Photocurable resin composition for imprint mold, resin mold, pattern formation method using said resin mold, composite having said resin mold, method for manufacturing said composite, and method for manufacturing optical member

Abstract

This photocurable resin composition for imprint molding contains a component (a): a fluorine-containing (meth)acrylate monomer having at least one (meth)acryloyloxy group and / or a dialkylsiloxane-containing (meth)acrylate monomer having at least one (meth)acryloyloxy group; and a component (b): a non-cyclic difunctional (meth)acrylate monomer represented by formula (1), which has two (meth)acryloyloxy groups. The blending ratio of component (a) and component (b) is 1-97 to 99-3 in terms of mass ratio. The molecular weight of component (b) is 700 or less.

Description

[Technical field]

[0001] One aspect of the present invention relates to a curable resin composition for an imprint mold. Another aspect of the present invention relates to a resin mold obtained using the curable resin composition for an imprint mold, a pattern forming method using the resin mold, a composite having the resin mold, a method for producing the composite, and a method for producing an optical member. [Background technology]

[0002] 2. Description of the Related Art In a method for producing optical members such as optical or electronic parts, an imprinting technique is used in which a mold on which a concave and convex pattern is formed is pressed against a photocurable resin composition to be transferred, thereby precisely transferring a fine pattern.

[0003] The imprinting method generally includes four steps: (1) applying a photocurable composition to be transferred, (2) pressing the composition with a mold, (3) transferring and curing (photocuring or thermal curing), and (4) releasing the mold from the cured product, and is a simple process that allows nano-sized processing. In addition, since the equipment is simple and high throughput is expected, it is expected to be a microfabrication technology that can be mass-produced at low cost. Therefore, efforts are being made to put it into practical use in various fields such as semiconductor devices, storage media, bio- and optical components.

[0004] Various resin molds have been proposed as molds used in the imprint method, and improvements have been made mainly to components with a high fluorine content from the viewpoint of demolding properties (see Non-Patent Document 1). [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] Angew.Chem.Int.Ed.2004,43,5796. Summary of the Invention [Problem to be solved by the invention]

[0006] The curable resin composition described in Non-Patent Document 1 has excellent releasability. However, the composition is mainly composed of a fluorinated urethane (meth)acrylate with a high fluorine content. Since the fluorinated urethane (meth)acrylate with a high fluorine content is expensive, there is a problem in terms of cost. In addition, fluorinated urethane (meth)acrylates with a high fluorine content have problems with compatibility with other components. There is a demand for a photocurable resin composition for imprint molds which can give a resin mold having excellent releasability and durability and is low cost. [Means for solving the problem]

[0007] The present invention has been made to solve the above-mentioned problems. The present inventors have found that the above-mentioned problems can be solved by using a combination of specific components as a photocurable resin composition for imprint molds, and have completed one embodiment of the present invention.

[0008] One embodiment of the present invention is a composition comprising component (a): at least one of a fluorine-based (meth)acrylate monomer having at least one (meth)acryloyloxy group and a dialkylsiloxane-based (meth)acrylate monomer having at least one (meth)acryloyloxy group; Component (b): a non-cyclic bifunctional (meth)acrylate monomer having two (meth)acryloyloxy groups, represented by the following formula (1): The blending ratio of the component (a) to the component (b) is 1 to 97:99 to 3 by mass ratio, The component (b) is a photocurable resin composition for imprint molds having a molecular weight of 700 or less.

[0009] [ka] In the above general formula (1), R 1R is independently a hydrogen atom or a methyl group. 2 represents a divalent organic group not having a ring structure, and the divalent organic group not having a ring structure contains at least one of a linear alkylene group which may have a substituent and a linear alkyleneoxy group which may have a substituent, the substituent having 1 to 4 carbon atoms, and at least one of the methylene groups contained in the alkylene group and the alkyleneoxy group may be replaced with a carbonyl group. Another aspect of the present invention is a resin mold obtained by curing the above-mentioned photocurable resin composition for imprint molds so as to have a plurality of concave and convex patterns. Another aspect of the present invention is a pattern forming method comprising the steps of forming a transfer layer on a substrate using a photocurable resin composition for imprint transfer, bringing the resin mold into contact with a surface of the transfer layer, and irradiating the transfer layer with light to form a concave-convex pattern. Another aspect of the present invention is a composite having the above-mentioned resin mold and a photocured layer formed by irradiating the transfer layer with light while the resin mold is in contact with the transfer layer. Another aspect of the present invention is a method for producing a composite, comprising the steps of forming a transfer layer on a substrate using a photocurable resin composition for imprint transfer, bringing the resin mold into contact with a surface of the transfer layer, and irradiating the transfer layer with light to form a photocured layer having a concave-convex pattern, thereby obtaining a composite having the resin mold and the photocured layer. Another aspect of the present invention is a method for producing an optical member using the above-mentioned pattern formation method. Effect of the Invention

[0010] According to one aspect of the present invention, a resin mold having releasability and durability can be obtained, and a low-cost photocurable resin composition for imprint molds can be provided. [Brief description of the drawings]

[0011] [Figure 1]1A to 1C are diagrams illustrating an example of a process for producing a resin mold according to one embodiment of the present invention. [Diagram 2] 1A to 1C are diagrams illustrating an example of a process for producing a photocured layer from a resin mold according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] <1> Photocurable resin composition for imprint mold A photocurable resin composition for imprint molds according to one embodiment of the present invention comprises component (a): at least one of a fluorine-based (meth)acrylate monomer having at least one (meth)acryloyloxy group and a dialkylsiloxane-based (meth)acrylate monomer having at least one (meth)acryloyloxy group, and component (b): an acyclic bifunctional (meth)acrylate monomer represented by the above formula (1). In the photocurable resin composition for imprint molds according to one embodiment of the present invention, the blending ratio of the above component (a) to the above component (b) is 1 to 97:99 to 3 in terms of mass ratio. Each monomer component of the photocurable resin composition for imprint molds according to one embodiment of the present invention will be described below.

[0013] [Component (a)] The above-mentioned component (a) is at least one of a fluorine-based (meth)acrylate monomer having at least one (meth)acryloyloxy group (hereinafter also referred to as "fluorine-based component (a1)") and a dialkylsiloxane-based (meth)acrylate monomer having at least one (meth)acryloyloxy group (hereinafter also referred to as "siloxane-based component (a2)"). The fluorine content of the fluorine-based component (a1) is preferably 30 to 65 mass %, more preferably 35 mass % or more, further preferably 40 mass % or more, particularly preferably 50 mass % or more.

[0014] (Fluorine-based component (a1)) The fluorine-based component (a1) may be a fluorine-containing monomer having one or more (meth)acryloyloxy groups. The fluorine-based component (a1) is preferably a monomer having one or two (meth)acryloyloxy groups, and more preferably a monomer having one (meth)acryloyloxy group. When the fluorine-based component (a1) is a monomer having one (meth)acryloyloxy group, the molecular weight is preferably 100 to 2500, more preferably 100 to 1000, and further preferably 200 to 700. When the fluorine-based component (a1) is a monomer having two (meth)acryloyloxy groups, the molecular weight is preferably 100 to 3000, and more preferably 250 to 2500. As the fluorine-based component (a1), two or more types of fluorine-based (meth)acrylate monomers having different structures may be used in combination.

