Resin composition, cured product, laminate, and method for manufacturing the laminate

Abstract

To provide a resin composition having excellent solvent resistance and moldability, as well as excellent coatability, and a cured product of the resin composition. [Solution] A resin composition comprising compound A having cresol novolac type (meth)acrylate units and / or phenol novolac type (meth)acrylate units, a 2- to 4-functional (meth)acrylate compound B, a photopolymerization initiator C, and a solvent D, wherein compound A has a (meth)acrylic equivalent of 200-290 g / mol, a viscosity of 30-3,000 mPa·s at a solid content concentration of 50% by mass at 25°C, and a carbon atom mass ratio of 60-84% by mass, and (meth)acrylate compound B has a (meth)acrylic equivalent of 120-290 g / mol, a viscosity of 0.5-20 mPa·s at a solid content concentration of 50% by mass at 25°C, and a carbon atom mass ratio of 60-84% by mass.

Description

Technical Field

[0001] The present invention relates to a resin composition, a cured product, a laminate, and a method for producing a laminate.

Background Art

[0002] In recent years, with the improvement in the integration density of semiconductor integrated circuits, methods for forming complex and fine patterns have been studied. Among these forming methods, the imprint method has attracted attention. In the imprint method, a mold having a fine pattern on its surface is pressed against a resin applied on a substrate and then press-molded and cured, thereby transferring the fine pattern of the mold to the resin to form a complex and fine pattern.

[0003] The resin composition used in the imprint method is required to have solvent resistance. Also, it is required to be excellent in coating properties and moldability. As such a resin composition used in the imprint method, Patent Document 1 discloses an imprint molding resin composition containing at least one (meth)acrylate oligomer (A) selected from the group consisting of urethane (meth)acrylate oligomer and epoxy (meth)acrylate oligomer, at least one (meth)acrylate monomer (B) selected from the group consisting of a hydroxyl group-containing (meth)acrylate monomer and a carboxyl group-containing (meth)acrylate monomer, and a photopolymerization initiator (C), and having a viscosity of 1000 mPa·s or less.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, when using the resin composition described in Patent Document 1 to form complex and fine patterns, it was found that deformation of the cured material was likely to occur when separating the mold, resulting in insufficient moldability. The object of the present invention is to provide a resin composition having excellent solvent resistance and moldability of the resulting cured product, as well as excellent coatability, a cured product of the resin composition, a laminate having the cured product, and a method for manufacturing the laminate using the resin composition. [Means for solving the problem]

[0006] The present invention has the following aspects. [1] A resin composition comprising compound A having either or both cresol novolac type (meth)acrylate units and phenol novolac type (meth)acrylate units, a 2- to 4-functional (meth)acrylate compound B, a photopolymerization initiator C, and a solvent D, wherein compound A has units with a (meth)acrylic equivalent of 200-290 g / mol, a viscosity of 30-3,000 mPa·s at a solid content concentration of 50% by mass at 25°C, and a carbon atom mass ratio calculated by the following formula f1 of 60-84% by mass, and (meth)acrylate compound B has a (meth)acrylic equivalent of 120-290 g / mol, a viscosity of 0.5-20 mPa·s at a solid content concentration of 50% by mass at 25°C, and a carbon atom mass ratio calculated by the following formula f1 of 60-84% by mass. Carbon atom mass ratio=(A1 C ×12) / (A1 C ×12+A1 H ×1+A1 O ×16)×100 formula f1 In the above formula f1, A1 C A1 is the number of carbon atoms contained in compound A or (meth)acrylate compound B, H A1 is the number of hydrogen atoms contained in compound A or (meth)acrylate compound B, and O This is the number of oxygen atoms contained in compound A or (meth)acrylate compound B. [2] The resin composition according to [1], wherein the compound A has a unit represented by the following formula 1. [Chemical formula] In the above formula 1, R 1 is a hydrogen atom, a monovalent hydrocarbon group, or a halogen atom, and R 2 is a hydrogen atom, a monovalent hydrocarbon group, or a halogen atom, and R 3 is a divalent hydrocarbon group, and R 4 is a divalent hydrocarbon group, and R 5 is a single bond or a divalent hydrocarbon group, and R 6 is a hydrogen atom or a monovalent hydrocarbon group, and X is a divalent hydrocarbon group. [3] The resin composition according to [1] or [2], wherein the (meth)acrylate compound B has either or both of an aromatic ring and an alicyclic ring. [4] The resin composition according to any one of [1] to [3], wherein the content of the compound A is 30 to 75 parts by mass with respect to a total of 100 parts by mass of the compound A and the (meth)acrylate compound B. [5] Further comprising a 5- to 15-functional (meth)acrylate compound E, wherein the (meth)acrylate compound E has a (meth)acrylic equivalent of 70 to 100 g / mol, a viscosity of 0.5 to 20 mPa·s at a solid content concentration of 50% by mass at 25°C, and a carbon atom mass ratio calculated by the following formula f2 of 45 to 84% by mass. The resin composition according to any one of [1] to [4]. Carbon atom mass ratio = (A2 C × 12) / (A2 C × 12 + A2 H × 1 + A2 O × 16) × 100 Formula f2 In the above formula f2, A2 C is the number of carbon atoms contained in the (meth)acrylate compound E, A2 H is the number of hydrogen atoms contained in the (meth)acrylate compound E, and A2 O is the number of oxygen atoms contained in the (meth)acrylate compound E. [6] The resin composition according to [5], wherein the content of (meth)acrylate compound E is 10 to 30 parts by mass with respect to 100 parts by mass of the total of (meth)acrylate compound B and (meth)acrylate compound E. [7] The resin composition according to any one of [1] to [6], further comprising a surfactant that does not have a fluoroalkyl group. [8] The resin composition according to [1] to [7], wherein the photopolymerization initiator C comprises an acylphosphine compound. [9] A resin composition according to any one of [1] to [8], wherein the solid content concentration is 1 to 50% by mass.

