TWI819083B - Curable composition for imprinting, method of manufacturing pattern, method of manufacturing semiconductor element, and cured product - Google Patents

Abstract

The present invention provides a curable composition for imprint, a method for manufacturing a pattern using the curable composition for imprint, a method for manufacturing a semiconductor element, and a cured product. The curable composition for imprint contains a polymerizable compound, A photopolymerization initiator and a release agent. The curable composition for imprinting contains, as the above-mentioned polymerizable compound, a translucent polymerizable compound that accounts for more than 50% by mass of the total solid content of the composition. The translucent polymerizable compound The maximum value of the absorption coefficient per unit mass of the chemical compound in the wavelength range of 250 to 400 nm is 1.8L/(g･cm) or less and the weight average molecular weight is 800 or more, and the content of the release agent is relative to the composition The total solid content is 0.1 mass% or more and less than 1.0 mass%.

Description

Curable composition for imprinting, method of manufacturing pattern, method of manufacturing semiconductor element, and cured product

The present invention relates to a curable composition for imprint, a method of manufacturing a pattern using the curable composition for imprint, a method of manufacturing a semiconductor element, and a cured product.

Imprinting is a technology that transfers fine patterns to materials by pressing a patterned mold (commonly called a casting mold or a stamp). By using the imprint method, precise fine patterns can be easily produced, and therefore applications in various fields are expected in recent years. In particular, nanoimprint technology, which forms nanometer-level fine patterns, has attracted attention. As the imprinting method, methods called thermal imprinting method and light imprinting method have been proposed from this transfer method. In the hot embossing method, a thermoplastic resin heated to a temperature higher than the glass transition temperature (hereinafter sometimes referred to as "Tg") is pressed into a mold, and then cooled and then released from the mold to form a fine pattern. This method can select a variety of materials, but has problems such as requiring high pressure when pressing and making it difficult to form fine patterns due to heat shrinkage and the like.

In the optical imprinting method, a curable composition for imprinting is applied to a substrate (adhesion treatment is performed if necessary), and then a mold made of a light-transmitting material such as quartz is pressed. The curable composition for imprinting is cured by light irradiation while the mold is pressed, and then the mold is demolded, thereby producing a cured product onto which a desired pattern is transferred. Examples of methods for applying the curable composition for imprinting on the substrate include spin coating or inkjet. The inkjet method has the advantage of less loss of the curable composition for imprinting, but there are still problems with the stability of coating. In addition, when imparting inkjet adaptability to the imprint curable composition, the physical properties of the liquid may be restricted, so the selection range of materials may be narrowed. On the other hand, the spin coating method uses the same coater as conventional photoresists, so the stability of the coating process is high and the range of materials that can be used is expanded. Specific examples of the curable composition for imprinting used in the spin coating method include Patent Documents 1 and 2. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2013-095833 [Patent Document 2] Japanese Patent Application Publication No. 2015-071741

However, as a result of research conducted by the present inventors, it was found that the curable composition for imprinting used in the spin coating method causes pattern collapse and roughness at the edges of the pattern during ultrafine pattern transfer with a small pattern size. Moreover, it was found that it does not have the releasability which can fully transfer the said fine pattern. An object of the present invention is to solve this problem, and an object thereof is to provide a curable composition for imprinting that is less likely to cause pattern collapse and pattern edge roughness during ultrafine pattern transfer with a small pattern size and has excellent mold releasability, and A method of manufacturing a pattern, a method of manufacturing a semiconductor element, and a cured product using the above-mentioned curable composition for imprint.

Based on the above subject, the inventors of the present invention have conducted research and found that using a specific amount of a light-transmitting polymerizable compound with a relatively large molecular weight together with a photopolymerization initiator with high light absorption capacity, the release agent can be The above-mentioned problems can be solved by setting the blending amount to be smaller than the usual amount. Specifically, the above problems are solved in the following manner.

<1> A curable composition for imprinting, which contains a polymerizable compound, a photopolymerization initiator, and a release agent. In the curable composition for imprinting, the polymerizable compound is the maximum of the following light absorption coefficient A A translucent polymerizable compound with a value of 1.8 L/(g･cm) or less and a weight average molecular weight of 800 or more, and the curable composition for imprint contains the above-mentioned polymer in 50 mass % or more of the total solid content of the composition The above-mentioned photopolymerization initiator has a maximum value of the following light absorption coefficient B of 5,000L/(mol･cm) or more and contains 0.5 to 8.0 mass % with respect to the total solid content of the composition. , the content of the above-mentioned release agent is 0.1 mass % or more and less than 1.0 mass % relative to the total solid content of the above composition; Absorption coefficient A: Absorption coefficient per unit mass in the wavelength range of 250 to 400 nm in the acetonitrile solution Absorption coefficient B: Mohr absorption coefficient in the wavelength range of 250 to 400 nm in an acetonitrile solution. <2> The curable composition for imprinting according to <1>, wherein the translucent polymerizable compound has two or more polymerizable groups. <3> The curable composition for imprinting according to <1>, wherein the translucent polymerizable compound has two or more polymerizable groups, and the polymerizable group equivalent weight is 150 or more. <4> The curable composition for imprinting according to any one of <1> to <3>, wherein the weight average molecular weight of the translucent polymerizable compound exceeds 2,000. <5> The curable composition for imprinting according to any one of <1> to <4>, wherein the translucent polymerizable compound has a silicon skeleton. <6> The curable composition for imprinting according to any one of <1> to <5>, wherein the translucent polymerizable compound has a silicone resin introduced into the side chain of the (meth)acrylic resin. Grafted structure. <7> The curable composition for imprinting according to any one of <1> to <6>, wherein the content of the release agent is 0.5 mass % or more based on the total solid content of the composition. <8> The curable composition for imprinting according to any one of <1> to <7>, further containing a solvent. <9> The curable composition for imprint according to any one of <1> to <8>, wherein the curable composition for imprint is in a film form and irradiated with an exposure dose of 300 mJ/cm ² The resulting cured film with a thickness of 300 nm has an elastic coefficient calculated by the Oliver-Pharr method of 2.0 GPa or more. <10> The curable composition for imprint according to any one of <1> to <9>, wherein the surface tension of the total solid content of the curable composition for imprint differs from the curable composition for imprint. The difference in surface tension of the components excluding the release agent from the total solid content of the composition is 1.0 mN/m or less. <11> The curable composition for imprinting according to any one of <1> to <10>, wherein the release agent does not substantially contain fluorine atoms and silicon atoms. <12> The curable composition for imprinting according to any one of <1> to <11>, further containing a polymerization inhibitor. <13> The curable composition for imprinting according to any one of <1> to <12>, which is used in a step-repetition method. <14> A method of manufacturing a pattern, which includes applying the curable composition for imprinting according to any one of <1> to <13> on a substrate or a casting mold, and using the above casting mold and the above substrate clamp The step of irradiating light is performed while holding the above-mentioned curable composition for imprinting. <15> The pattern manufacturing method according to <14>, wherein the imprinting method is performed in a step-repetition manner. <16> The method for producing a pattern according to <14> or <15>, wherein the curable composition for imprinting is applied on an upper surface of the adhesion layer. <17> The method for producing a pattern according to any one of <14> to <16>, wherein the curable composition for imprinting is applied to the substrate by a spin coating method. <18> A method of manufacturing a semiconductor element, including the method of manufacturing a pattern according to any one of <14> to <17>. <19> A hardened material formed from the curable composition for imprinting according to any one of <1> to <13>. [Effects of the invention]

According to the present invention, it is possible to provide a curable composition for imprinting that is less likely to cause pattern collapse and roughening of pattern edges during ultrafine pattern transfer with a small pattern size, and has excellent releasability, and a curable composition for imprinting using the above-mentioned curable composition for imprinting A method of manufacturing a pattern of a sexual composition, a method of manufacturing a semiconductor element, and a hardened product.

The contents of the present invention will be described in detail below. In this specification, "～" is used in the sense that the numerical values described before and after it are included as the lower limit value and the upper limit value. In this specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic acid" means acrylic acid and methacrylic acid, and "(meth)acrylyl" means acrylic group and Methacrylyl. "(Meth)acryloxy group" means an acryloxy group and a methacryloxy group. In this specification, "imprint" preferably refers to pattern transfer with a size of 1 nm to 10 mm, and more preferably refers to pattern transfer with a size of approximately 10 nm to 100 μm (nano imprint). Regarding the labels for groups (atomic groups) in this specification, labels that are not substituted or unsubstituted include both those that do not have a substituent and those that have a substituent. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In this specification, "light" includes not only light and electromagnetic waves with wavelengths in ultraviolet, near ultraviolet, far ultraviolet, visible, infrared and other regions, but also radiation. Examples of radiation include microwaves, electron beams, extreme ultraviolet (EUV), and X-rays. In addition, laser light such as 248nm excimer laser, 193nm excimer laser, and 172nm excimer laser can also be used. The light can use monochromatic light (single wavelength light) that passes through an optical filter, or can use multiple lights with different wavelengths (composite light). In this specification, unless otherwise stated, the weight average molecular weight (Mw) is defined as a polystyrene-converted value based on gel permeation chromatography (GPC measurement). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be, for example, HLC-8220 (manufactured by TOSOH CORPORATION), and a protective column HZ-L, TSKgel Super HZM-M, or TSKgel Super can be used as the column. HZ4000, TSKgel Super HZ3000 or TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). Unless otherwise stated, the eluent will be measured using THF (tetrahydrofuran). In addition, unless otherwise stated, detection is performed using a detector with a wavelength of 254 nm of UV rays (ultraviolet rays). Unless otherwise stated, the gas pressure when measuring the boiling point in the present invention is regarded as 101325 Pa (1 atmosphere). Unless otherwise specified, the temperature in the present invention is regarded as 23°C. In this specification, the term "step" is not only an independent step. Even if it cannot be clearly distinguished from other steps, it is also included in this term as long as the expected effect of the step can be achieved.