[0015] As the fluorine-based component (a1), a monofunctional or bifunctional fluorine atom-containing (meth)acrylate containing at least one of a fluorinated alkylene group and a fluorinated alkyleneoxy group is more preferable. By adjusting the molecular weight, good compatibility in the composition can be obtained. The fluorine-based component (a1) preferably has 9 to 50 carbon atoms. The fluorine-based component (a1) may have a urethane bond. Specific examples of the fluorine-based component (a1) include the compounds shown below. In the following formula, R is a hydrogen atom or a methyl group. In the following formula, n is preferably 0 to 9, p is preferably 0 to 18, and q is preferably 0 to 31. When the fluorine-based component (a1) is a polymer, the molecular weight can be calculated by referring to the method described in the non-patent literature (Macromol. Chem. Phys. 198, 1893-1907 (1997)). 19 It is calculated based on n, p, and q calculated by F-NMR.

[0016] [ka]

[0017] The fluorine-based component (a1) may be a commercially available product. When the fluorine-based component (a1) is a fluorinated urethane (meth)acrylate, it may be synthesized by a general method of reacting an alcohol with an isocyanate to obtain a urethane bond. In this case, a raw material in which at least one of the alcohol and the isocyanate is fluorinated may be used. Specifically, the fluorinated urethane diacrylate represented by the following formula (A) can be synthesized, for example, as follows.

[0018] [ka]

[0019] Fluorinated polytetramethylene glycol represented by the following formula (B) (product name "Fluorinated PTMG-250 DIOL", manufactured by Exfluor Research Corporation) is reacted with 2-isocyanatoethyl acrylate (product name "Kalends AOI", manufactured by Showa Denko K.K.) and dibutyltin dilaurate as a catalyst at 70 to 90°C for 3 to 10 hours to obtain the fluorinated urethane diacrylate represented by the above formula (A). The amount of each of the above compounds used may be appropriately determined within the same range as in the case of synthesizing a general urethane compound.

[0020] [ka]

[0021] The fluorinated urethane diacrylate represented by the following formula (C) can be synthesized, for example, as follows.

[0022] [ka]

[0023] The fluorinated polyether represented by the following formula (D) (product name "D2", manufactured by Solvay Specialty Polymers Japan Ltd.) is reacted with 2-isocyanatoethyl acrylate (product name "Kalends AOI", manufactured by Showa Denko K.K.) and dibutyltin dilaurate as a catalyst at 70 to 90°C for 3 to 10 hours to obtain the fluorinated urethane diacrylate represented by the above formula (C). The amount of each of the above compounds used may be appropriately determined within the same range as in the case of synthesizing a general urethane compound.

[0024] [ka]

[0025] (Siloxane-based component (a2)) The siloxane-based component (a2) is a dialkylsiloxane-based (meth)acrylate monomer having one or more (meth)acryloyloxy groups, and is preferably a monomer having the following structure:

[0026] [ka]

[0027] In the above formula, R c1 ~R c2 are each independently preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 to 2 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include linear alkyl groups such as a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. As the siloxane-based component (a2), in addition to the monomer having the above structure, (R c3 SiO 1.5 ) n Monomers having a silsesquioxane skeleton represented by the formula R c3 is preferably an alkyl group having 1 to 4 carbon atoms. Examples of the siloxane-based component (a2) include the compounds shown below: In the following formula, R is a hydrogen atom or a methyl group, and R' is an alkyl group having 1 to 4 carbon atoms. As the siloxane-based component (a2), two or more types of siloxane-based (meth)acrylate monomers having different structures may be used in combination.

[0028] [ka]

[0029] The siloxane-based component (a2) preferably has a molecular weight of 2000 or less, more preferably 1000 or less. The siloxane-based component (a2) preferably has a molecular weight of 600 or more.

[0030] In the photocurable resin composition for imprint molds, the compounding ratio of the component (a) to the component (b) is preferably 1-97:99-3, more preferably 1-50:99-50, and even more preferably 5-30:95-70, by mass ratio.

[0031] In the photocurable resin composition for imprint molds, the amount of component (a) is preferably 1 to 35% by mass based on the main components. It is more preferably 30% by mass or less, and even more preferably 25% by mass or less. It is more preferably 5% by mass or more, and even more preferably 10% by mass or more. By setting the amount within this range, the compatibility of the photocurable resin composition can be improved, and furthermore, the releasability after photocuring can be exhibited. The component (a) may be either the component (a1) or the component (a2) alone, or a combination of the components (a1) and (a2). Also, a (meth)acrylate monomer having both a fluorine atom and a siloxane structure may be used as the component (a).

[0032] [Component (b)] The component (b) is an acyclic bifunctional (meth)acrylate monomer represented by the following formula (1) having a molecular weight of not more than 700. The component (b) is a (meth)acrylate monomer other than the component (a) and is a monomer having no fluorine atom or siloxane structure.

[0033] [ka]

[0034] In the above general formula (1), R 1 each independently represents a hydrogen atom or a methyl group. R 2 is a divalent organic group not having a ring structure, the divalent organic group not having a ring structure contains at least one of a straight-chain alkylene group which may have a substituent (hereinafter also referred to as a "first substituent") and a straight-chain alkyleneoxy group which may have a substituent (hereinafter also referred to as a "second substituent"), the first substituent and the second substituent having 1 to 4 carbon atoms, and at least one of the methylene groups contained in the alkylene group and the alkyleneoxy group may be replaced with a carbonyl group.

[0035] The linear alkylene group which may have the first substituent preferably has at least one structure represented by the following formula (2).

[0036] [ka]

[0037] In the above formula (2), R a1 ~R a2 are each independently a hydrogen atom or the above first substituent, and the first substituent is preferably an alkyl group having 1 to 4 carbon atoms.

[0038] The alkyleneoxy group which may have a second substituent preferably has at least one structure represented by the following formula (3).

[0039] [ka]

[0040] In the above formula (3), R b1 ~R b4 are each independently a hydrogen atom or the above second substituent, and the second substituent is preferably an alkyl group having 1 to 4 carbon atoms. In the above formula (3), X is preferably an oxygen atom or a sulfur atom. At least one of the methylene groups contained in the alkylene group and the alkyleneoxy group may be replaced with a carbonyl group.

[0041] When the divalent organic group has two or more structures represented by the above formula (2) and / or has two or more structures represented by the above formula (3), R a1 ~R a2 and R b1 ~R b4 Each of may be the same or different.

[0042] The first substituent (R a1 ~R a2 ) or the second substituent (R b1 ~R b4 ) examples of the alkyl group having 1 to 4 carbon atoms include linear alkyl groups such as methyl groups, ethyl groups, n-propyl groups, and n-butyl groups; and branched alkyl groups such as isopropyl groups, isobutyl groups, and t-butyl groups.

[0043] The linear alkylene group may be represented by the general formula -C n H 2n -. There are no particular limitations on n as long as the molecular weight of the acyclic bifunctional (meth)acrylate monomer is 700 or less, but when the divalent organic group is one type of linear alkylene group, it preferably has 3 to 40 carbon atoms, more preferably 4 to 30 carbon atoms. At least one of the methylene groups contained in the linear alkylene group may be replaced with a carbonyl group.

