group Et.

[0125] Q 2 is preferably a polar group, and preferably an alkyl group having an alcoholic hydroxy group.

[0126] The above resin may further contain at least one of the following structural units (11), (21) and (31). In particular, in the resin included in the present invention, it is preferable that the structural unit (11) is combined with the structural unit (1), the structural unit (21) is combined with the structural unit (2), and the structural unit (31) is combined with the structural unit (3).

[0127]

Chemical formula

[0128] In the formula, R 11 and R 22 are each independently a hydrogen atom or a methyl group. R 17 is a substituent. R 27 is a substituent. n21 is an integer from 0 to 5. R 31is a substituent, and n31 is an integer from 0 to 3.

[0129] R 11 and R 22 are preferably methyl groups.

[0130] R 17 is preferably a group containing a polar group or a group containing a cyclic ether group. When R 17 is a group containing a polar group, it is preferably a group containing the above-mentioned polar group Po, more preferably the above-mentioned polar group Po or a substituent substituted with the above-mentioned polar group Po. When R 17 is a group containing a cyclic ether group, it is preferably a group containing the above-mentioned cyclic ether group Cyt, more preferably a substituent substituted with the above-mentioned cyclic ether group Cyt.

[0131] R 27 is a known substituent, and at least one of R 27 is preferably a polar group. n21 is preferably 0 or 1, more preferably 0. When there are a plurality of R 27 they may be linked to each other to form a cyclic structure. Examples of the cyclic structure formed include ring Cf, ring Cr, ring Cn, ring Co, and ring Cs.

[0132] R 31 is preferably a known substituent. n31 is an integer from 0 to 3, preferably 0 or 1, more preferably 0. When there are a plurality of R 31 they may be linked to each other to form a cyclic structure. Examples of the cyclic structure formed include ring Cf, ring Cr, ring Cn, ring Co, and ring Cs.

[0133] 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, still more preferably 2 to 3 carbon atoms), (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; the repeating number is preferably 1 to 50, more preferably 1 to 40, still more preferably 1 to 30), an arylene group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a thiocarbonyl group, -NR N -, and linking groups related to combinations thereof. The alkylene group, alkenylene group, and alkyleneoxy group may have a substituent. For example, the alkylene group may have a hydroxy group.

[0134] The linking chain length of the linking group L is preferably 1 to 24, more preferably 1 to 12, still more preferably 1 to 6. The linking chain length means the number of atoms located in the shortest path among the atomic groups involved in the linking. For example, in the case of -CH2-(C=O)-O-, it is 3.

[0135] In addition, the alkylene group, alkenylene group, and (oligo)alkyleneoxy group defined by the linking group L may be linear or cyclic, and may be straight-chain or branched.

[0136] As the atoms constituting the linking group L, it is preferably those containing a carbon atom and a hydrogen atom, and if necessary, a hetero atom (at least one selected from an oxygen atom, a nitrogen atom, a sulfur atom, etc.). The number of carbon atoms in the linking group is preferably 1 to 24, more preferably 1 to 12, still more preferably 1 to 6. The number of hydrogen atoms may be determined according to the number of carbon atoms and the like. The number of hetero atoms is preferably 0 to 12, more preferably 0 to 6, still more preferably 0 to 3, respectively, for an oxygen atom, a nitrogen atom, and a sulfur atom.

[0137] The synthesis of the above resin may be carried out according to a conventional method. For example, the resin having the structural unit of formula (1) can be appropriately synthesized by a known method related to the addition polymerization of olefins. The resin having the structural unit of formula (2) can be appropriately synthesized by a known method related to the addition polymerization of styrene. The resin having the structural unit of formula (3) can be appropriately synthesized by a known method related to the synthesis of phenolic resins.

[0138] The above resin may be used alone or in combination of a plurality of resins.

[0139] As the resin as the curable component, in addition to the above, those described in paragraphs 0016 to 0079 of International Publication No. 2016 / 152600, paragraphs 0025 to 0078 of International Publication No. 2016 / 148095, paragraphs 0015 to 0077 of International Publication No. 2016 / 031879, and paragraphs 0015 to 0057 of International Publication No. 2016 / 027843 can be used, and the contents thereof are incorporated herein.