The curable composition for imprinting of the present invention (hereinafter, sometimes referred to as the "composition of the present invention") is characterized by containing a polymerizable compound, a photopolymerization initiator, and a release agent. In the composition, the above-mentioned polymerizable compound is a translucent polymerizable compound with a maximum value of the following light absorption coefficient A of 1.8 L/(g･cm) or less and a weight average molecular weight of 800 or more, and in the curable composition for imprinting The composition contains the above-mentioned polymerizable compound in an amount of 50% by mass or more of the total solid content of the composition, and the above-mentioned photopolymerization initiator is the following: the maximum value of the absorption coefficient B is 5,000L/(mol･cm) or more and relative to the composition The total solid content of the composition contains 0.5 to 8.0 mass % of the photopolymerization initiator, and the content of the release agent is 0.1 mass % or more and less than 1.0 mass % with respect to the total solid content of the composition. Here, the absorption coefficient A is the absorption coefficient per unit mass in the wavelength range of 250 to 400 nm in the acetonitrile solution, and the absorption coefficient B is the molar absorption coefficient in the wavelength range of 250 to 400 nm in the acetonitrile solution. Unless otherwise stated, the maximum value of each absorption coefficient is the value measured based on the method described in the Examples described later. By using the curable composition for imprinting having such a structure, it is possible to provide an imprinting composition that is less likely to cause pattern collapse and roughness at the edges of the pattern during ultrafine pattern transfer with a small pattern size and has excellent releasability. Hardening composition. Although this is only speculation, it is believed that the mechanism is that the curable composition for imprint contains a specific amount of a polymerizable compound with high light transmittance, a specific amount of a photopolymerization initiator with high light absorbing ability, and a specific amount smaller than conventional ones. release agent. That is, by using a sufficient amount of a polymerizable compound with high translucency, the hardenability deep in the film is improved. In addition, by using an appropriate amount of a photopolymerization initiator with a high light absorbing ability, sufficient curing properties can be ensured and good resolution can be exhibited. In addition, the content of the release agent is reduced compared with the past, thereby improving the pattern strength deep in the film. It is thought that the above three components do not cancel out the above-mentioned effects of each other, but complement each other. Even when a fine pattern with a pattern size of about 50 nm is produced by the nanoimprint method using spin coating, the releasability can be ensured. At the same time, it is possible to form high-resolution patterns that suppress pattern collapse and pattern roughness. Furthermore, according to a preferred embodiment based on the above blended curable composition for imprinting, the cured film can have a high elastic modulus and processing resistance while ensuring the stability of the film thickness. Moreover, in the curable composition for imprinting based on the above blend, since the light transmittance of the coating film is improved, the exposure time is also shortened, and it is also suitable for a step where the imprinting process is complex and the output is small. Repeated pattern of nanoimprinters. Hereinafter, the present invention will be described in detail.

＜Light-transmitting polymerizable compound＞ ＜＜Maximum value of absorption coefficient A＞＞ The maximum value of the light absorption coefficient A of the light-transmitting polymerizable compound of the present invention is 1.8L/(g･cm) or less, preferably 1.5L/(g･cm) or less, and 1.2L/(g･cm) or less. More preferably, it is 1.0L/(g･cm) or less. When higher light transmittance is required, the maximum value of the light absorption coefficient A is preferably 0.8L/(g･cm) or less, 0.5L/(g･cm) or less is better, and 0.2L/(g･cm) The following is more preferred, and less than 0.01L/(g･cm) is still more preferred. The lower limit value is not particularly limited, but it is actually 0.0001L/(g･cm) or more. In the composition of the present invention, by setting the maximum value of the light absorption coefficient A to be equal to or less than the above-mentioned upper limit, the hardenability in the depth of the pattern is improved and the resolution of the pattern is excellent.

＜＜Weight average molecular weight＞＞ The weight average molecular weight of the translucent polymerizable compound is 800 or more, preferably 1,000 or more, more preferably 1,500 or more, and more preferably more than 2,000. The upper limit of the weight average molecular weight is not particularly limited. For example, it is preferably 100,000 or less, more preferably 50,000 or less, more preferably 10,000 or less, still more preferably 8,000 or less, still more preferably 5,000 or less, and 3,500 or less. Better still, especially below 3,000. By setting the molecular weight to be equal to or higher than the above lower limit, the volatility of the compound is suppressed, and the properties of the composition and the coating film become stable. In addition, good viscosity for maintaining the shape of the coating film can also be ensured. Furthermore, by supplementing the effect of suppressing the amount of the release agent to a small amount, good release properties of the film can be achieved. By setting the molecular weight to less than the above upper limit, it is easier to ensure low viscosity (fluidity) required for pattern filling, so it is preferable.

＜＜Content＞＞ The content of the above-mentioned translucent polymerizable compound in the curable composition for imprinting is 50% by mass or more of the total solid content of the composition, preferably 70% by mass or more, more preferably 90% by mass or more, and 95% by mass. The above is further preferred. As an upper limit, it is actually 99.9 mass % or less. By containing the translucent polymerizable compound in an amount equal to or more than the above lower limit, sufficient translucency can be obtained, and when the film is cured by light irradiation, curability deep in the film is improved, so this is preferable. One type of translucent polymerizable compound may be used, or a plurality of types may be used. When using multiple types, the total amount should be within the above range.

＜＜Polymerizable group equivalent＞＞ Among the light-transmitting polymerizable compounds used in the present invention, the polymerizable group equivalent weight is preferably 130 or more, more preferably 150 or more, further preferably 160 or more, further preferably 190 or more, and still more preferably 240 or more. Better. The upper limit of the polymerizable group equivalent is preferably 2,500 or less, more preferably 1,800 or less, more preferably 1,000 or less, still more preferably 500 or less, still more preferably 350 or less, and may be 300 or less. .

The polymerizable group equivalent is calculated from the following formula. (polymerizable basis equivalent) =(Number average molecular weight of the polymerizable compound)/(Number of polymerizable groups in the polymerizable compound)

If the polymerizable group equivalent of the translucent polymerizable compound is too low, the elastic modulus during hardening may increase and the mold releasability may deteriorate. On the other hand, if the polymerizable group equivalent of the translucent polymerizable compound is too high, the crosslinking density of the cured product pattern may significantly decrease, and the resolution of the transferred pattern may deteriorate.

In the case of the silicon-containing compound described below, the number of polymerizable groups in the translucent polymerizable compound is preferably 2 or more per molecule, more preferably 3 or more, and still more preferably 4 or more. The upper limit is preferably 50 or less, more preferably 40 or less, further preferably 30 or less, and still more preferably 20 or less. In the case of a ring-containing compound, two or more are preferably present in one molecule. As an upper limit, 4 or less is preferred, and 3 or less is more preferred. Alternatively, in the case of a dendrimer-type compound, the number is preferably 5 or more in one molecule, more preferably 10 or more, and still more preferably 20 or more. The upper limit is preferably 1,000 or less, more preferably 500 or less, and still more preferably 200 or less.

＜＜Viscosity＞＞ The viscosity of the translucent polymerizable compound at 23°C is preferably 100 mPa･s or more, more preferably 120 mPa･s or more, and further preferably 150 mPa･s or more. The upper limit of the viscosity is preferably 2000 mPa･s or less, more preferably 1500 mPa･s or less, and further preferably 1200 mPa･s or less.

Unless otherwise stated, the viscosity in this manual is assumed to be using an E-type rotational viscometer RE85L manufactured by Toki Sangyo Co., Ltd. and a standard cone and rod (1°34'×R24). The temperature of the sample cup is adjusted to Value measured at 23°C. Other details regarding measurement comply with JISZ8803:2011. Two samples were prepared for each level and measured three times. The arithmetic mean of a total of 6 times was adopted as the evaluation value.

＜＜Polymerizable group＞＞ The type of polymerizable group contained in the light-transmitting polymerizable compound is not particularly limited, and examples thereof include ethylenically unsaturated groups, cyclic ether groups (epoxy groups, glycidyl groups, oxetanyl groups), etc. Unsaturated groups are preferred. Examples of the ethylenically unsaturated group include (meth)acrylyl group, (meth)acryloxy group, (meth)acrylamide group, vinyl group, vinyloxy group, allyl group, and vinyl group. A phenyl group, a (meth)acrylyl group or a (meth)acryloxy group is more preferred, and an acrylyl group or an acryloxy group is still more preferred. The polymerizable group defined here is called Qp.

＜＜Silicon-containing compounds･Ring-containing compounds･dendrimer-type compounds＞＞ The type of the translucent polymerizable compound is not particularly limited as long as it has the above characteristics. In particular, from the viewpoint of setting the maximum value of the absorption coefficient A of the translucent polymerizable compound within a specific range, compounds containing silicon atoms (Si) (silicon-containing compounds) or compounds containing a cyclic structure (ring-containing compounds) compounds) are preferred, and compounds containing silicon are even more preferred.