[0044] The linear alkyleneoxy group is represented by the general formula -Cm H 2m and straight-chain alkyleneoxy groups represented by O-. m is not particularly limited as long as the molecular weight of the acyclic bifunctional (meth)acrylate monomer is 700 or less, but when the divalent organic group is one kind of straight-chain alkyleneoxy group, it preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms. At least one of the methylene groups contained in the straight-chain alkyleneoxy group may be replaced with a carbonyl group.

[0045] The divalent organic group may contain either one or a combination of a linear alkylene group and a linear alkyleneoxy group, and is preferably composed of either one or a combination of a linear alkylene group and a linear alkyleneoxy group. Furthermore, the linear alkylene group and the linear alkyleneoxy group may each have the above-mentioned first substituent and second substituent. Above R 2 Examples of the divalent organic group include a divalent organic group having the structure shown below, and it is preferable that the divalent organic group is one or a combination of two or more of the structures shown below.

[0046] [ka]

[0047] Above R 2 As, -C 4 H 8 -, -C 6 H 12 -, -C 9 H 18 -, -C 10 H 20 -, -(C 2 H 4 O) 3 -, -(C 2 H 4 O) 4 -, -(CH(CH 3 )CH 2 O) m -(CH 2 CH(CH 3 )O) nIn this case, m+n is preferably 2 to 3.

[0048] The acyclic bifunctional (meth)acrylate monomer preferably has a molecular weight of 700 or less, more preferably 540 or less, more preferably 530 or less, and even more preferably 450 or less. The molecular weight is preferably 150 or more, and more preferably 190 or more.

[0049] Specifically, the following monomers are preferably used as the acyclic bifunctional (meth)acrylate monomer: In the following formula, R is a hydrogen atom or a methyl group.

[0050] [ka]

[0051] In the monomer represented by the above chemical formula, m+n is preferably 2 to 10. Also, M+N is preferably 2 to 3.

[0052] In the photocurable resin composition for imprint molds, the blending amount of the component (b) is preferably 1 to 96% by mass based on the main components. It is more preferably 10% by mass or more, even more preferably 20% by mass or more, and particularly preferably 25% by mass or more. It is more preferably 90% by mass or less, and even more preferably 80% by mass or less. By setting the blending amount within this range, it is possible to improve the releasability and durability of a resin mold obtained from the photocurable resin composition for imprint molds. The component (b) is preferably an acrylate monomer because it has high photocuring reactivity and can obtain a high reaction rate. If the reaction rate is high, it tends to be difficult to react with the imprinting resin when used as a resin mold, and good releasability tends to be obtained. If the photocuring reactivity is high, it tends to be excellent in throughput during mass production of resin molds. Therefore, the component (b) is preferably an acrylate monomer.

[0053] [Other monomer components] (component (c)) The photocurable resin composition for imprint molds according to one embodiment of the present invention may further contain, as a monomer component, a component (c) other than the above-mentioned components (a) and (b). The molecular weight of component (c) is preferably 150 to 5000, more preferably 150 to 600, and even more preferably 200 to 550. By setting the molecular weight within this range, it is possible to improve the releasability and durability of a resin mold obtained from the photocurable resin composition for imprint molds.

[0054] Examples of the above component (c) include at least one selected from the group consisting of a non-cyclic bifunctional (meth)acrylate monomer having a hydroxyl group and two (meth)acryloyloxy groups (hereinafter also referred to as "component (c1)"); a urethane-based bifunctional (meth)acrylate monomer having two (meth)acryloyloxy groups (hereinafter also referred to as "component (c2)"); and a cyclic bifunctional (meth)acrylate monomer having a ring structure and two (meth)acryloyloxy groups (hereinafter also referred to as "component (c3)").

[0055] The component (c) is a (meth)acrylate monomer other than the components (a) and (b), and is a monomer having neither a fluorine atom nor a siloxane structure. The components (c1), (c2), and (c3) are monomers that do not overlap with each other. The components (b), (c1), and (c3) are monomers that do not have a urethane bond.

[0056] (component (c1)) The component (c1) is a bifunctional (meth)acrylate monomer having a non-cyclic structure and a hydroxyl group, and examples thereof include monomers represented by the following formula (4): The molecular weight of the component (c1) is more preferably 200 to 450.

[0057] [ka] In the above general formula (4), R 1 is R in the above general formula (1). 1 is selected from the same options.

[0058] R 4 is preferably a divalent group containing at least one of a straight-chain alkylene group having at least one hydroxyl group and optionally a third substituent; and a straight-chain alkyleneoxy group having at least one hydroxyl group and optionally a fourth substituent. The third substituent and the fourth substituent are preferably selected from the same options as the first substituent. As the component (c1), two or more types of bifunctional (meth)acrylate monomers having different structures may be used in combination.

[0059] As the component (c1), R in the general formula (1) representing the component (b) 2 In the following formula, at least one hydrogen atom of the monomer is substituted with a hydroxyl group. More specifically, the monomers shown below are exemplified. 1 is R in the above general formula (1). 1 is selected from the same options.

[0060] [ka]

[0061] (component (c2)) The component (c2) is a urethane-based bifunctional (meth)acrylate monomer having a urethane bond. The component (c2) may be linear or may have a ring structure. Examples of the ring structure include any ring structure selected from an alicyclic ring, a heterocyclic ring, an aromatic ring, and a heteroaromatic ring. The molecular weight of the component (c2) is more preferably 300 to 600. As the component (c2), two or more types of urethane-based bifunctional (meth)acrylate monomers having different structures may be used in combination. The details of the ring structure will be described in the section on component (c3).

[0062] (component (c3)) The component (c3) is a bifunctional (meth)acrylate monomer having a ring structure. The ring structure of the component (c3) may be any ring structure selected from an alicyclic ring, a heterocyclic ring, an aromatic ring, and a heteroaromatic ring. The molecular weight of the component (c3) is more preferably 400 to 5,000, and even more preferably 400 to 550. As the component (c3), two or more types of bifunctional (meth)acrylate monomers having different structures may be used in combination.

[0063] Examples of the alicyclic structure include cycloalkane structures having 3 to 10 carbon atoms, such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane. In addition, the alicyclic structure may be a bicyclic alicyclic structure, such as bicycloundecane, decahydronaphthalene, norbornene, and norbornadiene; a tricyclic alicyclic structure, such as tricyclodecane and adamantane; or the like. At least a part of the carbon-carbon single bonds contained in the alicyclic structure may be replaced with a carbon-carbon double bond. The alicyclic structure may have a substituent (hereinafter, also referred to as a "fifth substituent"). Examples of the fifth substituent include linear, branched or cyclic alkyl groups having 1 to 6 carbon atoms; aryl groups having 12 or less carbon atoms, such as phenyl and naphthyl groups; and the like.