[10] A resin composition according to any of [1] to [9] used for imprint molding.

[11] A cured product of any of the resin compositions described in [1] to

[10] .

[12] A laminate comprising a substrate and a thin film made of the cured product described in

[11] on one surface of the substrate, wherein the thickness of the thin film is 10 to 500 nm.

[13] The laminate according to

[12] , wherein the thin film has a fine pattern on its surface.

[0007]

[14] A method for manufacturing a laminate having a substrate and a thin film having a fine pattern on one surface of the substrate, comprising: sandwiching a resin composition described in any of [1] to

[10] between a mold having a fine pattern on its surface and the substrate; curing the resin composition to form a thin film having a fine pattern on its surface; and separating the thin film from the mold. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a resin composition having excellent solvent resistance and moldability of the resulting cured product, as well as excellent coatability, a cured product of the resin composition, a laminate having the cured product, and a method for manufacturing the laminate using the resin composition. [Brief explanation of the drawing]

[0009] [Figure 1] This is a schematic cross-sectional view showing an example of a laminate according to one embodiment. [Figure 2] This is a schematic cross-sectional view showing an example of a laminate according to one embodiment. [Figure 3] This is a schematic diagram showing a method for manufacturing a laminate according to one embodiment. [Modes for carrying out the invention]

[0010] The embodiments of the present invention will be described in detail below, but the following description is merely one example of an embodiment of the present invention, and the present invention is not limited to these contents and can be modified and implemented within the scope of its gist. Figures 1 to 3 are schematic diagrams, and the dimensional ratios differ from those of the actual figures for convenience.

[0011] The meanings and definitions of terms used in this invention are as follows: "Light" is a general term encompassing ultraviolet light, visible light, infrared light, electron beams, and radiation.

[0012] The number of functional groups refers to the number of monovalent groups represented by the following formula 1-1. CH2=CR 10 -C(=O)-O-* Formula 1-1 In formula 1 above, R 10 R is a hydrogen atom, a monovalent hydrocarbon group, or a halogen atom, and * is a bond. A preferred embodiment of the monovalent hydrocarbon group is R in Formula 1 described later. 1 This is the same as the preferred embodiment. "(Meth)acrylate" refers to a compound obtained by bonding a monovalent hydrocarbon group, which may have a heteroatom, to the bond of formula 1-1 above. "(meth)acrylic acid" refers to the compound obtained when the hydrogen atoms bonded in formula 1-1 above are combined.

[0013] (Meth)acrylic equivalent refers to the molecular weight per monovalent group represented by formula 1-1 above. That is, the (meth)acrylic equivalent is calculated by dividing the molecular weight of compound A, (meth)acrylate compound B, or (meth)acrylate compound E, described below, by the number of monovalent groups represented by formula 1-1 above. Furthermore, the (meth)acrylic equivalent of a unit in compound A is calculated by dividing the molecular weight of the unit by the number of monovalent groups represented by formula 1-1 above contained in the unit. Note that the molecular weights of (meth)acrylate compound B and (meth)acrylate compound E are formula weights. The (meth)acrylic equivalent of compound A is the same as the (meth)acrylic equivalent of the unit if compound A has only one type of unit. If compound A has two types of units, the (meth)acrylic equivalent is calculated by taking a weighted average of the (meth)acrylic equivalent of each unit and the number of each unit.