[0140] [Crosslinking agent] The crosslinking agent in the composition for forming the adhesion layer is not particularly limited as long as it can cause the curing to proceed by a crosslinking reaction. In the present invention, the crosslinking agent preferably forms a crosslinked structure by reacting with the polar group of the resin. By using such a crosslinking agent, the resin is more firmly bonded and a stronger film can be obtained.

[0141] Examples of the crosslinking agent include epoxy compounds (compounds having an epoxy group), oxetanyl compounds (compounds having an oxetanyl group), alkoxymethyl compounds (compounds having an alkoxymethyl group), methylol compounds (compounds having a methylol group), blocked isocyanate compounds (compounds having a blocked isocyanate group), etc. Among them, alkoxymethyl compounds (compounds having an alkoxymethyl group) are preferable because they can form a strong bond at low temperature.

[0142] [Other components] The composition for forming the adhesion layer may contain other components in addition to the above components.

[0143] Specifically, it may contain one or more of a solvent, a thermal acid generator, an alkylene glycol compound, a polymerization initiator, a polymerization inhibitor, an antioxidant, a leveling agent, a thickener, a surfactant, etc. Regarding the above components, the components described in JP-A-2013-036027, JP-A-2014-090133, and JP-A-2013-189537 can be used. Regarding the content and the like, the descriptions in the above publications can be referred to.

[0144] - Solvent - In the present invention, the composition for forming the adhesion layer preferably contains a solvent (hereinafter also referred to as "solvent for adhesion layer"). As the solvent, for example, a compound that is liquid at 23°C and has a boiling point of 250°C or lower is preferable. The composition for forming the adhesion layer preferably contains 99.0% by mass or more of the solvent for adhesion layer, more preferably 99.2% by mass or more, and may be 99.4% by mass or more. That is, the composition for forming the adhesion layer preferably has a total solid content concentration of 1% by mass or less, more preferably 0.8% by mass or less, and even more preferably 0.6% by mass or less. Also, the lower limit value is preferably more than 0% by mass, more preferably 0.001% by mass or more, even more preferably 0.01% by mass or more, and still more preferably 0.1% by mass or more. By setting the ratio of the solvent within the above range, the film thickness during film formation can be kept thin, and the pattern formability during etching processing tends to be improved.

[0145] The composition for forming the adhesion layer may contain only one type of solvent or two or more types of solvents. When two or more types are contained, it is preferable that the total amount thereof falls within the above range.

[0146] The boiling point of the solvent for the adhesion layer is preferably 230°C or lower, more preferably 200°C or lower, even more preferably 180°C or lower, still more preferably 160°C or lower, and even more preferably 130°C or lower. The lower limit value is preferably 23°C, and more preferably 60°C or higher. By setting the boiling point within the above range, it is preferable that the solvent can be easily removed from the adhesion layer.

[0147] The solvent for the adhesion layer is preferably an organic solvent. The solvent is preferably a solvent having at least one of an ester group, a carbonyl group, a hydroxy group, and an ether group. Among them, it is preferable to use an aprotic polar solvent.

[0148] Among the solvents for the adhesion layer, preferred solvents include alkoxy alcohols, propylene glycol monoalkyl ether carboxylates, propylene glycol monoalkyl ethers, lactate esters, acetate esters, alkoxypropionic acid esters, chain ketones, cyclic ketones, lactones, and alkylene carbonates. Propylene glycol monoalkyl ether and lactone are particularly preferred.

[0149] <Composition for forming a liquid film> In the present invention, it is also preferable to form a liquid film on the adhesion layer using a composition for forming a liquid film containing a radically polymerizable compound that is liquid at 23°C and 1 atm. In the present invention, the liquid film is obtained by applying the composition for forming a liquid film on a support and then drying the composition by the same method as the curable composition for imprinting. By forming such a liquid film, the adhesion between the support and the curable composition for imprinting is further improved, and the wettability of the curable composition for imprinting on the support is also improved. Hereinafter, the composition for forming a liquid film will be described.

[0150] The viscosity of the composition for forming a liquid film is preferably 1000 mPa·s or less, more preferably 800 mPa·s or less, still more preferably 500 mPa·s or less, and even more preferably 100 mPa·s or less. The lower limit value of the above viscosity is not particularly limited, but for example, it can be 1 mPa·s or more. The viscosity is measured according to the following method.