[0064] Examples of the heterocyclic structure include those in which at least one methylene group in the above alicyclic structure is substituted with a divalent heteroatom-containing group. Examples of the divalent heteroatom-containing group include -O-, -CO-, -COO-, -OCO-, -O-CO-O-, -NHCO-, -CONH-, -NH-, -N(R SP )-, -S-, -SO- and -SO 2 -, etc. Sp is preferably selected from the same options as for the fifth substituent. Examples of aromatic rings include those having 12 or less carbon atoms, such as benzene and naphthalene. Examples of heteroaromatic rings include those having 12 or less carbon atoms, such as furan, thiophene, pyrrole, imidazole, pyridine, pyrimidine, and pyrazine.

[0065] In the photocurable resin composition for imprint molds, the amount of component (c) is preferably 1 to 96% by mass based on the main components. It is more preferably 5% by mass or more, even more preferably 15% by mass or more, and particularly preferably 30% by mass or more. It is also more preferably 70% by mass or less, even more preferably 60% by mass or less, and particularly preferably 50% by mass or less. By setting the amount in this range, it is possible to improve the releasability and durability of a resin mold obtained from the photocurable resin composition for imprint molds.

[0066] In the photocurable resin composition for imprint molds, the total amount of the components (b) and (c) is preferably 30 to 98% by mass based on the main components. The total amount of the components (b) and (c) is more preferably 55% by mass or more, and even more preferably 70% by mass or more. The total amount of the components (b) and (c) is more preferably 95% by mass or less, and even more preferably 85% by mass or less.

[0067] In the photocurable resin composition for imprint molds, the total amount of the components (a), (b) and (c) is preferably 30 mass % or more, more preferably 50 mass % or more, even more preferably 60 mass % or more, and particularly preferably 80 mass % or more, based on the main components.

[0068] The component (c) is preferably an acrylate monomer because it has high photocuring reactivity and can obtain a high reaction rate. If the reaction rate is high, it tends to be difficult to react with the imprinting resin when used as a resin mold, and good releasability tends to be obtained. If the photocuring reactivity is high, it tends to be excellent in throughput during mass production of resin molds. Therefore, the component (c) is preferably an acrylate monomer.

[0069] (ingredient (d)) The photocurable resin composition for imprint molds according to one embodiment of the present invention may contain, as component (d), a monofunctional monomer other than the above components (a) to (c) and a tri- or higher functional polyfunctional (meth)acrylate monomer.

[0070] Examples of the monofunctional monomer include a monofunctional (meth)acrylate monomer; a monofunctional (meth)acrylamide monomer; a monofunctional vinyl monomer; and the like. Examples of monofunctional (meth)acrylate monomers other than the above components (a) to (c) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate. aliphatic (meth)acrylates such as butanyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate; (meth)acrylates having an aromatic ring such as benzyl (meth)acrylate, phenoxymethyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyethylene glycol-modified (meth)acrylate, and hydroxyphenoxyethyl (meth)acrylate; and the like. Examples of the monofunctional (meth)acrylamide monomer include dimethyl(meth)acrylamide, (meth)acryloylmorpholine, hydroxyethyl(meth)acrylamide, isopropyl(meth)acrylamide, diethyl(meth)acrylamide, dimethylaminopropyl(meth)acrylamide, dimethylaminopropyl(meth)acrylamide methyl chloride quaternary salt, and diacetone(meth)acrylamide. Examples of the monofunctional vinyl monomer include styrene, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, N-methyl-N-vinylacetamide, and N-vinylformamide. The monofunctional monomer preferably does not have a fluorine atom or a siloxane structure.

[0071] The amount of the monofunctional monomer in the photocurable resin composition for imprint molds is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 10% by mass or less, based on the main components. The amount of the monofunctional monomer, including not only component (d) but also all the monofunctional monomers of all the components (components (a) to (d), etc.) contained in the composition, is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 10% by mass or less. By setting the blend amount within this range, it is possible to enhance the durability of a resin mold obtained from the photocurable resin composition for imprint molds.

[0072] There are no particular limitations on the tri- or higher functional (meth)acrylate monomer other than the above components (a) to (c) as component (d). Examples of the trifunctional or higher polyfunctional (meth)acrylate monomer as component (d) include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol poly(meth)acrylate.

[0073] The amount of the trifunctional or higher polyfunctional (meth)acrylate monomer in the photocurable resin composition for imprint molds is preferably less than 50% by mass, more preferably 30% by mass or less, based on the main components. By setting the amount in this range, it is possible to obtain a resin mold obtained from the photocurable resin composition for imprint molds with good releasability.

[0074] [Photopolymerization initiator and other components] (Photopolymerization initiator) The photocurable resin composition for imprint molds according to one embodiment of the present invention may contain a photopolymerization initiator, additives, and the like in addition to the above-mentioned monomer components.

[0075] The photopolymerization initiator is preferably an α-hydroxyalkylphenone-based or acylphosphine oxide-based initiator. Examples of the α-hydroxyalkylphenone-based photopolymerization initiator include Omnirad184, Omnirad1173, Omnirad127, and Omnirad2959 manufactured by IGM, and ESACUREONE, ESACURE KIP150, ESACURE KIP75LT, ESACURE KIP IT, and ESACURE KIP100F manufactured by Lamberti. Examples of the acylphosphine oxide-based photopolymerization initiator include Omnirad819, Omnirad TPO, and Omnirad1800 manufactured by BASF. The photopolymerization initiator may be used alone or in combination of multiple types.

[0076] The photopolymerization initiator is preferably contained in the photocurable resin composition for imprint molds in an amount of 0.01 to 20% by mass based on the main components. The photopolymerization initiator is more preferably contained in the photocurable resin composition for imprint molds in an amount of 0.1% by mass or more based on the main components, and even more preferably contained in the photocurable resin composition for imprint molds in an amount of 15% by mass or less.

[0077] (Other Ingredients) The photocurable resin composition for an imprint mold according to one embodiment of the present invention may contain a solvent. The solvent may be any solvent that is commonly used in photocurable resin compositions for imprint molds, such as MEK, MIBK, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, and ethyl lactate. In the above, the term "major component basis" refers to the calculation of the components of the composition excluding the solvent as the "major components". The monomer components, photopolymerization initiator, and additives described below are considered to be the major components. When the photocurable resin composition for imprint molds contains a solvent, 1 to 10,000 parts by mass of the solvent can be used per 100 parts by mass of the major components. The photocurable resin composition for imprint molds according to one embodiment of the present invention may contain an additive. Examples of additives include release agents, silane coupling agents, ultraviolet absorbers, antioxidants, light stabilizers, plasticizers, adhesion promoters, thermal polymerization initiators, colorants, fine particles, photoacid generators, photobase generators, surfactants, defoamers, and dispersants. Any additives that are commonly used in photocurable resin compositions for imprint molds can be used. The additives in the photocurable resin composition for imprint molds can be added at will, but when added, the amount is preferably 10% by mass or less based on the main components. A thermal polymerization initiator may be included, but if curing by a photopolymerization initiator is sufficient, it does not necessarily have to be included.