[0014] The carbon atom mass ratios of compound A, (meth)acrylate compound B, and (meth)acrylate compound E, described below, can be calculated using the following formula f3. Carbon atom mass ratio = (A C ×12) / (A C ×12+A H ×1+A O ×16)×100 formula f3 In the above formula f3, A C This is the number of carbon atoms contained in compound A, (meth)acrylate compound B, or (meth)acrylate compound E, and A H This is the number of hydrogen atoms contained in compound A, (meth)acrylate compound B, or (meth)acrylate compound E, and A O This is the number of oxygen atoms contained in compound A, (meth)acrylate compound B, or (meth)acrylate compound E.

[0015] The number-average molecular weight (hereinafter also referred to as "Mn") and weight-average molecular weight (hereinafter also referred to as "Mw") are polystyrene-equivalent molecular weights obtained by measuring them using gel permeation chromatography (hereinafter also referred to as "GPC") with a calibration curve prepared using polystyrene as a standard sample.

[0016] The viscosity of compound A, (meth)acrylate compound B, and (meth)acrylate compound E at a solid content concentration of 50% by mass at 25°C can be measured using a rotational viscometer at 25±0.2°C. The rotational speed during measurement is set according to the viscosity, as shown in the examples described later. For example, propylene glycol monomethyl ether acetate can be used as solvent D. The solid content concentration is calculated by (solid content mass / sample mass) × 100, where the sample mass is the mass of the sample before heating, and the solid content mass is the mass of the sample after drying it in a convection dryer at 120°C for 4 hours. The refractive index can be measured using a refractive index measuring device. The "~" symbol indicating a numerical range means that the numbers before and after it are included as the lower and upper limits, respectively.

[0017] ≪Resin composition≫ The resin composition of this embodiment comprises compound A having either or both of cresol novolac-type (meth)acrylate units and phenol novolac-type (meth)acrylate units, a 2- to 4-functional (meth)acrylate compound B, a photopolymerization initiator C, and a solvent D. In one embodiment of the present invention, resin compositions containing any one of an alkali-soluble polymer compound, carboxylic acid-added caprolactone-modified tetramethylolmethane triacrylate, and a thermal crosslinking agent are excluded from the resin composition. Furthermore, in yet another embodiment of the present invention, resin compositions containing an alkali-soluble polymer compound, carboxylic acid-added caprolactone-modified tetramethylolmethane triacrylate, and a thermal crosslinking agent are excluded from the resin composition. The resin composition may further contain components other than compound A, (meth)acrylate compound B, photopolymerization initiator C, and solvent D (optional components) as needed, as long as they do not impair the effects of the present invention.

[0018] <Compound A> Compound A has either one or both of the following: a cresol novolac type (meth)acrylate unit and a phenol novolac type (meth)acrylate unit. A cresol novolac-type (meth)acrylate unit refers to a unit obtained by reacting a cyclic ether group in a cresol novolac unit having a cyclic ether group with (meth)acrylic acid. Examples of cresol novolac units having a cyclic ether group include cresol novolac epoxy units and cresol novolac oxetane units. A phenol novolac-type (meth)acrylate unit refers to a unit obtained by reacting a cyclic ether in a phenol novolac unit having a cyclic ether group with (meth)acrylic acid. Examples of phenol novolac units having a cyclic ether group include phenol novolac epoxy units and phenol novolac oxetane units. The above cyclic ether group may be a cyclic ether group other than an epoxy group or an oxetane group. In this specification, derivatives in which the methyl group bonded to the benzene ring in a cresol novolac-type (meth)acrylate unit is substituted with other monovalent hydrocarbon groups or halogen atoms are also included in the cresol novolac-type (meth)acrylate unit.

[0019] The units represented by the following formula 1 are preferred as cresol novolac type (meth)acrylate units and phenol novolac type (meth)acrylate units.

[0020] [ka] In formula 1 above, R 1 R is a hydrogen atom, a monovalent hydrocarbon group, or a halogen atom. 2 R is a hydrogen atom, a monovalent hydrocarbon group, or a halogen atom. 3 It is a divalent hydrocarbon group, R 4 It is a divalent hydrocarbon group, R 5 R is a single bond or a divalent hydrocarbon group. 6 X is a hydrogen atom or a monovalent hydrocarbon group, and X is a divalent hydrocarbon group.