<<<Silicon-containing compounds>>>> Examples of silicon-containing compounds include compounds having a silicon skeleton. Specific examples include compounds having at least one of a siloxane structure of a D unit represented by the following formula (S1) and a siloxane structure of a T unit represented by the formula (S2). [Chemical formula 1] R ^S1 to R ^S3 are each independently a hydrogen atom or a monovalent substituent, and a monovalent substituent is preferred. As a substituent, 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, and more preferably 1 to 12 carbon atoms) More preferably, 1 to 6 are further preferred), among which a cyclic or chain (linear or branched) alkyl group (carbon number 1 to 12 is preferred, 1 to 6 is more preferred, 1 to 3 is more preferred) or a group containing a polymerizable group is preferred. The preferable range of the number of polymerizable groups contained in the silicon-containing compound is as described above.

As specific structural examples of the silicon-containing compound, when expressed as a partial structure, the following formulas s-1 to s-9 can be cited. Q in the formula is a group containing a polymerizable group Qp. A plurality of these structures may exist in the compound, or they may exist in combination.

[Chemical formula 2]

The compound containing silicon is preferably a reaction product of silicon resin and (meth)acrylic resin (for example, hydroxyalkyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate is preferred). . More specifically, a graft resin in which a silicone resin is introduced into a side chain of a (meth)acrylic resin, such as a hydroxyl group, is preferred. Examples of reactive silicone resins include modified silicone resins having the above-mentioned silicone skeleton, such as monoamine-modified silicone resins, diamine-modified silicone resins, special amine-modified silicone resins, epoxy-modified silicone resins, and lipid-modified silicone resins. Cyclic epoxy modified silicone resin, methanol modified silicone resin, thiol modified silicone resin, carboxyl modified silicone resin, hydrogen modified silicone resin, amine/polyether modified silicone resin, epoxy/polyether modified silicone Resin, epoxy/aralkyl modified silicone resin, etc.

＜＜＜Compounds containing rings＞＞ Examples of the cyclic structure of the ring-containing compound (ring-containing compound) include aromatic rings and alicyclic rings. Examples of the aromatic ring include aromatic hydrocarbon rings and aromatic heterocyclic rings. As the aromatic hydrocarbon ring, one having 6 to 22 carbon atoms is preferred, one having 6 to 18 carbon atoms is more preferred, and one having 6 to 10 carbon atoms is even more preferred. Specific examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a sulfa ring, a fentanyl ring, a benzocyclooctene ring, an acenaphthene ring, a biphenyl ring, an indene ring, an indene ring, Tribenzene ring, pyrene ring, pyrene ring, perylene ring, tetrahydronaphthalene ring, etc. Among them, a benzene ring or a naphthalene ring is preferred, and a benzene ring is even more preferred. The aromatic ring may have a plurality of connected structures, and examples thereof include a biphenyl structure and a diphenylalkane structure (for example, 2,2-diphenylpropane). (The aromatic hydrocarbon ring specified here is called aCy) As the aromatic heterocyclic ring, those having 1 to 12 carbon atoms are preferred, those having 1 to 6 carbon atoms are more preferred, and those having 1 to 5 carbon atoms are still 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,㗁oxadiazole ring, 㗁ethazole ring, pyridine ring, pyridine ring, pyrimidine ring, tetrazole ring, isoindole ring, indole ring, indazole ring, purine ring, quinine ring, isoquinoline ring , quinoline ring, quinoline ring, neridine ring, quinoline ring, quinazoline ring, cinnoline ring, carbazole ring, acridine ring, quinoline ring, phenidine ring, quinoline ring Thiene ring, coffee mouth ejector well ring, etc. (The aromatic heterocycle specified here is called hCy) The alicyclic ring preferably has 3 to 22 carbon atoms, more preferably 4 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms. Specifically, examples of aliphatic hydrocarbon rings include cyclopropane ring, cyclobutane ring, cyclobutene ring, cyclopentane ring, cyclohexane ring, cyclohexene ring, cycloheptane ring, and cyclooctane ring. Alkane ring, dicyclopentadiene ring, spiral decane ring, spiral nonane ring, tetrahydrodicyclopentadiene ring, octahydronaphthalene ring, decahydronaphthalene ring, hexahydroindane ring, bornane ring, Bornane ring, norbornene ring, isobornane ring, tricyclodecane ring, tetracyclododecane ring, adamantane ring, etc. As aliphatic heterocyclic rings, pyrrolidine ring, imidazolidine ring, piperidine ring, piperidine ring, morpholine ring, ethylene oxide ring, oxybutane ring, oxolane ring, guchisakisan ring, di Kuchikakou Mountain Ring and so on. (The alicyclic ring specified here is called fCy)

In the present invention, when the light-transmitting polymerizable compound is a compound containing a ring, a compound containing an aromatic hydrocarbon ring is preferred, and a compound having a benzene ring is more preferred. For example, compounds having the structure of the following formula C-1 can be cited.

[Chemical formula 3] In the formula, Ar represents the above-mentioned aromatic hydrocarbon ring or aromatic heterocyclic ring. L ¹ and L ² are each independently a single bond or a linking group. Examples of the linking group include an oxygen atom (oxygen group), a carbonyl group, an amino group, an alkylene group (preferably the number of carbon atoms is 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3), or a combination thereof. The formed group. Among them, a (poly)alkyleneoxy group is preferred. The (poly)alkyleneoxy group may have one alkyleneoxy group, or may have a plurality of repeating alkyleneoxy groups connected. In addition, the sequential combination of an alkylene group and an oxy group is particularly limited. The repeating number of the alkyleneoxy group is preferably 1 to 24, more preferably 1 to 12, and still more preferably 1 to 6. In addition, the (poly)alkyleneoxy group is connected to the ring Ar that serves as the core or the polymerizable group Q, and an alkylene group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms) may be present in the middle. , 1 to 6 are further preferred). Therefore, it can become (poly)alkyleneoxy=alkylene group. R ³ is an optional substituent, and examples thereof include an alkyl group (preferably with a carbon number of 1 to 12, more preferably with a carbon number of 1 to 6, and even more preferably with a carbon number of 1 to 3), and an alkenyl group (preferably with a carbon number of 2 to 12, 2 to 6 is more preferred, 2 to 3 is further preferred), aryl group (carbon number 6 to 22 is preferred, 6 to 18 is more preferred, 6 to 10 is further preferred), aralkyl group (carbon number 7 to 23 are preferred, 7 to 19 are more preferred, 7 to 11 are further preferred), hydroxyl group, carboxyl group, alkoxy group (carbon number 1 to 24 is preferred, 1 to 12 is more preferred, 1 to 6 More preferably), acyl group (carbon number 2 to 12 is preferred, 2 to 6 is more preferred, 2 to 3 is further preferred), aryl group (carbon number 7 to 23 is preferred, 7 to 19 is better, and 7 to 11 is even better). L ³ is a single bond or connecting group. Examples of the linking group include the above-mentioned L ¹ and L ² . When n3 is 3 or less, it is preferable, 2 or less is more preferable, 1 or less is still more preferable, and 0 is extremely good. Q ¹ and Q ² are each independently a polymerizable group, and the above-mentioned example of the polymerizable group Qp is preferred. In a ring-containing compound, an increase in the number of side chains having a polymerizable group allows a strong cross-linked structure to be formed upon hardening, thereby tending to improve resolution. From this point of view, nq is preferably 2 or more. The upper limit is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. Similarly, from the viewpoint of easily forming a uniform cross-linked structure, when introducing a polymerizable group-containing group or substituent into the cyclic structure, it is preferable to arrange the substituent in a series.

＜＜＜Dendrimer type compounds＞＞ The light-transmitting polymerizable compound may be a dendrimer type compound. Dendrimers represent dendrimers having a structure that branches regularly from a center. Dendrimers are composed of a central molecule (the backbone) called the core and side chain portions (the branches) called the dendrites. Generally, a compound that is fan-shaped as a whole may also be a dendritic polymer whose dendrites are expanded into a semicircular or circular shape. A polymerizable compound having a group having a polymerizable group can be introduced into the dendritic portion of the dendrimer (for example, the terminal portion remote from the core). If a (meth)acryl group is used as the polymerizable group to be introduced, the polyfunctional (meth)acrylate can be a dendrimer type. The preferable range of the number of polymerizable groups in the dendrimer-type compound is as described above. Regarding the dendrimer type compound, for example, the matters disclosed in Japanese Patent No. 5512970 can be referred to, and this description is incorporated into this specification by reference.

＜Other polymerizable compounds＞ The curable composition for imprinting of the present invention may contain polymerizable compounds other than the translucent polymerizable compound (hereinafter, may be referred to as other polymerizable compounds). The other polymerizable compound is preferably a polyfunctional polymerizable compound having two or more polymerizable groups. The number of polymerizable groups of other polymerizable compounds is preferably two or more per molecule. The upper limit is preferably 4 or less, more preferably 3 or less, and still more preferably 2 or less.