[0078] <2> Preparation of photocurable resin composition for imprint mold The composition in some aspects of the present invention can be prepared by blending and mixing the above-mentioned monomer components, the above-mentioned photopolymerization initiator, and, if necessary, other additives. The photocurable resin composition for imprint molds is preferably prepared so as to have the following viscosity: In other words, it is preferable to prepare a photocurable resin composition for imprint molds having a viscosity such that, when a resin mold is produced using the photocurable resin composition for imprint molds, the concave-convex pattern of a master mold can be quickly filled without air bubbles becoming trapped therein.

[0079] <3> Resin mold One embodiment of the present invention is a resin mold obtained by curing the above-mentioned photocurable resin composition for imprint molds so as to have a plurality of concave and convex patterns. The resin mold can be obtained by a normal resin mold manufacturing method. Specifically, the resin mold of one embodiment of the present invention can be obtained by a manufacturing method including a step of forming a composition layer of a photocurable resin composition for imprint molds, a step of contacting a metal mold for resin molds (hereinafter also referred to as a "master mold") with the surface of the composition layer, a step of irradiating the composition layer with light to obtain a photocured product having a concave-convex pattern formed thereon, and a step of peeling off the metal mold from the photocured product to obtain a resin mold.

[0080] The light irradiation conditions are preferably such that the reaction rate of the composition of the composition layer is 80% or more from the viewpoint of durability. The reaction rate can be measured using IR based on the peak of the (meth)acryloyl group. Since the conditions for achieving a reaction rate of 80% or more vary depending on the blending ratio of each component in the composition, it is preferable to determine the above conditions in advance by curing the composition to be used. Details will be provided later. The resin mold according to one embodiment of the present invention uses a specific composition, and therefore has good durability and excellent releasability with respect to the transfer layer.

[0081] An example of a method for producing a resin mold according to one embodiment of the present invention will be described below. Specifically, first, as shown in Fig. 1(a), a transparent substrate 1 and a master mold 3 having a concave-convex pattern are prepared, and a photocurable resin composition 2 for imprint molds according to one embodiment of the present invention is disposed on the substrate 1 to form a resin composition layer. Next, as shown in Fig. 1(b), the composition 2 is brought into contact with the substrate 1 and the master mold 3, and the concave portions of the concave-convex pattern of the master mold 3 are filled with the composition 2 (filling step). Note that, although Fig. 1 shows the composition 2 disposed on the substrate 1, the composition 2 may be provided on the master mold 3.

[0082] The substrate 1 is appropriately selected. For example, when the photocurable resin composition for imprint molds according to one embodiment of the present invention is sandwiched between the master mold 3 and the substrate 1 and the composition is cured by light irradiation, a substrate that transmits light is suitable. Examples of the substrate include transparent inorganic substrates such as glass, quartz, and sapphire; ceramic substrates; and synthetic resin substrates such as polycarbonate, PET (polyethylene terephthalate), and triacetyl cellulose. The surface of the substrate 1 may be pretreated to adjust the affinity with the composition 2. Specific examples of the pretreatment include wet surface cleaning; surface modification using plasma, ozone cleaning, and the like; and surface treatments such as with silane coupling agents.

[0083] The method for disposing the composition 2 on the substrate 1 or the master mold 3 is not particularly limited, and examples thereof include coating and dripping of the composition diluted with a solvent etc. as necessary. Specific examples of the method include spin coating, roll coating, dip coating, gravure coating, die coating, curtain coating, inkjet coating, and dispenser coating.

[0084] The composition 2 may be disposed so as to cover the entire surfaces of the master mold 3 and the substrate 1, but it may also be disposed only on a part of them.

[0085] The master mold 3 has a desired pattern, such as a concave-convex pattern, formed on its surface. Examples of materials for the mold 3 include synthetic resins, such as quartz glass and PDMS (polydimethylsiloxane), as well as inorganic compounds, such as silicon, silicon carbide, silicon oxide, and nickel. The appearance of the master mold 3 may be similar to that of a mold used in a typical photoimprint method, and may be, for example, rectangular or roll-shaped.

[0086] In order to improve the releasability, the surface of the master mold 3 may be subjected to a treatment for improving the releasability (mold release treatment). The mold release treatment can be performed by a gas phase method, a liquid phase method, or the like, using a known mold release treatment agent, exemplified by perfluoro-based or hydrocarbon-based polymer compounds, alkoxysilane compounds, trichlorosilane compounds, diamond-like carbon, and the like. Commercially available fluorine-based mold release treatment agents include "OPTOOL" manufactured by Daikin Industries, Ltd. (e.g., OPTOOL DSX, HD1100Z, HD2100Z, HD1100TH), and the like.

[0087] The uneven pattern formed on the surface of the master mold 3 is appropriately selected. For example, it may be the same as the uneven pattern formed on the surface of a mold used in a normal photoimprinting method. For example, the recess may be formed by forming a depression on the surface of the material of the master mold 3, and in this case, the portion relatively protruding toward the surface side becomes the protrusion. The protrusion may be formed by providing a protrusion on the surface of the material of the master mold 3, and in this case, the portion relatively recessed inward becomes the recess. Furthermore, a master having an uneven pattern formed by providing a depression or protrusion on the surface of the material of the master may be used, and a mold formed using this master as a mold may be used as the master mold 3. The cross-sectional shape of each recess of the uneven pattern may be, for example, a square, a rectangle, a triangle, a circle, a semicircle, or a shape similar to these shapes. Each recess may have a depth of about 0.00001 to 3 mm, and an opening diameter of about 0.00001 to 5 mm.

[0088] After the composition 2 is placed on the substrate 1 or the master mold 3 in this manner, the substrate 1 and the master mold 3 are placed opposite each other, and as shown in Fig. 1(b), the composition 2 is brought into contact with the surface of the master mold 3 on which the concave-convex pattern is formed, thereby filling the concaves of the concave-convex pattern of the master mold 3 with the composition. When filling the concaves of the concave-convex pattern with the composition 2, a force of about 0.01 to 10 MPa may be applied, if necessary. Note that a conventional device for a photoimprint method can be used for the filling step.

[0089] Next, as shown in FIG. 1(c), the composition 2 is brought into contact with a master mold 3, and the concave portions of the relief pattern of the master mold 3 are filled with the composition 2. The composition 2 is then irradiated with light to harden it, forming a resin mold 4, which is a photocured product (photocuring process).

[0090] The light source used for light irradiation may be any light source capable of irradiating light with a wavelength at which the composition is cured, for example, light with a wavelength of 200 to 500 nm, but preferably light with a wavelength that is transmitted through at least a part of the substrate 1 or the master mold 3. Examples of the light source include a low pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc, a mercury xenon lamp, an excimer laser such as XeCl or KrF, an ultraviolet or visible light laser, and an ultraviolet or visible light LED. The amount of light irradiation may be any amount that can cure the composition. When carrying out the present invention, the amount is usually 0.1 to 500 J / cm. 2 The amount of irradiation may be selected within the range above, and is appropriately selected depending on the composition and / or the desired thickness of the resin layer, etc. The composition 2 is irradiated with light from the side of the member, out of the substrate 1 and the master mold 3, that is substantially transparent to the irradiated light.