[0021] R 1 and R 2 Examples of monovalent hydrocarbon groups include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 5 to 20 carbon atoms, and aryl groups having 6 to 20 carbon atoms. R 1 and R 2 Preferably, the group consists of a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms. Examples of monovalent hydrocarbon groups having 1 to 4 carbon atoms include alkyl groups, alkenyl groups, and cycloalkyl groups. Alkyl groups and alkenyl groups may be linear or branched. Among these, methyl groups, ethyl groups, and propyl groups are preferred, with methyl groups being more preferred.

[0022] R 3 of and R 4 As the divalent hydrocarbon group, an alkylene group having 1 to 10 carbon atoms is preferred, an alkylene group having 1 to 4 carbon atoms is more preferred, and a methylene group is even more preferred. When the number of carbon atoms is 2 or more, R 3 and R 4 The chain can be either straight or branched, but a straight chain is preferred. R 5 As such, a single bond or an alkylene group is preferred, a single bond or an alkylene group having 1 to 4 carbon atoms is more preferred, and a single bond is even more preferred. When the number of carbon atoms is 2 or more, R 5 The chain can be either straight or branched, but a straight chain is preferred. R 6 As such, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is preferred, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is more preferred, and a hydrogen atom is even more preferred. When the number of carbon atoms is 2 or more, R 6 The chain can be either straight or branched, but a straight chain is preferred.

[0023] Examples of X include alkylene groups and alkenylene groups having 1 to 20 carbon atoms, cycloalkylene groups and cycloalkenylene groups having 5 to 20 carbon atoms, and arylene groups having 6 to 20 carbon atoms. Cycloalkylene groups, cycloalkenylene groups, and arylene groups may have a fused ring structure. Among these, methylene groups, ethylene groups, trimethylene groups, cyclohexylene groups, phenylene groups, dicyclopentadienyl groups, and naphthylene groups are preferred as X, with methylene groups and dicyclopentadienyl groups being more preferred.

[0024] Compound A is preferably the compound represented by the following formula 2.

[0025] [ka] In equation 2 above, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and X are the same as in equation 1 above. Multiple R 1 They may be the same or different, but being the same is preferable. Multiple R 2 They may be the same or different, but being the same is preferable. Multiple R 3 They may be the same or different, but being the same is preferable. Multiple R 4 They may be the same or different, but being the same is preferable. Multiple R 5 They may be the same or different, but being the same is preferable. Multiple R 6 X may be the same or different, but it is preferable that they be the same. Multiple X values ​​may be the same or different, but it is preferable that they be the same. y is an integer greater than or equal to 1, and is determined according to Mw, Mn, meth(acrylic) equivalent, etc., as described later.

[0026] Compound A has units with a (meth)acrylic equivalent of 200 to 290 g / mol. The (meth)acrylic equivalent of the above units is preferably 205 to 275 g / mol, more preferably 215 to 265 g / mol, and even more preferably 230 to 255 g / mol. If the (meth)acrylic equivalent is above the lower limit of the above range, curing shrinkage of the cured product can be suppressed. If the (meth)acrylic equivalent is below the upper limit of the above range, moldability tends to improve.

[0027] The content of a unit of compound A with a (meth)acrylic equivalent of 200 to 290 g / mol relative to the total mass is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 99% by mass or more.

[0028] The (meth)acrylic equivalent of compound A is preferably 200-290 g / mol, more preferably 205-275 g / mol, even more preferably 215-265 g / mol, and particularly preferably 230-255 g / mol. If the (meth)acrylic equivalent is above the lower limit of the above range, curing shrinkage of the cured product can be suppressed. If the (meth)acrylic equivalent is below the upper limit of the above range, moldability tends to improve.

[0029] The viscosity of compound A at a solid content concentration of 50% by mass at 25°C is 30 to 3,000 mPa·s, preferably 50 to 2,000 mPa·s, more preferably 65 to 1,000 mPa·s, and even more preferably 80 to 800 mPa·s. If the viscosity is above the lower limit of the above range, the applicability to the substrate and moldability tend to improve. If the viscosity is below the upper limit of the above range, the temperature and pressure during imprinting can be reduced.

[0030] The carbon atom mass ratio of compound A is 60 to 84% by mass, preferably 62 to 80% by mass, more preferably 63 to 75% by mass, and even more preferably 64 to 70% by mass. If the carbon atom mass ratio is above the lower limit of the above range, the solvent resistance of the resulting cured product tends to improve. If the carbon atom mass ratio is below the upper limit of the above range, the solubility of compound A in the solvent improves.