Examples of other polymerizable compounds include compounds represented by the following formulas. [Chemical formula 4]

In the formula, R ²¹ is an organic group with q valence, R ²² is a hydrogen atom or a methyl group, and q is an integer of 2 or more. It is preferable that q is an integer from 2 to 7, an integer from 2 to 4 is more preferable, 2 or 3 is still more preferable, and 2 is still more preferable. It is preferable that R ²¹ is an organic group having a valence of 2 to 7, an organic group having a valence of 2 to 4 is more preferable, an organic group having a valence of 2 or 3 is still more preferable, and a divalent organic group is still more preferable. R ²¹ is preferably a hydrocarbon group having at least one structure selected from linear, branched and cyclic structures. The carbon number of the hydrocarbon group is preferably 2 to 20, more preferably 2 to 10. When R ²¹ is a divalent organic group, an organic group represented by the following formula (1-2) is preferred. [Chemical formula 5] In the formula, Z ¹ and Z ² are each independently a single bond, -Alk- or -Alk-O- (the order of Alk and O has nothing to do, and it can be -O-Alk- in the formula). Alk represents an alkylene group (the number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 3), and may have a substituent within a range that does not impair the effects of the present invention.

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

[Chemical formula 6]

R ¹⁰¹ to R ¹¹⁷ are optional substituents. Among them, alkyl group (carbon number 1 to 12 is preferred, 1 to 6 is more preferred, 1 to 3 is even more preferred), aralkyl group (carbon number 7 to 21 is preferred, 7 to 15 is more preferred, 7 to 11 are more preferred), aryl group (carbon number 6 to 22 is preferred, 6 to 18 is more preferred, 6 to 10 is further preferred), thienyl, furyl, (meth)acrylyl group , (meth)acryloxy group, (meth)acryloxyalkyl group (the alkyl group has preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and further preferably 1 to 6 carbon atoms) is Better. 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 , R ¹¹¹ when there are plural ones, R 112 when there are plural ones, R ¹¹² when there are plural ones R ¹¹³ , R ¹¹⁴ when there are plural ones, R ¹¹⁵ when there are plural ones, R ¹¹⁶ when there are plural ones, and R ¹¹⁷ when there are plural ones, may be bonded to each other to form a ring. Ar is an aryl group (the number of carbon atoms is preferably 6 to 22, more preferably 6 to 18, and still more preferably 6 to 10). Specific examples include phenyl group, naphthalenediyl, anthracenediyl, and phenanthrenediyl. Two bases, two bases. hCy ¹ is a heterocyclic group (the number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, and further preferably 2 to 5), and more preferably a 5- or 6-membered ring. Specific examples of the heterocyclic ring constituting hCy ¹ include the above-mentioned aromatic heterocyclic hCy, pyrrolidone ring, tetrahydrofuran ring, tetrahydropyran ring, morpholine ring, etc. Among them, thiophene ring, furan ring, dibenzo Furan ring is preferred. n and m are natural numbers of 100 or less, 1 to 12 are preferred, 1 to 6 are more preferred, and 1 to 3 are further preferred. p is an integer equal to or greater than 0 and equal to or less than the maximum number of substitutions possible for each ring. In each case, the upper limit is preferably half or less of the maximum number that can be substituted independently, more preferably 4 or less, and still more preferably 2 or less.

In addition, as for other polymerizable compounds, the polymerizable group equivalent weight defined above is preferably 150 or more, more preferably 160 or more, further preferably 190 or more, and still more preferably 240 or more. The upper limit is preferably 2,500 or less, more preferably 1,800 or less, and further preferably 1,000 or less.

It is preferable that other polymerizable compounds have a cyclic structure. Examples of the cyclic structure include aromatic hydrocarbon ring aCy, aromatic heterocyclic ring hCy, and alicyclic ring fCy.

Examples of other polymerizable compounds include compounds described in paragraphs 0017 to 0024 and Examples of Japanese Patent Application Laid-Open No. 2014-090133, and compounds described in paragraphs 0024 to 0089 of Japanese Patent Application Laid-Open No. 2015-009171. , the compounds described in paragraphs 0023 to 0037 of Japanese Patent Application Laid-Open No. 2015-070145, and the compounds described in paragraphs 0012 to 0039 of International Publication No. 2016/152597, and these are incorporated by reference in this specification.

The other polymerizable compound may be contained in the curable composition for imprinting in an amount of 10% by mass or more. The upper limit is actually less than 30% by mass relative to the translucent polymerizable compound. As for other polymerizable compounds, one type may be used or a plurality of types may be used. When using multiple types, the total amount should be within the above range.

<Photopolymerization initiator> The curable composition for imprinting used in the present invention contains a photopolymerization initiator. The maximum value of the absorption coefficient B of the photopolymerization initiator is 5,000L/(mol･cm) or more, preferably 10,000L/(mol･cm) or more, and more preferably 25,000L/(mol･cm) or more. The upper limit of the maximum value of the absorption coefficient B is, for example, 100,000 L/(mol･cm) or less, and actually it is 50,000 L/(mol･cm) or less. Examples of the photopolymerization initiator include oxime ester-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, arylylphosphine oxide-based photopolymerization initiators, and alkylphosphine oxide-based photopolymerization initiators. starter. Among them, in the curable composition for imprinting of the present invention, it is preferable to use an oxime ester-based photopolymerization initiator. Here, the oxime ester refers to a compound having a connection structure of the following formula (1) in the molecule, preferably having a connection structure of the formula (2). * in the formula represents the bond bonded to the organic group. [Chemical Formula 7] The molecular weight of the photopolymerization initiator is not particularly limited, but it is preferably 100 or more, more preferably 150 or more, and still more preferably 200 or more. The upper limit is preferably 2,000 or less, more preferably 1,500 or less, and still more preferably 1,000 or less. Specific examples of the photopolymerization initiator include BASF SE's IRGACURE819 (8,200), OXE-01 (17,300), OXE-02 (21,500), OXE-04 (33,000), Darocure1173, IrgacureTPO, and ADEKA's NCI. -831 (31,500), NCI-831E (32,000), etc. (all are trade names, and the maximum value of the absorption coefficient B is in parentheses.).

The content of the photopolymerization initiator is 0.5% by mass or more, preferably 1% by mass or more, and more preferably 2.0% by mass or more based on the total solid content of the curable composition for imprinting. The upper limit is 8.0 mass% or less, preferably 6.0 mass% or less. If the content of the photopolymerization initiator is equal to or more than the above-mentioned lower limit, sufficient curing properties can be ensured and good resolution can be exerted. On the other hand, by setting it below the above-mentioned upper limit, it is possible to prevent the initiator from precipitating during coating and refrigerated storage, causing coating defects and the like. One type of photopolymerization initiator may be used, or a plurality of types may be used. When using multiple types, the total amount should be within the above range.

＜Mold release agent＞ The curable composition for imprinting of the present invention contains a release agent. The content of the release agent is 0.1 mass% or more, preferably 0.3 mass% or more, more preferably 0.5 mass% or more, and still more preferably 0.6 mass% or more, based on the total solid content of the composition. The upper limit is less than 1.0 mass%, preferably 0.9 mass% or less, and more preferably 0.85 mass% or less. By setting the content of the release agent to be equal to or more than the above-mentioned lower limit, the releasability becomes good and it is possible to prevent peeling of the cured film and damage to the mold during release. Furthermore, by setting it below the above-mentioned upper limit, the influence of the release agent does not cause an excessive decrease in the pattern strength during curing, and the effects of the specific translucent polymerizable compound and the specific photopolymerization initiator can be exerted. The synergistic effect enables good resolution. One type of release agent may be used, or a plurality of types may be used. When using multiple types, the total amount should be within the above range. The type of release agent is not particularly limited, but it is preferred that the release agent has the function of segregating at the interface with the casting mold and effectively promoting release from the casting mold. In the present invention, it is preferred that the release agent contains substantially no fluorine atoms and silicon atoms. Substantially free means that the total amount of fluorine atoms and silicon atoms is 1 mass % or less of the release agent, preferably 0.5 mass % or less, more preferably 0.1 mass % or less, and still more preferably 0.01 mass % or less. By using a release agent that does not contain substantially fluorine atoms and silicon atoms, it is relatively feasible to change the curable composition for imprint into one that achieves high release properties of the film and has excellent processing resistance against etching and the like. good. The release agent used in the present invention is preferably a surfactant. Alternatively, an alcohol compound having at least one hydroxyl group at the terminal or a compound having a (poly)alkylene glycol structure in which the hydroxyl group is etherified ((poly)alkylene glycol compound) is preferred. The surfactant and the (poly)alkylene glycol compound are preferably non-polymerizable compounds that do not have a polymerizable group Qp. In addition, (poly)alkylene glycol may have one alkylene glycol structure, or may have a plurality of repeated alkylene glycol structures connected.

＜＜Surfactant＞＞ As the surfactant that can be used as a release agent in the present invention, a nonionic surfactant is preferred. Nonionic surfactants are compounds having at least one hydrophobic part and at least one nonionic hydrophilic part. The hydrophobic part and the hydrophilic part may exist respectively at the ends of the molecule, or they may exist inside. The hydrophobic part is composed of, for example, a hydrocarbon group. The number of carbon atoms in the hydrophobic part is preferably 1 to 25, more preferably 2 to 15, more preferably 4 to 10, and even more preferably 5 to 8. The nonionic hydrophilic part has an alcoholic hydroxyl group, a phenolic hydroxyl group, an ether group (preferably a (poly)alkyleneoxy group, a cyclic ether group), a amide group, a amide imine group, a urea group, and an amine group. At least one group selected from the group consisting of a hydroxyformate group, a cyano group, a styrylamide group, a lactone group, a lactam group and a cyclic carbonate group is preferred. Among them, compounds having an alcoholic hydroxyl group or an ether group (preferably a (poly)alkyleneoxy group or a cyclic ether group) are more preferred.