[0091] Next, as shown in FIG. 1(d), the master mold 3 is released from the resin mold 4 of one embodiment of the present invention, and, if necessary, the resin mold 4 is peeled off from the substrate 1 to form the resin mold 4 in which the concave-convex pattern of the master mold 3 is transferred in an inverted manner. The method of using the obtained resin mold 4 can be appropriately selected. For example, in a photo-nanoimprint method, the resin mold can be used in a method of producing a resin using the resin mold and a precursor of a photocurable resin for pattern formation.

[0092] <4> Pattern Formation Method One aspect of the present invention is a pattern forming method comprising the steps of forming a transfer layer on a substrate using a photocurable resin composition for imprint transfer, contacting the surface of the transfer layer with the resin mold, and irradiating the transfer layer with light to form a concave-convex pattern. A pattern can be formed in the same manner as in a normal imprint method, except that the resin mold according to one embodiment of the present invention is used. As the photocurable resin composition for imprint transfer, a conventional one can be used.

[0093] An example of a pattern forming method according to one embodiment of the present invention will be described below. Specifically, first, as shown in Fig. 2(a), a substrate 5 and a resin mold 4 according to one embodiment of the present invention having a concave-convex pattern are prepared, and a photocurable resin composition 6 for imprint transfer is placed on the substrate 5 to form a transfer layer. Next, as shown in Fig. 2(b), the composition 6 is sandwiched between the substrate 5 and the resin mold 4, and the concaves of the concave-convex pattern of the resin mold 4 are filled with the composition 6 (filling step). Note that, although Fig. 2(b) shows the composition 6 placed on the substrate 5, the composition 6 may be placed on the resin mold 4.

[0094] The substrate 5 may be any substrate on which the composition 6 can be placed, and may be, for example, a substrate used in a typical photoimprint method. Specific examples include semiconductor substrates such as silicon wafers; compound semiconductor substrates such as GaAs, InAs, and GaN; transparent inorganic substrates such as glass, quartz, and sapphire; ceramic substrates; synthetic resin substrates such as polycarbonate, PET (polyethylene terephthalate), and triacetyl cellulose; metal substrates; or metal oxide substrates. Examples of the transparent substrate 5 include glass substrates, quartz substrates, sapphire substrates, and transparent synthetic resin substrates. The surface of the substrate 5 may be pretreated to adjust the affinity with the composition 6. Specific examples of the pretreatment include surface modification by wet surface cleaning, plasma, ozone cleaning, and treatment with an adhesion improver such as a silane coupling agent.

[0095] The method for disposing the composition 6 on the substrate 5 or the resin mold 4 is not particularly limited, and examples thereof include coating or dripping the composition 6 diluted with a solvent or the like as necessary. Specific examples of the method include spin coating, roll coating, dip coating, gravure coating, die coating, curtain coating, inkjet coating, and dispenser coating.

[0096] The composition 6 may be disposed so as to cover the entire surfaces of the resin mold 4 and the substrate 5, but may also be disposed only on a part of them.

[0097] The appearance of the resin mold 4 may be similar to that of the master mold 3 used in a typical photoimprint method, and may be, for example, a rectangular parallelepiped or roll-shaped. The concave-convex pattern formed on the surface of the resin mold 4 is an inverted concave-convex pattern of the master mold 3.

[0098] After the composition 6 is placed on the substrate 5 or the resin mold 4 in this manner, the substrate 5 and the resin mold 4 are placed opposite each other, and the composition 6 is brought into contact with the surface of the resin mold 4 on which the concave-convex pattern is formed, as shown in Fig. 2(b), to fill the resin composition 6 into the concaves of the concave-convex pattern of the resin mold 4. During this filling, a force of about 0.01 to 10 MPa may be applied, if necessary. Note that an imprinting device used in a conventional optical imprinting method can be used for the filling step.

[0099] Next, as shown in FIG. 2(c), the composition 6 is brought into contact with the resin mold 4 to fill the recesses of the uneven pattern of the resin mold 4 with the composition 6, and the composition 6 is cured by light irradiation to form a photocured layer 7 (photocuring process).

[0100] Examples of light sources used for light irradiation include those similar to those used in the photocuring step in producing the resin mold 4. The amount of light irradiation may be an amount sufficient to cure the composition 6. When carrying out the present invention, the amount of light irradiation varies depending on the composition of the composition 6 to be cured, the layer thickness, etc., but is usually 0.1 to 10 J / cm. 2 The amount of irradiation may be selected within the range of 1. The composition 6 is irradiated with light from the side of the member, out of the substrate 5 and the resin mold 4, which is substantially transparent to the irradiated light.

[0101] Next, as shown in FIG. 2(d), the resin mold 4 is released from the photocured layer 7, and if necessary, the photocured layer 7 is peeled off from the substrate 5, thereby forming a photocured layer 7 to which the concave-convex pattern of the resin mold 4 has been transferred.

[0102] The photocurable layer having a pattern obtained by the pattern forming method in some embodiments of the present invention can be used as an optical member as described below. Furthermore, the photocured layer having a pattern obtained by the pattern formation method in some aspects of the present invention may be used as an etching resist.

[0103] <5> Complex One aspect of the present invention is a composite having the above-mentioned resin mold and a photocured layer formed by irradiating a transfer layer formed using a photocurable resin composition for imprint transfer with light while the resin mold is in contact with the transfer layer. The above composite can be obtained by the same manufacturing method as a general imprint method, except that the resin mold according to one embodiment of the present invention is used. The photocurable resin composition for imprint transfer may be a conventional one.

[0104] The resin mold according to one embodiment of the present invention has excellent releasability and durability, and is low-cost, so that it can also be used as a protective member for the member obtained by the pattern forming method. That is, the photocured layer and the resin mold are not peeled off immediately after the photocuring step, so that the resin mold functions as a protective member that protects the uneven structure of the photocured layer. This protective member / resin mold can then be peeled off from the photocured layer. In this way, by using the resin mold after the photocuring step as a protective member, it is possible to prevent damage to the concave-convex structure during transportation and to prevent foreign matter from entering the concave-convex structure. In addition, even if the composition is other than the resin composition for imprint molds used in the examples described later, if the composition contains the above components (a) and (b) in the above specific ratio, the resulting resin mold tends to have excellent long-term releasability and is useful as the protective member / resin mold.

[0105] <6> Method for producing the composite One aspect of the present invention is a method for producing a composite, comprising the steps of forming a transfer layer on a substrate using a photocurable resin composition for imprint transfer, contacting the resin mold with a surface of the transfer layer, and irradiating the transfer layer with light to form a photocured layer having a concave-convex pattern, thereby obtaining a composite having the resin mold and the photocured layer.

[0106] <7> Manufacturing method of optical member One aspect of the present invention is a method for producing an optical member by using the above-mentioned pattern formation method.

[0107] Except for using the resin mold according to one embodiment of the present invention, an optical member may be manufactured by a normal imprint pattern forming method. Specifically, the method for manufacturing an optical member according to one embodiment of the present invention is a method for manufacturing an optical member having a cured layer having a concave-convex structure, comprising the steps of forming a composition layer on a substrate using the photocurable resin composition for imprint transfer, pressing the resin mold against the surface of the composition layer to transfer the concave-convex structure to the composition layer to form a pattern-forming layer, and photocuring the pattern-forming layer to form a cured layer having a concave-convex structure.