[0151] The viscosity is measured using an E-type rotational viscometer RE85L manufactured by Toki Sangyo Co., Ltd., with a standard cone and rotor (1°34’×R24), and adjusting the temperature of the sample cup to 23°C. The unit is expressed in mPa·s. Other details regarding the measurement comply with JIS Z8803:2011. Two samples are prepared for each level and measured three times each. The arithmetic mean value of a total of six measurements is adopted as the evaluation value.

[0152] 〔Radical polymerizable compound A〕 The composition for forming a liquid film contains a radical polymerizable compound (radical polymerizable compound A) that is liquid at 23°C and 1 atm.

[0153] The viscosity of the radical polymerizable compound A at 23°C is preferably 1 to 100,000 mPa·s. The lower limit is preferably 5 mPa·s or more, more preferably 11 mPa·s or more. The upper limit is preferably 1000 mPa·s or less, more preferably 600 mPa·s or less.

[0154] The radical polymerizable compound A may be a monofunctional radical polymerizable compound having only one radical polymerizable group in one molecule, or a polyfunctional radical polymerizable compound having two or more radical polymerizable groups in one molecule. A monofunctional radical polymerizable compound and a polyfunctional radical polymerizable compound may be used in combination. Among them, due to the reason of suppressing pattern collapse, the radical polymerizable compound A contained in the composition for forming a liquid film preferably contains a polyfunctional radical polymerizable compound, more preferably contains a radical polymerizable compound having 2 to 5 radical polymerizable groups in one molecule, still more preferably contains a radical polymerizable compound having 2 to 4 radical polymerizable groups in one molecule, and particularly preferably contains a radical polymerizable compound having 2 radical polymerizable groups in one molecule.

[0155] In addition, the radically polymerizable compound A preferably contains at least one of an aromatic ring (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms) and an alicyclic ring (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and even more preferably 3 to 6 carbon atoms), and more preferably contains an aromatic ring. The aromatic ring is preferably a benzene ring. Further, the molecular weight of the radically polymerizable compound A is preferably 100 to 900.

[0156] Examples of the radically polymerizable group possessed by the radically polymerizable compound A include ethylenically unsaturated bond-containing groups such as a vinyl group, an allyl group, and a (meth)acryloyl group, and a (meth)acryloyl group is preferred.

[0157] The radically polymerizable compound A is also preferably a compound represented by the following formula (I-1).

[0158] [Chemical formula]

[0159] L 20 is a (1 + q)-valent linking group. For example, a (1 + q)-valent group having an alkane structure (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms), a group having an alkene structure (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 3 carbon atoms), a group having an aryl structure (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms), a group having a heteroaryl structure (preferably having 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, and even more preferably 1 to 10 carbon atoms, and examples of the heteroatom include a nitrogen atom, a sulfur atom, and an oxygen atom, and a 5-membered ring, 6-membered ring, or 7-membered ring is preferred), or a linking group containing a combination of these groups. Examples of a group formed by combining two aryl groups include groups having structures 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 structures such as indole, benzimidazole, quinoxaline, and carbazole.

[0160] L 20 is preferably a linking group containing at least one selected from an aryl structure group and a heteroaryl structure group, and more preferably a linking group containing an aryl structure group.

[0161] R 21 and R 22 each independently represent a hydrogen atom or a methyl group.

[0162] L 21 and L 22 each independently represent a single bond or the above linking group L, and are preferably a single bond or an alkylene group.

[0163] L 20 and L 21 or L 22 may be bonded with or without passing through the linking group L to form a ring. L 20 L 21 and L 22 may have a substituent. A plurality of substituents may combine to form a ring. When there are a plurality of substituents, they may be the same or different from each other.

[0164] q2 is an integer from 0 to 5, preferably an integer from 0 to 3, more preferably an integer from 0 to 2, still more preferably 0 or 1, and particularly preferably 1.

[0165] As the radical polymerizable compound A, the compounds described in paragraphs 0017 to 0024 and the examples of JP-A-2014-090133, the compounds described in paragraphs 0024 to 0089 of JP-A-2015-009171, the compounds described in paragraphs 0023 to 0037 of JP-A-2015-070145, and the compounds described in paragraphs 0012 to 0039 of WO 2016 / 152597 can also be used.