[0031] The content of atoms other than carbon atoms, oxygen atoms, and hydrogen atoms relative to the total mass of compound A is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0032] The Mw of compound A is preferably 500 to 30000, more preferably 600 to 20000, even more preferably 700 to 10000, and particularly preferably 800 to 8000. When Mw is above the lower limit of the above range, the coating properties and moldability on the substrate tend to improve. When Mw is below the upper limit of the above range, the temperature and pressure during imprinting can be reduced.

[0033] The Mn of compound A is preferably 250 to 17000, more preferably 300 to 11000, even more preferably 350 to 5500, and particularly preferably 450 to 4500. When Mn is above the lower limit of the above range, the coating properties and moldability on the substrate tend to improve. When Mn is below the upper limit of the above range, the temperature and pressure during imprinting can be reduced.

[0034] Compound A may be used alone or in combination of two or more types. When using two or more types in combination, it is preferable that all of Compound A satisfy the above-mentioned ranges for (meth)acrylic equivalent, viscosity at a solid content concentration of 50% by mass at 25°C, and carbon atom mass ratio.

[0035] Compound A can be produced by conventionally known manufacturing methods. For example, in formula 2 above, R 1 is a hydrogen atom, and R 2 is a hydrogen atom, and R 3 and R 4 The methylene group is R 5 It is a single bond, R 6 Compound A, which consists only of phenol novolac-type epoxy acrylate units in which is a hydrogen atom and X is a methylene group, can be produced by reacting phenol with formaldehyde to obtain phenol novolac, adding epichlorohydrin to the phenol novolac, and then reacting it with acrylic acid. Also, in formula 2 above, R 1 is a hydrogen atom, and R 2 is a methyl group, R 3 and R 4 The methylene group is R 5Compound A, which consists only of cresol novolac-type epoxy acrylate units in which R6 is a single bond, R6 is a hydrogen atom, and X is a methylene group, can be produced by reacting cresol with formaldehyde to obtain cresol novolac, adding epichlorohydrin to the cresol novolac, and then reacting it with acrylic acid.

[0036] Compound A may be a commercially available product. Examples of commercially available products include "EA-6320 (phenol novolac type epoxy acrylate)", "EA-7120 (cresol novolac type epoxy acrylate)", and "EA-7420 (cresol novolac type epoxy acrylate)" manufactured by Shin Nakamura Chemical Co., Ltd.

[0037] <(meth)acrylate compound B> (Meth)acrylate compound B is a 2- to 4-functional (meth)acrylate compound. The number of functional groups of (meth)acrylate compound B is preferably 2 to 3, and more preferably 2.

[0038] The (meth)acrylic equivalent of (meth)acrylate compound B is 120 to 290 g / mol, preferably 128 to 275 g / mol, more preferably 136 to 260 g / mol, and even more preferably 145 to 245 g / mol. If the (meth)acrylic equivalent is above the lower limit of the above range, curing shrinkage of the cured product can be suppressed. If the (meth)acrylic equivalent is below the upper limit of the above range, moldability tends to improve.

[0039] The viscosity of (meth)acrylate compound B at a solid content concentration of 50% by mass at 25°C is 0.5 to 20 mPa·s, preferably 0.8 to 18 mPa·s, more preferably 1.2 to 15 mPa·s, and even more preferably 2 to 12 mPa·s. If the viscosity is above the lower limit of the above range, the applicability to the substrate and moldability tend to improve. If the viscosity is below the upper limit of the above range, the temperature and pressure during imprinting can be reduced.

[0040] The carbon atom mass ratio of (meth)acrylate compound B is 60 to 84% by mass, preferably 63 to 82% by mass, more preferably 67 to 79% by mass, and even more preferably 70 to 77% by mass. If the carbon atom mass ratio is above the lower limit of the above range, the solvent resistance of the resulting cured product tends to improve. If the carbon atom mass ratio is below the upper limit of the above range, the solubility of compound B in the solvent improves.

[0041] The content of atoms other than carbon atoms, oxygen atoms, and hydrogen atoms relative to the total mass of (meth)acrylate compound B is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0042] The molecular weight of (meth)acrylate compound B is preferably 100 to 800, more preferably 160 to 730, even more preferably 220 to 660, and particularly preferably 280 to 600. The molecular weight of (meth)acrylate compound B is the formula weight of (meth)acrylate compound B. When the molecular weight is above the lower limit of the above range, the coating properties and moldability on the substrate tend to improve. When Mw is below the upper limit of the above range, the temperature and pressure during imprinting can be reduced.