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

The (poly)alkylene glycol compound is preferably a (poly)alkylene glycol compound having an alkyleneoxy group or a polyalkyleneoxy group, and more preferably a (poly)alkyleneoxy group having an alkylene group containing 1 to 6 carbon atoms. . Specifically, it is preferable to have a (poly)ethyleneoxy group, a (poly)propyleneoxy group, a (poly)butyleneoxy group or a mixed structure thereof, and it is preferable to have a (poly)ethyleneoxy group, (poly)propyleneoxy group Or a mixed structure of these is more preferable, and having a (poly)propyleneoxy group is even more preferable. The (poly)alkylene glycol compound may be substantially composed only of (poly)alkyleneoxy groups by removing the terminal substituent. Here, substantially it means that the constituent elements other than the (poly)alkyleneoxy group are 5 mass % or less of the total, and preferably 1 mass % or less. In particular, the (poly)alkylene glycol compound is preferably a compound consisting essentially only of a (poly)propyleneoxy group.

The number of repeating alkyleneoxy groups in the (poly)alkylene glycol compound is preferably 3 to 100, more preferably 4 to 50, further preferably 5 to 30, and still more preferably 6 to 20.

As long as the terminal hydroxyl group of the (poly)alkylene glycol compound is etherified, the remaining terminal may be a hydroxyl group, or the hydrogen atom of the terminal hydroxyl group may be substituted. As a group in which the hydrogen atom of the terminal hydroxyl group may be substituted, an alkyl group (that is, (poly)alkylene glycol alkyl ether) or a hydroxyl group (that is, (poly)alkylene glycol ester) is preferred. Compounds having a plurality of (preferably 2 or 3) (poly)alkylene glycol chains via a linking group can also be suitably used.

Preferable specific examples of the (poly)alkylene glycol compound include polyethylene glycol, polypropylene glycol (for example, manufactured by Wako Pure Chemical Industries, Ltd.), mono- or dimethyl ethers thereof, and monomethyl ethers thereof. Or dibutyl ether, mono or dioctyl ether, mono or dicetyl ether, monostearate, monooil ester, polyoxyethylene glyceryl ether, polyoxypropylene glyceryl ether, polyoxyethylene lauryl ether, Such trimethyl ethers.

The (poly)alkylene glycol compound is preferably a compound represented by the following formula (P1) or (P2). [Chemical formula 8] R ^P1 in the formula can be chain or cyclic, straight chain or branched alkylene group (carbon number 1 to 12 is preferred, 1 to 6 is more preferred, 1 to 3 is further better). R ^P2 and R ^P3 can be hydrogen atoms or chain or cyclic, and can be linear or branched alkyl groups (carbon number is preferably 1 to 36, more preferably 2 to 24, 3 to 24) 12 is further better). It is preferable that p is an integer of 1-24, and it is more preferable that it is an integer of 2-12. R ^P4 is a q-valent linking group. The linking group composed of organic groups is preferred, and the linking group composed of hydrocarbons is preferred. Specifically, examples of the linking group composed of hydrocarbons include linking groups of an alkane structure (preferably, the number of carbon atoms is 1 to 24, more preferably 2 to 12, and further preferably 2 to 6), and a linking group of an olefin structure. (The number of carbon atoms is preferably 2 to 24, and the number of carbon atoms is preferably 2 to 12, and the number of carbon atoms is 2 to 12, and the number of carbon atoms is 2 to 6, and the number of carbon atoms is 2 to 6, and the number of carbon atoms is 6 to 22, and the number of carbon atoms is 6 to 18, and the number of carbon atoms is 6 to 18, and the number of carbon atoms is 6 to 18, and the number of carbon atoms is 6 to 18. ~10 is further preferred). It is preferable that q is an integer of 2 to 8, more preferably an integer of 2 to 6, and still more preferably an integer of 2 to 4.

The weight average molecular weight of the alcohol compound or (poly)alkylene glycol compound used as the release agent is preferably 150 to 6,000, more preferably 200 to 3,000, further preferably 250 to 2,000, and 300 to 1,200. Better still. Examples of commercially available (poly)alkylene glycol compounds that can be used in the present invention include OLFIN E1010 (manufactured by Nissan Chemical Industries, Ltd.) and Brij35 (manufactured by KISHIDA CHEMICAL Co., Ltd.). wait.

<Polymerization Inhibitor> The curable composition for imprinting of the present invention preferably contains at least one polymerization inhibitor. The polymerization inhibitor has the function of quenching (deactivating) reactive substances such as free radicals generated from the photopolymerization initiator, and inhibits the reaction of the curable composition for imprinting at low exposure levels. In particular, when other polymerizable compounds are contained, the polymerization inhibitor can be sufficiently dissolved and the above-mentioned effects can be easily exhibited. As the polymerization inhibitor, for example, hydroquinone, 4-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylpyrocatechol, 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-phenylhydroxylamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine Tetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquin Phinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamine)phenol, N- Nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, etc. In addition, the polymerization inhibitor described in paragraph 0060 of Japanese Patent Application Laid-Open No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used. Specific examples of commercially available polymerization inhibitors include Q-1300, Q-1301, TBHQ (manufactured by Wako Pure Chemical Industries, Ltd.), Quino Power series (manufactured by KAWASAKI KASEI CHEMICALS LTD.), and the like. Furthermore, the following compounds (Me is methyl) can also be used. [Chemical formula 9] The content of the polymerization inhibitor is preferably 0.1 to 5% by mass, and more preferably 0.5 to 3% by mass. By setting the content to be equal to or more than the above-mentioned lower limit, the reactivity of the photopolymerization initiator can be effectively exerted. Furthermore, by setting it to less than the above-mentioned upper limit, collapse of the transfer pattern can be prevented and effective patterning can be performed. One type of polymerization inhibitor may be used, or a plurality of types may be used. When using plural types, the total amount is preferably within the above range.

＜Solvent＞ The above-mentioned curable composition for imprinting may contain a solvent. Solvent refers to a compound that is liquid at 23°C and has a boiling point below 250°C. When a solvent is contained, the content is preferably 1% by mass or more, more preferably 10% by mass or more, and still more preferably 30% by mass or more. In addition, the content is preferably 99.5% by mass or less, more preferably 99% by mass or less, and still more preferably 98% by mass or less. 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 most abundant component in the solvent is preferably 200°C or lower, and more preferably 160°C or lower. By setting the boiling point of the solvent to be equal to or lower than the above-mentioned temperature, the solvent in the curable composition for imprint can be removed by baking. The lower limit of the boiling point of the solvent is not particularly limited, but is actually above 60°C, and may be above 80°C or even above 100°C. 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, acetate, alkoxypropionate, chain ketone, and cyclic ketone. , lactones and alkylene carbonates. Examples of the alkoxy alcohol include methoxyethanol, ethoxyethanol, methoxypropanol (for example, 1-methoxy-2-propanol), ethoxypropanol (for example, 1-ethoxypropanol) methyl-2-propanol), propoxypropanol (e.g., 1-propoxy-2-propanol), methoxybutanol (e.g., 1-methoxy-2-butanol, 1-methyl oxy-3-butanol), ethoxybutanol (e.g., 1-ethoxy-2-butanol, 1-ethoxy-3-butanol), methylpentanol (e.g., 4-methylpentanol -2-pentanol), etc. As the propylene glycol monoalkyl ether carboxylate, at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate is preferred. , Propylene glycol monomethyl ether acetate is particularly preferred. Furthermore, as the propylene glycol monoalkyl ether, propylene glycol monomethyl ether or propylene glycol monoethyl ether is preferred. As the lactic acid ester, ethyl lactate, butyl lactate or propyl lactate is preferred. As acetate, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate or acetic acid 3- Methoxybutyl ester is preferred. As the alkoxypropionate ester, methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferred. As chain ketones, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, phenyl Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetone acetone, ionone, diacetone alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone or methyl pentyl Base ketone is preferred. 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-mentioned components, it is preferable to use an ester-based solvent having a carbon number of 7 or more (preferably 7 to 14, more preferably 7 to 12, and even more preferably 7 to 10) and with a number of hetero atoms of 2 or less. 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, and propyl acetate. Amyl acid, hexyl propionate, butyl propionate, isobutyl isobutyrate, heptyl propionate, butyl butyrate, etc., isoamyl acetate is particularly preferred. In addition, those having a flash point (hereinafter also referred to as fp) of 30° C. or higher are also preferably used. As this component (M2), propylene glycol monomethyl ether (fp: 47°C), ethyl lactate (fp: 53°C), ethyl 3-ethoxypropionate (fp: 49°C), methylpentyl Ketone (fp: 42℃), cyclohexanone (fp: 30℃), amyl acetate (fp: 45℃), methyl 2-hydroxyisobutyrate (fp: 45℃), γ-butyrolactone (fp : 101℃) or propylene carbonate (fp: 132℃) is preferred. Among these, propylene glycol monoethyl ether, ethyl lactate (EL), amyl acetate, or cyclohexanone are further preferred, and propylene glycol monoethyl ether or ethyl lactate are particularly preferred. In addition, the "flash point" here refers to the value described in the reagent catalog of Tokyo Chemical Industry Co., Ltd. or Sigma-Aldrich Co. LLC. As a better solvent, it is selected from the group consisting of water, propylene glycol monomethyl ether acetate (PGMEA), ethoxyethyl propionate, cyclohexanone, 2-heptanone, γ-butyrolactone, butyl acetate At least one of the group consisting of ester, propylene glycol monomethyl ether (PGME), ethyl lactate and 4-methyl-2-pentanol, at least one selected from the group including PGMEA and PGME is further preferred. good.