[0166] The content of the radically 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 even more preferably 0.1% by mass or more. As the upper limit, it is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less.

[0167] The content of the radically polymerizable compound A in the solid content of the composition for forming a liquid film is preferably 50% by mass or more, more preferably 75% by mass or more, and even more preferably 90% by mass or more. The upper limit may be 100% by mass. Only one kind of the radically polymerizable compound A may be used, or two or more kinds may be used. When two or more kinds are used, it is preferable that the total amount thereof falls within the above range.

[0168] Also, it is preferable that the solid content of the composition for forming a liquid film consists essentially of only the radically polymerizable compound A. The case where the solid content of the composition for forming a liquid film consists essentially of only the radically polymerizable compound A means that the content of the radically polymerizable compound A in the solid content of the composition for forming a liquid film is 99.9% by mass or more, more preferably 99.99% by mass or more, and even more preferably it consists of only the polymerizable compound A.

[0169] 〔Solvent〕 The composition for forming a liquid film preferably contains a solvent (hereinafter sometimes referred to as "solvent for liquid film"). Examples of the solvent for liquid film include those described in the section of the solvent for the adhesion layer mentioned above, and these can be used. The composition for forming a liquid film preferably contains 90% by mass or more of the solvent for liquid film, more preferably 99% by mass or more, and may be 99.99% by mass or more.

[0170] The boiling point of the solvent for the liquid film is preferably 230°C or lower, more preferably 200°C or lower, still more preferably 180°C or lower, even more preferably 160°C or lower, and yet even more preferably 130°C or lower. The lower limit is preferably 23°C, and more preferably 60°C or higher. By setting the boiling point within the above range, it is preferable because the solvent can be easily removed from the liquid film.

[0171] 〔Radical polymerization initiator〕 The composition for forming the liquid film may contain a radical polymerization initiator. Examples of the radical polymerization initiator include thermal radical polymerization initiators and photo radical polymerization initiators, and a photo radical polymerization initiator is preferred. As the photo radical polymerization initiator, known compounds can be arbitrarily used. For example, halogenated hydrocarbon derivatives (such as compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, acetophenone compounds, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron arene complexes, etc. Regarding the details of these, the descriptions in paragraphs 0165 to 0182 of JP-A 2016-027357 can be referred to, and this content is incorporated herein. Among these, acetophenone compounds, acylphosphine compounds, and oxime compounds are preferred. Commercially available products include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-127, IRGACURE-819, IRGACURE-379, IRGACURE-369, IRGACURE-754, IRGACURE-1800, IRGACURE-651, IRGACURE-907, IRGACURE-TPO, IRGACURE-1173, etc. (manufactured by BASF), Omnirad 184, Omnirad TPO H, Omnirad 819, Omnirad 1173 (manufactured by IGM Resins B.V.).

[0172] When a radical polymerization initiator is contained, it is preferably 0.1 to 10% by mass, more preferably 1 to 8% by mass, and still more preferably 2 to 5% by mass based on the solid content of the composition for forming a liquid film. When two or more radical polymerization initiators are used, the total amount thereof is preferably within the above range.

[0173] 〔Other Components〕 In addition to the above, the composition for forming a liquid film may contain one or more of a polymerization inhibitor, an antioxidant, a leveling agent, a thickener, a surfactant, and the like.

Examples

[0174] The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, treatment details, treatment procedures, etc. shown in the following examples can be appropriately changed 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.

[0175] <Preparation of Curable Composition for Imprinting> The various compounds listed in the table were mixed, and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization inhibitor was added so as to be 200 ppm by mass (0.02% by mass) based on the total amount of the polymerizable compounds. In the following table, A-1 corresponds to the above polymerizable compound. The components in the columns described as "-" in the table were not used. The solvents used were those described in the table, and the amount of the solvent added was adjusted so that the nonvolatile component concentration (solid content concentration) of the composition was the value of "nonvolatile component concentration (% by mass)" in the table. This was filtered through a 0.02 μm Nylon filter and a 0.003 μm UPE filter to prepare a curable composition for imprinting.