[0108] In some embodiments of the present invention, the pattern of the optical member is a pattern having a size of several nm to several mm. The method for producing an optical member according to one embodiment of the present invention can be applied to pattern transfer in the nano-order, micro-order, milli-order, etc., and is particularly effective for minute pattern transfer in the nano-order and micro-order. In the present invention, "light" includes not only light and electromagnetic waves with wavelengths in the ultraviolet, near ultraviolet, far ultraviolet, visible, infrared, and other regions, but also radiation. The optical members produced by the above-mentioned method can be used for applications such as camera lenses such as condenser lenses, light guide plates, anti-reflection films, films for optical waveguides, and glasses. EXAMPLES

[0109] Some aspects of the present invention will be described below based on examples, but the present invention is not limited to these examples in any way.

[0110] (Component (a)) The following was prepared as component (a):

[0111] [ka]

[0112] Details of the component (a) used in the examples and comparative examples are shown below. HDFD-A (Tokyo Chemical Industry Co., Ltd., fluorine content: 62.3% by mass) FAAC-6 (manufactured by Unimatec Co., Ltd., fluorine content: 59.1% by mass) FAAC-4 (manufactured by Unimatec Co., Ltd., fluorine content: 53.7% by mass) TFEA (Tokyo Chemical Industry Co., Ltd., fluorine content: 33.9% by mass)

[0113] (ingredient (b)) The following was prepared as component (b):

[0114] [ka]

[0115] Details of the component (b) used in the examples and comparative examples are shown below. 1.6HX-A (Kyoeisha Chemical Co., Ltd.) A-NOD-N (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) A-200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) APG-100 (manufactured by Shin-Nakamura Chemical Co., Ltd.) FA-124AS ​​(Hitachi Chemical Co., Ltd.) HX-220 (manufactured by Nippon Kayaku Co., Ltd.) A-600 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) APG-700 (Shin-Nakamura Chemical Co., Ltd.)

[0116] (component (c)) As component (c), the following was prepared.

[0117] [ka]

[0118] Details of the component (c) used in the examples and comparative examples are shown below. A-DCP (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 70PA (Kyoeisha Chemical Co., Ltd.) 200PA (Kyoeisha Chemical Co., Ltd.) ADBE-200 (manufactured by Nippon Oil & Fats Co., Ltd.) R-604 (manufactured by Nippon Kayaku Co., Ltd.)

[0119] The alicyclic urethane diacrylate shown above was synthesized as follows. Into a three-neck flask equipped with a water-cooled condenser, 9.78 g (0.044 mol) of isophorone diisocyanate (Tokyo Chemical Industry Co., Ltd.), 10.3 g (0.089 mol) of 2-hydroxyethyl acrylate (Tokyo Chemical Industry Co., Ltd.), and 5 mg of dibutyltin dilaurate as a catalyst were added and stirred at 80° C. for 5 hours. After that, the mixture was left to cool to room temperature to obtain an alicyclic urethane diacrylate.

[0120] The above-mentioned linear urethane diacrylate was synthesized as follows. In a three-neck flask equipped with a water-cooled condenser, 9.50 g (0.045 mol) of trimethylhexamethylene diisocyanate (Tokyo Chemical Industry Co., Ltd.), 10.6 g (0.091 mol) of 2-hydroxyethyl acrylate (Tokyo Chemical Industry Co., Ltd.), and 5 mg of dibutyltin dilaurate as a catalyst were added and stirred at 80° C. for 3 hours. After that, the mixture was left to cool to room temperature to obtain a chain urethane diacrylate.

[0121] Details of the component (d) used in the examples are given below. CHA: Cyclohexyl acrylate (Osaka Organic Chemical Industry Co., Ltd.) TMPTA: Trimethylolpropane triacrylate (Osaka Organic Chemical Industry Co., Ltd.)

[0122] <Preparation of Photocurable Resin Composition Sample for Imprint Mold> The components having the compositions and amounts (parts by mass) shown in Tables 1 to 8 were stirred and mixed at room temperature to prepare photocurable resin composition samples for imprint molds (Examples 1 to 43 and Comparative Examples 1 to 4). Details of the photopolymerization initiators in the table are as follows: Omnirad1173 (manufactured by IGM Resins B.V.)

[0123] <Appearance Evaluation of Photocurable Resin Composition for Imprint Mold> First, the appearance of each of the prepared resin compositions for imprint molds (Examples 1 to 43 and Comparative Examples 1 to 4) was visually observed and evaluated according to the following criteria. ◯: The composition is transparent and no phase separation is observed. ×: The composition is opaque or phase separation is observed. In addition, it was determined that the resin composition for imprint molds that was rated as × could not be used to produce a resin mold, and the reaction rate of the resin mold, the releasability of the resin mold, and the transfer durability of the resin mold were not evaluated. The results are shown in Tables 1 to 8.

[0124] <Making a resin mold> Each of the above photocurable resin compositions for imprint molds was dropped with a dropper onto a 100 μm thick adhesive-treated PET film (Cosmoshine A4100, manufactured by Toyobo Co., Ltd.) and uniformly coated to a film thickness of approximately 10 μm using a bar coater. Next, the PET films coated with each of the above photocurable resin compositions for imprint molds were pressed against a nickel mold (length 50 mm, width 50 mm, thickness 1 mm) with a fine uneven pattern that had been release-treated with a commercially available fluorine-based release treatment agent (Optool HD2101Z, manufactured by Daikin Industries, Ltd.). In this state, the composition was photocured by irradiating the PET film side with light using an LED light source having a wavelength of 365 nm under a nitrogen atmosphere. The irradiation dose was 1500 mJ / cm. 2 After photocuring, the nickel mold was released to obtain a resin mold having a fine concave-convex pattern.

[0125] <Evaluation of releasability of resin mold> A photocurable resin composition for imprint transfer was dropped onto the resin mold (Examples 1 to 43 and Comparative Examples 1 to 4) prepared as described above. Next, a PET film was placed on the photocurable resin composition for imprint transfer, and the photocurable resin composition for imprint transfer was sandwiched between the PET film and the resin mold. An LED light source was used from the PET film side to provide 1 J / cm 2 The photocurable resin composition for imprint transfer was cured by irradiating light under the conditions of 1. to form a photocured layer. The photocured layer was then peeled off from the resin mold. The amount of force applied at this time, i.e., the mold releasability, was judged by touch, and the mold releasability of the resin mold was evaluated as follows. ◎◎ (Very good releasability); Can be easily released with very little force, enabling pattern transfer. ◎ (Very good releasability); Can be easily released with slight force, enabling pattern transfer. Good (good releasability); requires some force but pattern can be transferred. × (poor releasability): Defects were observed in some or all areas, making it impossible to transfer the pattern.

[0126] In addition, after photocuring, the releasability (long-term releasability) was also evaluated after 168 hours or more had elapsed under the condition of 25° C. The evaluation criteria at that time were the same as those described above.