[0043] (Meth)acrylate compound B preferably has either an aromatic ring or an alicyclic ring, or both. The number of aromatic rings and alicyclic rings in one molecule of (meth)acrylate compound B is preferably 1 to 6, more preferably 1 to 4, and even more preferably 2 to 3. When the aromatic ring and alicyclic ring are fused, the number of aromatic rings and alicyclic rings is counted as one closed ring. For example, naphthalene is a compound that has two aromatic rings. Examples of aromatic rings include benzene rings and naphthalene rings, with benzene rings being preferred. Examples of alicyclic rings include cyclohexane rings and norbornane rings, with norbornane rings being more preferred.

[0044] Examples of (meth)acrylate compound B include (meth)acrylate compound B in which 2 to 4 hydrogen atoms bonded to carbon atoms of the aromatic ring or alicyclic ring are substituted with a monovalent group represented by formula 1-1. Furthermore, the aromatic ring or alicyclic ring may have alkyl groups or polyoxyalkylene groups as substituents. In this case, examples of (meth)acrylate compound B include (meth)acrylate compound B in which 2 to 4 hydrogen atoms bonded to carbon atoms in these alkyl groups or polyoxyalkylene groups are substituted with a monovalent group represented by formula 1-1. The number of carbon atoms in the alkyl group and polyoxyalkylene group is, for example, 1 to 5. (Meth)acrylate compound B may be a urethane (meth)acrylate having a urethane bond, or a polyester (meth)acrylate having an ester bond.

[0045] Compound B may be a commercially available product. Examples of commercially available products include "Bisphenol A di(meth)acrylate" and "Bisphenol A polyethylene glycol diether di(meth)acrylate" manufactured by Tokyo Chemical Industry Co., Ltd., and "A-DCP)" manufactured by Shin Nakamura Chemical Industry Co., Ltd.

[0046] (Meth)acrylate compound B may be used alone or in combination of two or more types. When using two or more types in combination, it is preferable that all (meth)acrylate compound B satisfy the above-mentioned ranges for (meth)acrylic equivalent, viscosity at a solid content concentration of 50% by mass at 25°C, and carbon atom mass ratio.

[0047] <Photopolymerization initiator C> Examples of photopolymerization initiator C include conventionally known photopolymerization initiators, with molecular cleavage type and hydrogen abstraction type photopolymerization initiators being preferred.

[0048] Examples of photopolymerization initiators include acylphosphine-based photopolymerization initiators (acylphosphine compounds), α-hydroxyalkylphenone-based photopolymerization initiators, α-hydroxyacetophenone-based photopolymerization initiators, α-aminoalkylphenone-based photopolymerization initiators, oxime ester-based photopolymerization initiators, benzophenone-based photopolymerization initiators, and benzyldimethylketal-based photopolymerization initiators, with acylphosphine-based photopolymerization initiators (acylphosphine compounds) being preferred.

[0049] Examples of acylphosphine-based photopolymerization initiators (acylphosphine compounds) include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (manufactured by IGM Resins, product name "Omnirad 819"), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (manufactured by IGM Resins, product name "Omnirad TPO N"), and ethyl(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (manufactured by IGM Resins, product name "Omnirad TPO-L"). Examples of α-hydroxyalkylphenone-based photopolymerization initiators include 1-hydroxycyclohexylphenyl ketone (manufactured by IGM Resins, product name "Omnirad 184").

[0050] Examples of α-hydroxyacetophenone-based photopolymerization initiators include 2-hydroxy-2-methyl-1-phenyl-propan-1-one (manufactured by IGM Resins, product name "Omnirad 1173"), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (manufactured by IGM Resins, product name "Omnirad 659"), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one (manufactured by IGM Resins, product name "Omnirad 127"), and oligo(2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)propanone) (manufactured by IGM Resins, product names "ESACUREONE" and "ESACUREKIP160"). Examples of α-aminoalkylphenone-based photopolymerization initiators include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (manufactured by IGM Resins, product name "Omnirad 907"), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (manufactured by IGM Resins, product name "Omnirad 369"), and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-1-butanone (manufactured by IGM Resins, product name "Omnirad 379"). Examples of oxime ester-based photopolymerization initiators include 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyl oxime)] (manufactured by BASF, product name "IRGACUREOXE01") and ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime) (manufactured by BASF, product name "IRGACUREOXE02"). Examples of benzophenone-based photopolymerization initiators include benzophenone, 4-phenylbenzophenone, isophthalphenone, 4-benzoyl-4'-methyl-diphenyl sulfide (manufactured by IGM Resins, product name "Omnirad BMS"), and 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one (manufactured by IGM Resins, product name "ESACURE1001M"). Examples of benzyldimethyl ketal-based photopolymerization initiators include 2,2-dimethoxy-1,2-diphenylethane-1-one (manufactured by IGM Resins, product name "Omnirad BDK"). Other examples of photopolymerization initiators include intramolecular hydrogen abstraction type photopolymerization initiators such as phenylglyoxylic acid methyl ester (manufactured by IGM Resins, product name "Omnirad MBF").