＜UV absorber＞ The curable composition for imprinting of the present invention may contain an ultraviolet absorber. The ultraviolet absorber has the function of inhibiting the reaction light from reaching the photopolymerization initiator by absorbing light leakage (light spots) generated during exposure, thereby inhibiting the reaction of the curable composition for imprinting at low exposure levels. Examples of types of ultraviolet absorbers include benzotriazole-based, Sankui-based, cyanoacrylate-based, benzophenone-based, and benzoic acid-based absorbers. The content of the ultraviolet absorber is preferably 0.01 to 5% by mass, and more preferably 0.02 to 3% by mass. One type of ultraviolet absorber may be used, or a plurality of types may be used. When using plural types, the total amount is preferably within the above range.

＜Other ingredients＞ Other components can also be used in the curable composition for imprinting of the present invention. For example, sensitizers, antioxidants, etc. may also be included. The content is not particularly limited, and about 0.01 to 20% by mass of the total solid content of the composition can be appropriately blended.

<Physical Properties> In the present invention, a cured film with a thickness of 300 nm formed by taking the curable composition for imprinting into a film shape and irradiating it with an exposure dose of 300 mJ/cm ² has an elastic coefficient calculated by the Oliver-Pharr method of 1.5 GPa or more. It is preferable, and it is more preferable that it is 1.8 GPa or more, and it is still more preferable that it is 2.0 GPa or more. As an upper limit, it is actually 4.0GPa or less. When the elastic coefficient of the cured film of the curable composition for imprint is not less than the above-mentioned lower limit, sufficient strength can be provided to the imprint pattern, and resolution can be improved. On the other hand, by setting it below the upper limit, the releasability from the mold is improved and defects are reduced.

The difference between the surface tension of the total solid content of the curable composition for imprinting of the present invention and the surface tension of the total solid content of the curable composition for imprinting excluding the release agent is 1.5 mN/m or less. It is better, 1.0mN/m or less is more preferable, and 0.8mN/m or less is still more preferable. The lower limit value is, for example, 0.01 mN/m or more, and actually it is 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 a homogeneous cured film can be formed.

＜Save Container＞ As a container for containing the curable composition for imprint used in the present invention, a conventionally known container can be used. In addition, as a storage container, in order to prevent impurities from being mixed into raw materials or compositions, it is also preferable to use a multi-layer bottle with an inner wall of six types of six-layer resins or a bottle with six types of resins formed into a seven-layer structure. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.

＜Method for manufacturing hardened material and its pattern＞ ＜＜Application to substrates＞＞ The pattern manufacturing method of the present invention includes applying the present invention to a substrate, an adhesion layer (a layer between a substrate and a curable composition layer for imprinting including an underlayer film, a primer layer, etc.), etc. The step of imprinting the hardening composition. The curable composition for imprinting is preferably applied to the substrate by spin coating. As the adhesive layer, for example, those described in paragraphs 0017 to 0068 of Japanese Patent Application Laid-Open No. 2014-024322, paragraphs 0016 to 0044 of Japanese Patent Application Laid-Open No. 2013-093552, and those described in Japanese Patent Application Laid-Open No. 2014-093385 can be used. The adhesive layer, the adhesive layer described in Japanese Patent Application Publication No. 2013-202982, and these contents are incorporated into this specification. The method of manufacturing a pattern of the present invention may be a method of manufacturing a semiconductor element including this. The pattern size, that is, the width of the pattern in the pattern manufacturing method of the present invention is preferably 50 nm or less, more preferably 30 nm or less, and further preferably 25 nm or less. As a lower limit value, it is actually 5 nm or more.

＜＜Optical nanoimprint lithography＞＞ Optical nanoimprint lithography using a curable composition for imprinting is used as at least one of the casting mold material and the substrate to select a light-transmitting material. In one embodiment of the present invention, the above-mentioned curable composition for imprinting of the present invention is applied to a substrate or a mold, and the curable composition for imprinting (pattern forming layer) is sandwiched between the mold and the substrate. Light irradiation is performed below to form a pattern. Usually, a translucent mold is pressure-welded to the imprint curable composition, and light is irradiated from the back side of the mold to harden the pattern forming layer. Furthermore, in another embodiment, the curable composition for imprinting can be applied to a translucent substrate, the mold can be pressed against the curable composition for imprinting, and light can be irradiated from the back surface of the substrate to cause the imprinting process to be formed. Hardened with a hardening composition. The above-mentioned light irradiation may be performed while the mold is in close contact, or may be performed after peeling off the mold. It is preferably performed in the state of the mold being in close contact. It is better to use a mold with a pattern to be transferred. The pattern on the above-mentioned mold can be formed according to the desired processing accuracy by, for example, photolithography or electron beam scanning, but the method of forming the mold pattern is not particularly limited. Furthermore, a pattern formed by a pattern forming method can also be used as a mold. The translucent molding material is not particularly limited as long as it has predetermined strength and durability. Specific examples include glass, quartz, PMMA, translucent resins such as polycarbonate resin, transparent metal vapor-deposited films, flexible films such as polydimethylsiloxane, photocurable films, metal films, and the like. The non-translucent molding material used when using a translucent substrate is not particularly limited as long as it has a predetermined strength. Specific examples include ceramic materials, vapor-deposited films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, and substrates such as SiC, silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon. etc., there are no special restrictions. When imprinting is performed using a curable composition for imprinting, it is usually best to perform the imprinting at a mold pressure of 10 atmospheres or less. By setting the mold pressure to 10 atmospheres or less, the mold or the substrate is less likely to deform and the pattern accuracy tends to be improved. Furthermore, it is also preferable in that the device tends to be smaller due to low pressure. Regarding the mold pressure, it is preferable to select a range that can ensure the uniformity of mold transfer within a range in which the residual film of the curable composition for imprinting on the convex portion of the mold is reduced.

The amount of light irradiation in the step of irradiating the imprinting curable composition layer with light may be sufficiently larger than the irradiation amount required for curing. The amount of irradiation required for curing is appropriately determined by checking the consumption of unsaturated bonds of the curable composition for imprinting. Among them, in the present invention, in order to prevent excessive hardening of adjacent parts of the mold, it is preferable to set the exposure dose to a low level. The substrate temperature during light irradiation is usually at room temperature, but in order to improve reactivity, light irradiation may be performed while heating. If the vacuum state is used as the previous stage of light irradiation, it has the effect of preventing air bubbles from being mixed in, suppressing the decrease in reactivity caused by the mixing of oxygen, and improving the adhesion between the mold and the curable composition for imprinting. Therefore, in the vacuum state Under light irradiation. Moreover, the preferable degree of vacuum during light irradiation is in the range of 10 ^-1 Pa to normal pressure.

During exposure, it is appropriate to set the exposure illuminance to a range of 1 mW/cm ² to 500 mW/cm ² . Among them, if the preferred embodiment of the present invention is applied to a step-repetitive nanoimprint process, from the perspective of throughput (shortened exposure time), 10 mW/cm ² or more is preferred. It is more preferable that it is 100mW/ ^cm2 or more, and it is further more preferable that it is 200mW/cm2 ^or more. The exposure time is preferably 1.0 seconds or less, more preferably 0.5 seconds or less, and further preferably 0.2 seconds or less. As a lower limit value, it is actually 0.01 seconds or more. It may include the step of hardening the pattern forming layer (a layer composed of a curable composition for imprinting) by irradiation with light, and then heating the hardened pattern to further harden it if necessary. The temperature at which the composition of the present invention is heated and hardened after light irradiation is preferably 150 to 280°C, and more preferably 200 to 250°C. In addition, the heating time is preferably 5 to 60 minutes, and further preferably 15 to 45 minutes. When using the curable composition for imprinting of the present invention to produce a cured product pattern, the imprinting method is preferably carried out by repeating steps. As an embodiment of the step repetition method, the mold processing method shown in Figure 1(a) to Figure 1(c) can be cited.

In the steps of flashing, imprinting, and lithography in this embodiment, as shown in Figures 1(a) to 1(c), the mold 3 is sequentially shifted toward the surface direction of the substrate, and imprinting is performed step by step (based on the imprinting process). Welding and release printing). In the illustrated embodiment, a layer (curable composition layer for imprint) 2 is formed on the upper surface of the substrate 1 by applying a curable composition for imprint and disposed thereon (Fig. 1(a)). The mold 3 is fixed at a predetermined position, and pressure welding 4a is performed at this position. Next, the mold 3 is separated from the imprinting curable composition layer to release the mold 4b. In this way, the pattern (recessed portion) 5a printed on the imprinting curable composition layer in a shape corresponding to the convex portion 3x of the mold is formed (Fig. 1 (b)). Although not shown in the figure, in this embodiment, exposure is performed after pressing the mold 4a. A translucent material such as quartz is used for the mold, and the curable composition for imprinting is irradiated with light through the mold. The curable composition for imprint has photocurability and is cured by exposure. Thereby, the shape of the recessed part 5a is fixed. Next, the casting mold 3 is shifted and fixed by a predetermined amount from the original position 3a in the surface direction with respect to the substrate. Therefore, the pressure welding 4a/exposure/release 4b are performed sequentially in the same manner as described above to form the recessed portion 5b in the imprint curable composition layer (Fig. 1(c)). Move the mold further (from 3b to 3), and perform pressure welding, exposure, and demolding. By repeating this operation, the imprint layer 2a in which a desired pattern is widely formed on the substrate can be formed.