[0176] <Method for Measuring Molecular Weight of Polymerizable Compound> The weight average molecular weight (Mw) of the resin 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 the columns used were 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). Detection was performed using a UV (ultraviolet) detector with a wavelength of 254 nm. The weight average molecular weight Mw of low molecular compounds with a molecular weight of less than 1500 was measured using LC-MS (liquid chromatography mass spectrometer). The conditions were as follows. Apparatus: LC / MS G1956B manufactured by Agilent Column: TOSOH ODS-80Ts Mobile phase: 10 mM ammonium acetate aqueous solution / 10 mM acetic acid methanol aqueous solution Flow rate: 0.2 mL / min Injection volume: 2 μL Column temperature: 40 °C Detector: ESI-Posi-SIM mode

[0177] <Evaluation of release force> On a silicon wafer, the composition for forming an adhesion layer shown in Example 6 of JP-A-2014-24322 was spin-coated and heated for 1 minute using a hot plate at 220°C to form an adhesion layer with a thickness of 5 nm. Further, a curable composition for imprint was spin-coated on the adhesion layer and heated for 1 minute using a hot plate at 80°C to obtain a pattern formation layer with a film thickness of 53 nm in Example 43, a film thickness of 107 nm in Example 44, and a film thickness of 80 nm in other examples. Next, a quartz mold (in Example 43, the width of the mold protrusion is 40 nm, the width of the mold recess is 20 nm, and the depth is 50 nm; in Example 44, the width of the mold protrusion is 20 nm, the width of the mold recess is 40 nm, and the depth is 50 nm; in other examples, the width of the mold protrusion is 20 nm and the width of the mold recess is 20 nm, and the depth is 50 nm line pattern) was pressed against the pattern formation layer in a He atmosphere (substitution rate 90% or more) to fill the curable composition for imprint into the mold. When 10 seconds had elapsed after the pressing, a high-pressure mercury lamp was used from the mold side, and the maximum wavelength of the irradiation light source was 365 nm, the exposure illuminance was 10 mW / cm 2 , and the exposure time was 15 seconds (exposure amount 150 mJ / cm 2 ). After exposure under these conditions, the mold was peeled off to transfer the pattern to the pattern formation layer. The release force required at the time of peeling was measured using a load cell. The above release force was evaluated according to the following evaluation criteria. The evaluation results are shown in the column of "Evaluation of Release Force" in the table. - Evaluation Criteria - A: Release force ≦ 15 N B: 15 N < Release force ≦ 20 N C: 20 N < Release force ≦ 25 N D: Release force > 25 N

[0178]

Table 1

[0179]

Table 2

[0180]

Table 3

[0181] The details of each component in the table are as follows.

[0182]

Table 4

[0183] 〔Synthesis of silicone acrylate resin〕 Silicone resin X-40-9225 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) (10 parts), 2-hydroxyethyl acrylate (58.1 parts), and p-toluenesulfonic acid monohydrate (0.034 parts) were mixed, and then the temperature was raised to 120 °C. While distilling off the methanol produced by the condensation reaction, the mixture was stirred for 3 hours to react, and 48 parts of silicone acrylate resin 1 was obtained. Also, in the same manner as the above silicone acrylate resin 1, silicone acrylate resins 2 to 6 were synthesized.

[0184]

Table 5

[0185]

Table 6

[0186]

Table 7

[0187] In the above structural formula, the subscript in parentheses represents the repetition number.

[0188]

Table 8

[0189] In the above structural formula, the subscript in parentheses represents the repetition number.

[0190]

Table 9

[0191]

Table 10

[0192] As can be seen from the above results, according to the curable composition for imprinting of the present invention, a cured product with a small release force was obtained. In comparison, the compositions according to Comparative Examples 1 and 2 that do not contain a compound having a monovalent hydrocarbon group having 4 to 11 carbon atoms and a poly(oxyalkylene) group had a large release force.