[0051] Photopolymerization initiator C may be used alone or in combination of two or more types.

[0052] <Solvent D> The solvent D is not particularly limited as long as it is a solvent capable of dissolving compound A and (meth)acrylate compound B, etc.

[0053] The boiling point of solvent D at atmospheric pressure is preferably 50 to 250°C, more preferably 70 to 200°C, and even more preferably 100 to 180°C. If the boiling point is above the lower limit, uneven coating is less likely to occur. If the boiling point is below the upper limit, the baking time can be shortened.

[0054] The solvent D is preferably aromatic hydrocarbons, aliphatic hydrocarbons, ketones, alcohols, ethers, or esters, more preferably aromatic hydrocarbons, ketones, ethers, or esters, and even more preferably ethers or esters. The solvent D may be derived from plants or petroleum.

[0055] Aromatic hydrocarbons are not particularly limited, but examples include benzene, toluene, xylene, anisole, and tetramethylbenzene.

[0056] Examples of aliphatic hydrocarbons, though not particularly limited, include pentane, hexane, heptane, octane, decane, and cyclohexane.

[0057] Examples of ketones, though not particularly limited, include cyclohexanone, 2-pentanone, cyclopentanone, and γ-butyrolactone.

[0058] Examples of alcohols, though not particularly limited, include 3-methoxy-3-methyl-1-butanol, benzyl alcohol, and cyclohexanol.

[0059] Examples of ethers, though not particularly limited, include propylene glycol monomethyl ether, dipropylene glycol dimethyl ether, and dipropylene glycol diethyl ether.

[0060] Examples of esters, though not particularly limited, include butyl acetate, isobutyl acetate, and propylene glycol monomethyl ether acetate.

[0061] Solvent D may be used alone or in combination of two or more types. When using two or more types in combination, it is preferable that the mixture satisfies the boiling point range described above.

[0062] (optional ingredient) The resin composition may contain optional components as needed. Examples of optional components include reactive epoxy monomers, reactive oxetane monomers, reactive acrylic monomers other than (meth)acrylic compound B, sensitizers, coupling agents, ion catchers, inorganic fillers, antioxidants, surfactants, and the like. Examples of reactive epoxy monomers, sensitizers, coupling agents, ion catchers, and inorganic fillers include the components described in Japanese Patent Application Publication No. 2008-142940. Furthermore, it is preferable that the resin composition is substantially free of compounds having a fluoroalkyl group. Substantially free of compounds having a fluoroalkyl group means that the content of compounds having a fluoroalkyl group relative to the total mass of the resin composition is 0.1% by mass or less, preferably 0.01% by mass or less, and particularly preferably 0% by mass. Optional components preferably include reactive acrylic monomers other than (meth)acrylic compound B and surfactants. Among the reactive acrylic monomers other than (meth)acrylic compound B, the following (meth)acrylate compound E is preferred.

[0063] ((meth)acrylate compound E) (Meth)acrylate compound E is a (meth)acrylate compound with 5 to 15 functional groups. When a resin composition contains (meth)acrylate compound E, its moldability tends to improve. The number of functional groups of (meth)acrylate compound E is preferably 5 to 10, and more preferably 5 to 7.

[0064] The (meth)acrylic equivalent of (meth)acrylate compound E is 70 to 100 g / mol, preferably 75 to 100 g / mol, more preferably 80 to 100 g / mol, and even more preferably 85 to 98 g / mol. If the (meth)acrylic equivalent is above the lower limit of the above range, curing shrinkage of the cured product can be suppressed. If the (meth)acrylic equivalent is below the upper limit of the above range, moldability tends to improve.