As mentioned above, in the pattern manufacturing method of the present invention, it is preferable to adopt a repetitive method of dividing the imprinted area on the wafer and repeating the steps of imprinting and exposure a plurality of times. The distance between adjacent grooves is usually about 10 to 100 μm. As one embodiment of the present invention, a method for manufacturing a circuit board including the pattern manufacturing method of the present invention can be exemplified. Furthermore, as another embodiment of the present invention, a method of manufacturing a semiconductor element including the method of manufacturing a pattern of the present invention can be exemplified. The pattern size can be set appropriately according to the needs, preferably below 50nm and below 30nm. The lower limit value is not particularly limited, but is actually 1 nm or more.

＜Application form＞ Furthermore, one embodiment of the present invention includes the use of a cured product formed of a curable composition for imprinting. The curable composition for imprinting of the present invention is preferably used as a cured product for photocuring. More specifically, it is used by forming a pattern by photoimprinting.

The hardened material pattern obtained by the pattern manufacturing method of the present invention can be used for various purposes. For example, it can also be used as a permanent film such as a protective layer or insulating film for liquid crystal displays (LCDs), etc., and as an etching resist for semiconductor integrated circuits, recording materials, flat panel displays, etc. The hardened material pattern according to the preferred embodiment of the present invention also has excellent etching resistance and can be suitably used as an etching resist for dry etching using fluorocarbon or the like. [Example]

Hereinafter, the present invention will be described in further detail by taking examples as examples. The materials, usage amounts, proportions, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed within the scope that does not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

＜Preparation of curable composition for imprint＞ Various compounds described in Tables 1 to 3 were mixed (details and characteristics of these are shown in Tables 4 to 9), and 200 mass ppm (0.02 mass %) was added as a polymerization inhibitor based on the total amount of polymerizable compounds. 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl radical (manufactured by Tokyo Chemical Industry Co., Ltd.). This was filtered through a Nylon filter with a pore size of 0.02 μm and a UPE filter with a pore size of 0.001 μm, thereby preparing a curable composition for imprinting. Those listed in the solvent usage table added non-volatile components in amounts corresponding to the concentrations listed in Tables 1 to 3.

<Measurement method of molecular weight of polymerizable compounds> The weight average molecular weight (Mw) of the resin is defined as a polystyrene-converted value according to gel permeation chromatography (GPC measurement). HLC-8220 (manufactured by TOSOH CORPORATION) was used as the device, and protection column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) were used as the column. THF (tetrahydrofuran) was used as the eluent. The detection uses a UV ray (ultraviolet) wavelength detector of 254nm. The weight average molecular weight Mw of low molecular weight compounds with a molecular weight less than 1500 was measured using LC-MS. The conditions are set as follows. Device: LC/MS G1956B made by Agilent Column: TOSOH ODS-80Ts Mobile phase: 10mM ammonium acetate aqueous solution/10mM acetic acid methanol aqueous solution Flow: 0.2mL/min Injection volume: 2μL Tube string temperature: 40℃ Detector: ESI-Posi-SIM mode

＜Measurement of Absorption Coefficient＞ The absorbance coefficient per unit mass of the polymerizable compound (unit: L/(g･cm)) and the molar absorption coefficient of the polymerization initiator (unit: L/(mol･cm)) were measured using a spectrophotometer. Each material was diluted to 0.0001 mass/volume % with acetonitrile to prepare a sample solution. The prepared sample liquid was filled into a quartz cell (optical path length 1 cm), and the absorbance and absorption coefficient were measured using a spectrophotometer. The measurement wavelength range was 250 to 400 nm, the measurement interval was 1 nm, and the scanning speed was 50 nm/minute. Details regarding the measurement sequence etc. comply with JISK0115:2004. Two samples were prepared for each level and measured three times. The arithmetic mean of a total of 6 times was adopted as the evaluation value. The results are shown in Tables 4 to 7.

<Evaluation of film thickness stability> The adhesive layer forming composition shown in Example 6 of Japanese Patent Application Laid-Open No. 2014-024322 was spin-coated on a silicon wafer and heated using a hot plate at 220° C. for 1 minute to form an adhesive layer with a thickness of 5 nm. Next, the curable composition for imprinting was spin-coated on the surface of the adhesion layer and heated using a hot plate at 80° C. for 1 minute, thereby forming a curable composition layer (film) for imprinting on the adhesion layer. The thickness of the formed film is approximately 100 nm. The film thickness (FT1) of the newly formed film was measured using an ellipsometer. After that, after leaving it for 24 hours at 23°C and 1 atmosphere (humidity control at 40 to 60% RH), the film thickness (FT2) was measured again, and the film thickness difference ΔFT (|FT1-FT2|) was calculated. A: ΔFT≦5.0nm B: 5.0nm＜ΔFT≦10nm C: 10nm＜ΔFT≦20nm D: ΔFT>20nm

<Evaluation of mold release force> The adhesive layer forming composition shown in Example 6 of Japanese Patent Application Laid-Open No. 2014-024322 was spin-coated on a silicon wafer and heated using a hot plate at 220° C. for 1 minute to form A bonding layer with a thickness of 5nm. Further, a curable composition for imprinting was spin-coated on the adhesion layer and heated using a hot plate at 80° C. for 1 minute to obtain a pattern forming layer with a film thickness of 80 nm. Next, a quartz mold (line pattern with a line width of 20 nm and a depth of 50 nm) was pressure-bonded on the pattern formation layer in a He environment (substitution rate of 90% or more), and the mold was filled with a curable composition for imprinting. After 10 seconds of stamping, use a high-pressure mercury lamp to illuminate the light source from the side of the mold under the conditions of maximum wavelength of the light source: 365nm, exposure illumination: 10mW/cm ² , exposure time: 15 seconds (exposure: 150mJ/cm ² ) After exposure, the mold is peeled off, whereby the pattern is transferred to the pattern forming layer. The release force required for peeling was measured using a load cell. A: Release force≦15N B: 15N＜Release force≦20N C: 20N＜Release force≦25N D: Release force＞25N

<Evaluation of Analytical Properties> The composition for forming an adhesive layer shown in Example 6 of Japanese Patent Application Laid-Open No. 2014-024322 was spin-coated on a silicon wafer and heated using a hot plate at 220° C. for 1 minute to form a Adhesive layer with a thickness of 5nm. Further, a curable composition for imprinting was spin-coated on the adhesion layer and heated using a hot plate at 80° C. for 1 minute to obtain a pattern forming layer with a film thickness of 80 nm. Next, a quartz mold (line pattern with a line width of 25 nm and a depth of 75 nm) was pressure-bonded on the pattern formation layer in a He environment (substitution rate of 90% or more), and the mold was filled with a curable composition for imprinting. After 10 seconds of stamping, use a high-pressure mercury lamp to illuminate the light source from the side of the mold under the conditions of maximum wavelength of the light source: 365nm, exposure illumination: 10mW/cm ² , exposure time: 15 seconds (exposure: 150mJ/cm ² ) After exposure, the mold is peeled off, whereby the pattern is transferred to the pattern forming layer. The transferred pattern was checked for pattern collapse by scanning electron microscopy (SEM) observation. A: Neither pattern collapse nor pattern edge roughness was confirmed. B: Pattern collapse was not confirmed, but pattern edge roughness was confirmed. C: Collapse was confirmed in part of the pattern transfer area. D: It was confirmed in the entire pattern transfer area. Arrive at collapse

<Measurement of elastic modulus> The composition for forming an adhesive layer shown in Example 6 of Japanese Patent Application Laid-Open No. 2014-024322 was spin-coated on a silicon wafer and heated using a hot plate at 220° C. for 1 minute to form a Adhesive layer with a thickness of 5nm. Further, a curable composition for imprinting was spin-coated on the adhesion layer and heated using a hot plate at 80° C. for 1 minute to obtain an uncured film. Then, the quartz substrate is pressure-welded to the hardening composition for imprinting in a He environment (substitution rate is more than 90%). After 10 seconds of imprinting, a high-pressure mercury lamp is used to illuminate the maximum wavelength of the light source from the side of the mold: After exposure at 365 nm, exposure illumination: 10 mW/cm ² , and exposure time: 30 seconds (exposure amount: 300 mJ/cm ² ), the quartz substrate was peeled off to obtain a flat cured film (film thickness 300 nm). The obtained cured film was cut into approximately 2 cm squares, and the elastic coefficient was measured using a nano in-situ measuring instrument (TI-950 manufactured by Hysitron, Inc.). The indenter uses a diamond corner indenter (radius of curvature 150nm), and presses in with a maximum load of 3 μN at a constant load speed for 5 seconds. After maintaining the load for 2 seconds, the load is removed at a constant load speed for 5 seconds to obtain The load deloading curve (n=10) is obtained. The elastic coefficient was calculated using the Oliver-Pharr method.