[0193] Also, in the same manner as the above-described evaluation of releasability, an adhesion layer was formed on a silicon wafer using the composition for forming an adhesion layer, and on the adhesion layer of this silicon wafer with an adhesion layer, the curable composition for imprinting according to each example was used to form a line & space structure, a contact hole structure, a dual damascene structure, and a staircase structure. Then, using this pattern as an etching mask, the silicon wafers were each dry-etched, and semiconductor elements were each fabricated using the silicon wafers. There were no problems with the performance of any of the semiconductor elements. Furthermore, using the above-described composition for forming an adhesion layer and the curable composition for imprinting according to each example, semiconductor elements were fabricated on a substrate having an SOC (spin-on carbon) layer in the same procedure as above. There were no problems with the performance of this semiconductor element.

Claims

1. An organopolysiloxane having a radically polymerizable group, a radical generator, and a compound having a monovalent hydrocarbon group having 4 to 11 carbon atoms and a poly(oxyalkylene) group, wherein part or all of the hydrogen atoms of the monovalent hydrocarbon group may be substituted by halogen atoms, the compound is a compound represented by the following formula (C-1), a curable composition for imprinting. 【Chemical 1】 In formula (C-1), R11 and R12 are each independently a monovalent hydrocarbon group having 4 to 11 carbon atoms, L11 each independently represents an alkylene group, and n1 represents an integer of 4 or more and 40 or less.

2. The curable composition for imprinting according to claim 1, wherein in formula (C-1), L11 is an alkylene group having 2 to 10 carbon atoms.

3. The curable composition for imprinting according to claim 1 or 2, wherein in formula (C-1), n1 is 4 or more and 20 or less.

4. The curable composition for imprinting according to any one of claims 1 to 3, wherein in formula (C-1), L11 is an ethylene group or a propylene group.

5. The curable composition for imprinting according to any one of claims 1 to 4, wherein in formula (C-1), R11 and R12 are a linear alkyl group or a branched alkyl group.

6. The curable composition for imprinting according to any one of claims 1 to 5, wherein in formula (C-1), R11 and R12 are unsubstituted hydrocarbon groups.

7. The curable composition for imprinting according to any one of claims 1 to 6, wherein the content of the poly(oxyalkylene) group in the compound is 30 to 90% by mass.

8. An organopolysiloxane having a radically polymerizable group, a radical generator, and a compound represented by the following formula (C-2), a curable composition for imprinting. [Chemical Formula 2] In formula (C-2), R ２１ and R ２２ are each independently an alkyl group, and L ２１ each independently represents an alkylene group, and n2 represents an integer of 4 or more and 40 or less.

9. The curable composition for imprinting according to claim 8, wherein in formula (C-2), R21 and R22 are each independently an alkyl group having 1 to 20 carbon atoms.

10. The curable composition for imprinting according to claim 8 or 9, wherein in formula (C-2), L21 is an alkylene group having 2 to 10 carbon atoms.

11. The curable composition for imprinting according to any one of claims 1 to 10, wherein the weight average molecular weight of the compound is 300 to 1000.

12. The curable composition for imprint according to any one of claims 1 to 11, wherein the content of the compound is 0.5 to 10% by mass based on the total solid content of the composition.

13. The curable composition for imprint according to any one of claims 1 to 12, wherein the compound has no radically polymerizable group.

14. The curable composition for imprint according to any one of claims 1 to 13, wherein the content of the compound is 0.5 to 10% by mass based on the total mass of the organopolysiloxane.

15. The curable composition for imprint according to any one of claims 1 to 14, wherein the content of the solvent is 90 to 99% by mass based on the total mass of the composition.

16. A coating film of the curable composition for imprint according to any one of claims 1 to 15.

17. A method for producing a film, comprising a step of applying the curable composition for imprint according to any one of claims 1 to 15 onto a support or a mold.

18. A cured product obtained by curing the curable composition for imprint according to any one of claims 1 to 15.

19. An application step of applying the curable composition for imprint according to any one of claims 1 to 15 to an application member selected from the group consisting of a support and a mold, A contact step of bringing a member not selected as the application member from the group consisting of the support and the mold into contact with the curable composition for imprint as a contact member, A curing step of curing the curable composition for imprint into a cured product, and A peeling step of peeling the mold from the cured product, A method for producing an imprint pattern.

20. The method for producing an imprint pattern according to claim 19, wherein the support is a member provided with an adhesion layer on the surface on which the curable composition for imprint is applied.

21. A method for producing a device, comprising the method for producing an imprint pattern according to claim 19 or 20.

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