[0127] <Evaluation of transfer durability of resin mold> A series of operations (durability test) consisting of dropping, irradiating, and peeling off the resin composition for imprint transfer was repeated, and the surface of the resin mold was observed to see if there was any noticeable roughness that could be visually identified. From the results, the transfer durability of each resin mold (Examples 1 to 43 and Comparative Examples 1 to 4) was evaluated as follows. The occurrence of significant roughness on the surface of the resin mold is due to a decrease in the releasability of the resin mold caused by deterioration of the surface of the resin mold, etc. When significant roughness occurs on the surface of the resin mold, significant roughness is observed on the surface of the obtained photocured layer. ⊚ (Good): After 200 durability tests, there is little or no roughness on the surface of the resin mold. ○ (fairly good); Significant roughness occurred on the surface of the resin mold after 51 to 200 cycles of durability testing. × (bad): Significant roughness was observed on the surface of the resin mold after 10 to 50 durability tests.

[0128] In the above results, "x (poor)" refers to an evaluation of the durability of the resin mold based on the above criteria, and does not mean that it cannot be used in all cases. In other words, even a resin composition judged to be "x (poor)" can be used as a material for forming a resin mold depending on the number of transfers required and the level of definition. Of course, this does not prevent it from being used as a composition for forming a transfer layer other than a resin mold.

[0129] <Reaction rate of resin mold> The photocurable composition for imprint molds before curing and the resin mold after curing were measured by the ATR method of FT-IR. This measurement revealed that the 810 cm -1 The reduction rate of the peak at 1720 cm originating from the carbonyl group contained in the (meth)acryloyl group was calculated before and after photocuring, and the reaction rate was derived. -1 The reaction rate was evaluated based on the following criteria: 〇 (Good); Response rate is 80% or more × (poor); response rate is less than 80%

[0130] [Table 1]

[0131] [Table 2]

[0132] [Table 3]

[0133] [Table 4]

[0134] [Table 5]

[0135] [Table 6]

[0136] [Table 7]

[0137] [Table 8]

[0138] As shown in the table, the resin molds obtained from the photocurable resin compositions for imprint molds of some embodiments of the present invention are excellent in releasability, long-term releasability and durability, while the resin molds obtained from the photocurable resin compositions for imprint molds of the comparative examples are inferior in releasability, long-term releasability and durability. [Industrial Applicability]

[0139] According to the present invention, a resin mold having releasability and durability can be obtained, and a low-cost photocurable resin composition for imprint molds can be provided. [Explanation of symbols]

[0140] 1 Board 2. Photocurable resin composition for imprint mold 3 Master Mold 4 Resin mold 5 Substrate 6 Photocurable resin composition for imprint transfer 7 Photo-curing layer

Claims

1. Component (a): at least one selected from the group consisting of a fluorine-based (meth)acrylate monomer having at least one (meth)acryloyloxy group and a dialkylsiloxane-based (meth)acrylate monomer having at least one (meth)acryloyloxy group; Component (b): at least one selected from the group consisting of acyclic bifunctional (meth)acrylate monomers having two (meth)acryloyloxy groups, represented by the following formula (1): Component (c): at least one selected from the group consisting of urethane-based bifunctional (meth)acrylate monomers having two (meth)acryloyloxy groups; The component (a) and the component (b) do not contain a monomer corresponding to the component (c), The blending ratio of the component (a) to the component (b) is 1 to 97:99 to 3 by mass ratio, The blending amount of the component (c) is 1 to 96 mass% based on the main components, excluding the solvent, of the photocurable resin composition for imprint molds, The component (b) has a molecular weight of 700 or less, The component (c) is a photocurable resin composition for imprint molds having a molecular weight of 150 to 600. 【Chemistry 1】 (In the general formula (1), R １ each independently represents a hydrogen atom or a methyl group, R ２ is a divalent organic group having no ring structure, The divalent organic group not having a ring structure includes at least one of a linear alkylene group which may have a substituent and a linear alkyleneoxy group which may have a substituent, the substituent having 1 to 4 carbon atoms, and at least one of the methylene groups included in the linear alkylene group and the linear alkyleneoxy group may be replaced with a carbonyl group.

2. the divalent organic group not having a ring structure is at least one of a linear alkylene group which may have a substituent and a linear alkyleneoxy group which may have a substituent, 2. The photocurable resin composition for imprint molds according to claim 1, wherein the substituent has 1 to 4 carbon atoms, and at least one of methylene groups contained in the linear alkylene group and the linear alkyleneoxy group is optionally substituted with a carbonyl group.

3. The linear alkylene group which may have a substituent has at least one structure represented by the following formula (2): 【Chemistry 2】 (In the above formula (2), R ａ１ ~R ａ２ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The linear alkyleneoxy group which may have a substituent has at least one structure represented by the following formula (3): 【Chemistry 3】 (R ｂ１ ~R ｂ４ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X is an oxygen atom or a sulfur atom. At least one of methylene groups contained in the linear alkylene group and the linear alkyleneoxy group may be replaced with a carbonyl group, When the divalent organic group has two or more structures represented by the formula (2) and / or two or more structures represented by the formula (3), R ａ１ ~R ａ２ and R ｂ１ ~R ｂ４ 3. The photocurable resin composition for imprint molds according to claim 1 or 2, wherein each of the above may be the same or different.

4. The photocurable resin composition for imprint molds according to any one of claims 1 to 3, wherein the component (a) is at least one of a fluorine-based (meth)acrylate monomer having at least one (meth)acryloyloxy group and a dialkylsiloxane-based (meth)acrylate monomer having at least one (meth)acryloyloxy group, and wherein the fluorine content is 34 to 65 mass%.

5. The photocurable resin composition for imprint molds according to any one of claims 1 to 4, wherein the acyclic difunctional (meth)acrylate monomer is an acyclic difunctional acrylate monomer.

6. 6. The photocurable resin composition for imprint molds according to claim 1, wherein the amount of the monofunctional monomer is 50 mass% or less based on the total amount of monomers in the photocurable resin composition for imprint molds.

7. The photocurable resin composition for imprint molds according to any one of claims 1 to 6, wherein the blending amount of the component (a) is 1 to 35 mass% based on the main components of the photocurable resin composition for imprint molds.

8. The photocurable resin composition for imprint molds according to any one of claims 1 to 7, wherein the blending amount of the component (b) is 1 to 96 mass% based on the main components of the photocurable resin composition for imprint molds.

9. 9. A resin mold obtained by curing the photocurable resin composition for imprint molds according to claim 1 so as to have a plurality of concave-convex patterns.

10. forming a transfer layer on a substrate using a photocurable resin composition for imprint transfer; A step of contacting the resin mold according to claim 9 with a surface of the transfer layer; and forming a concave-convex pattern by irradiating the transfer layer with light.

11. The resin mold according to claim 9 ; a photocured layer formed by irradiating a transfer layer formed using a photocurable resin composition for imprint transfer with light while the resin mold is in contact with the transfer layer.

12. forming a transfer layer on a substrate using a photocurable resin composition for imprint transfer; A step of contacting the resin mold according to claim 9 with a surface of the transfer layer; and irradiating the transfer layer with light to form a photocured layer having a concave-convex pattern, thereby obtaining a composite having the resin mold and the photocured layer.

13. A method for producing an optical member, comprising the step of: producing an optical member by using the pattern forming method according to claim 10 .

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