<Evaluation of Processing Resistance> A thin film (film thickness approximately 300 nm) of the curable composition for imprint was obtained by the same method as the method for measuring the elastic coefficient. The above-mentioned sample was introduced into an etching device (Centura-DPS manufactured by Applied Materials, Inc.) and etched under the following conditions. Etching conditions: Gas pressure: 10mTorr (1Torr is 133.322Pa.) Gas type (flow rate): O ₂ (10sccm) (for 1sccm=1.69x10 ^-4 Pa･m ³ /sec) Source voltage (W): 50W Bias voltage (W ): 100W Etching time: 20sec, 40sec, 60sec The film thickness of the above sample was measured by an ellipsometer, and the etching etching ratio (unit: nm/minute) was calculated based on the film thickness change rate before and after etching. A: less than 10nm/minute B: more than 10nm/minute less than 100nm/minute C: more than 100nm/minute less than 200nm/minute D: more than 200nm/minute

＜Evaluation of surface tension difference＞ The difference (Δγ=| γ1-γ2|) were measured. The surface tension of each sample was measured at 23° C. using a surface tensiometer SURFACE TENS-IOMETER CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd. and a glass plate. The unit is expressed as mN/m. Two samples were prepared for each level and measured three times. The arithmetic mean of a total of 6 times was adopted as the evaluation value. The results are shown as "Δγ" in Tables 1 to 3.

[Table 1] [Table 2] The solvent of Example 15 used a mixed solution containing PGMEA (propylene glycol monomethyl ether acetate) and γ-BL (γ-butyrolactone) in a volume ratio of 90:10. In addition, the EL of the solvent (Example 12) was ethyl lactate. [table 3] [Table 4] The silicon-containing acrylate resins of A-1 to A-6 have a graft structure in which silicon resin is introduced into the hydroxyl group of the side chain of 2-hydroxyethylacrylate. [table 5] [Table 6] [Table 7] [Table 8] [Table 9]

From the above results, it can be seen that the curable composition for imprinting according to the embodiment of the present invention contains a specific amount of a specific photopolymerization initiator, a specific amount of a specific light-transmitting polymerizable compound, and a specific amount of mold release. agent, the results showed excellent performance of B or higher in terms of mold release force and resolution (Examples 1 to 16). Furthermore, in terms of film thickness stability, elastic modulus, and processing resistance, excellent performance of B or higher was also demonstrated (Examples 1 to 16).

On the other hand, in the composition of Comparative Example 1 in which the release agent exceeds the predetermined amount, or Comparative Example 8 in which a surfactant containing fluorine atoms is used as the release agent in an excess of the predetermined amount, the release force is A, but Resolution was poor to D, and collapse was observed throughout the pattern transfer area. On the contrary, in Comparative Example 2 with too little release agent, the resolution was A, but the release force result was as bad as D. Among the polymerizable compounds, those with poor light transmittance whose maximum value of the light absorption coefficient A exceeded the upper limit (Comparative Examples 3 to 5) were used, and the resolution was as poor as C, and was observed in part of the pattern transfer area. Collapse. In addition, in these comparative examples, the processing resistance results were also C and D, and the performance as an etching resist was poor. In Comparative Example 6, a translucent polymerizable compound whose maximum value of the light absorption coefficient A was within a specific range was used, but the amount was less than the specified amount. As a result, although the mold release force was B, the resolution was as poor as C. In Comparative Example 7, a polymerizable compound whose maximum value of the absorption coefficient A is within a specific range but whose molecular weight is too small is used. In this curable composition for imprinting, the resolution was B, but the film release force was C, which failed to meet the technical requirements. Moreover, the film thickness stability is also as bad as D. In Comparative Examples 9 and 10, those having a maximum value of the absorption coefficient B smaller than a predetermined range were used as polymerization initiators, resulting in poor resolution.

Imprinting was carried out using the curable composition for imprinting of each of the above-described Examples by repeating the steps described in Japanese Patent Publication No. 2005-533393. As a result, excellent pattern transfer with both resolution and mold releasability was achieved. print.

1:Substrate 2: Hardening composition layer for imprinting 2a: Curable composition for patterned imprinting (imprinting layer) 3: Casting mold (template) 3a, 3b: Original position of the mold 3x:Mold convex part 4a: Pressure welding direction 4b: Demold direction 5a, 5b: Pattern (concave)

1(a) to 1(c) are step explanatory diagrams schematically illustrating an example of a step-repeating nanoimprinting process in a cross-sectional view.

1:Substrate

2: Hardening composition layer for imprinting

2a: Curable composition for patterned imprinting (imprinting layer)

3: Casting mold (template)

3a, 3b: Original position of the mold

3x:Mold convex part

4a: Pressure welding direction

4b: Demold direction

5a, 5b: Pattern (concave)

Claims (23)

A curable composition for imprinting, which contains a polymerizable compound, a photopolymerization initiator and a release agent. In the curable composition for imprinting, the polymerizable compound has the following light absorption coefficient A with a maximum value of 1.8 L/(g.cm) or less and a weight average molecular weight of 800 or more, wherein the polymerizable group equivalent in the polymeric compound is between 130 and 2,500, and the imprint hardening compound is The polymerizable compound in the polymeric composition contains 80% by mass or more of the total solid content of the composition, and the photopolymerization initiator is the following: the maximum value of the absorption coefficient B is 5,000L/(mol.cm) or more and relative to The total solid content of the composition contains 0.5 mass% to 8.0 mass% of the photopolymerization initiator, and the content of the release agent is 0.1 mass% or more and less than 1.0 mass% relative to the total solid content of the composition; the light absorption coefficient A: The absorption coefficient per unit mass in the wavelength range of 250 nm to 400 nm in the acetonitrile solution. Absorption coefficient B: The molar absorption coefficient in the wavelength range of 250 nm to 400 nm in the acetonitrile solution. The curable composition for imprinting described in claim 1, wherein the translucent polymerizable compound has two or more polymerizable groups. The curable composition for imprinting described in claim 1, wherein the translucent polymerizable compound has two or more polymerizable groups, and the polymerizable group equivalent weight is 150 or more. The curable composition for imprinting as described in any one of items 1 to 3 of the patent application scope The weight average molecular weight of the light-transmitting polymerizable compound exceeds 2,000. The curable composition for imprinting as described in any one of items 1 to 3 of the patent application, wherein the light-transmitting polymerizable compound has a silicon skeleton. The curable composition for imprinting as described in any one of items 1 to 3 of the patent application, wherein the light-transmitting polymerizable compound has a silicone resin introduced into the side chain of the (meth)acrylic resin. Grafted structure. The curable composition for imprinting described in any one of items 1 to 3 of the patent application scope, wherein the content of the release agent is 0.5% by mass or more relative to the total solid content of the composition. The curable composition for imprinting described in any one of items 1 to 3 of the patent application further contains a solvent. The curable composition for imprinting as described in any one of items 1 to 3 of the patent application, wherein the curable composition for imprinting is in a film shape and irradiated with an exposure dose of 300 mJ/cm ² The resulting cured film with a thickness of 300 nm has an elastic coefficient calculated by the Oliver-Pharr method of 2.0 GPa or more. The curable composition for imprinting as described in any one of items 1 to 3 of the patent application, wherein the surface tension of the total solid content of the curable composition for imprinting is equal to the curable composition for imprinting. The difference in surface tension of the components excluding the release agent from the total solid content of the composition is 1.0 mN/m or less. For the curable composition for imprinting described in any one of items 1 to 3 of the patent application, the release agent does not substantially contain fluorine atoms and silicon atoms. The curable composition for imprinting described in any one of items 1 to 3 of the patent application further contains a polymerization inhibitor. The curable composition for imprinting described in any one of items 1 to 3 of the patent application is used in a step-repetition method. The curable composition for imprinting as described in any one of items 1 to 3 of the patent application, wherein the polymerizable compound has two or more ethylenically unsaturated groups. The curable composition for imprinting as described in any one of items 1 to 3 of the patent application, wherein the polymerizable group equivalent in the polymerizable compound is 1000 or less, and the polymerizable compound has two The above ethylenically unsaturated groups. The curable composition for imprinting as described in any one of items 1 to 3 of the patent application, wherein the light-transmitting polymerizable compound contains silicon atoms and has three or more ethylenically unsaturated groups. A compound, a compound having a cyclic structure and two or more ethylenically unsaturated groups, or a dendritic compound having five or more ethylenically unsaturated groups. The curable composition for imprinting as described in any one of items 1 to 2 of the patent application, wherein the equivalent weight of the polymerizable group in the polymerizable compound is between 130 and 1000. The curable composition for imprinting as described in any one of items 1 to 2 of the patent application, wherein the equivalent weight of the polymerizable group in the polymerizable compound is between 147 and 608. A method for manufacturing a pattern, which includes applying the curable composition for imprinting described in any one of items 1 to 18 of the patent application on a substrate or a casting mold, and using the casting The step of irradiating light is performed with the curable composition for imprinting sandwiched between the mold and the substrate. The method for manufacturing a pattern as described in Item 19 of the patent application, wherein the curable composition for imprinting is applied on the top of the adhesion layer. In the method for manufacturing a pattern as described in Item 19 of the patent application, the curable composition for imprinting is applied to the substrate by a spin coating method. A method of manufacturing a semiconductor element, which includes a method of manufacturing a pattern described in any one of items 19 to 21 of the patent application scope. A hardened material formed from the curable composition for imprinting described in any one of items 1 to 18 of the patent application.