[0065] The viscosity of (meth)acrylate compound E at a solid content concentration of 50% by mass at 25°C is 0.5 to 20 mPa·s, preferably 0.8 to 18 mPa·s, more preferably 1.2 to 15 mPa·s, and even more preferably 2 to 12 mPa·s. If the viscosity is above the lower limit of the above range, the applicability to the substrate and moldability tend to improve. If the viscosity is below the upper limit of the above range, the temperature and pressure during imprinting can be reduced.

[0066] The carbon atom mass ratio of (meth)acrylate compound E is 45 to 84% by mass, preferably 47 to 78% by mass, more preferably 47 to 72% by mass, and even more preferably 50 to 65% by mass. If the carbon atom mass ratio is above the lower limit of the above range, the solvent resistance of the resulting cured product tends to improve. If the carbon atom mass ratio is below the upper limit of the above range, the solubility of compound E in the solvent improves.

[0067] The content of atoms other than carbon atoms, oxygen atoms, and hydrogen atoms relative to the total mass of (meth)acrylate compound E is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0068] The molecular weight of (meth)acrylate compound E is preferably 100 to 800, more preferably 160 to 730, even more preferably 220 to 660, and particularly preferably 280 to 600. The molecular weight of (meth)acrylate compound E is the formula weight of (meth)acrylate compound E. When the molecular weight is above the lower limit of the above range, the coating properties and moldability on the substrate tend to improve. When Mw is below the upper limit of the above range, the temperature and pressure during imprinting can be reduced.

[0069] (Meth)acrylate compound E, like (meth)acrylate compound B, may have either an aromatic ring or an alicyclic ring, or both, or neither. In particular, it is preferable that it does not have an aromatic ring or an alicyclic ring. Examples of (meth)acrylate compound E include (meth)acrylate compound E in which 5 to 15 hydrogen atoms bonded to carbon atoms of a linear or branched alkane are substituted with a monovalent group represented by formula 1-1 above. The alkane may also have an etheric oxygen atom between the carbon-carbon bonds. The number of carbon atoms in the alkane is, for example, 2 to 6. (Meth)acrylate compound E may be a urethane (meth)acrylate having a urethane bond, or a polyester (meth)acrylate having an ester bond.

[0070] Compound E may be a commercially available product. An example of a commercially available product is "A-DPH)" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

[0071] (Meth)acrylate compound E may be used alone or in combination of two or more. When using two or more in combination, it is preferable that all (meth)acrylate compounds E satisfy the above-mentioned ranges for (meth)acrylic equivalent, viscosity at a solid content concentration of 50% by mass at 25°C, and carbon atom mass ratio.

[0072] (Surfactants) Examples of surfactants include acrylic surfactants, silicone surfactants, fluorine-based surfactants, siloxane-modified acrylic surfactants, and vinyl surfactants, with acrylic surfactants being preferred. Furthermore, surfactants that do not contain fluoroalkyl groups are preferred. A fluoroalkyl group refers to a monovalent group in which at least one hydrogen atom in the alkyl group is replaced by a fluorine atom.

[0073] Examples of commercially available acrylic surfactants include products from BYK-Chemie Japan, such as "BYK-350," "BYK-352," "BYK-354," "BYK-355," "BYK-358N," "BYK-361N," "BYK-380N," "BYK-381," and "BYK-392."

[0074] As silicone-based surfactants, copolymers of polyoxyalkylene and polydimethylsiloxane can be used. Commercially available silicone-based surfactants include, for example, products from Toray Dow Corning such as "FZ-2118," "FZ-77," and "FZ-2161," products from Shin-Etsu Chemical Co., Ltd. such as "KP321," "KP323," "KP324," "KP326," "KP340," and "KP341," and products from Momentive Performance Materials Japan LLC such as "TSF4440," "TSF4441," "TSF4445," "TSF4450," "TSF4446," "TSF4452," "TSF4453," and "TSF4460." Examples include polyester-modified silicone oils manufactured by Kukemi Japan Co., Ltd., such as "BYK-300", "BYK-302", "BYK-306", "BYK-307", "BYK-320", "BYK-325", "BYK-330", "BYK-331", "BYK-333", "BYK-337", "BYK-341", "BYK-344", "BYK-345", "BYK-346", "BYK-348", "BYK-377", "BYK-378", "BYK-UV3500", "BYK-3510", and "BYK-UV3570".

[0075] As fluorinated surfactants, copolymers of polyoxyalkylene and fluorocarbons can be used. Examples of commercially available fluorinated surfactants include the "MEGAFAC series" from DIC Corporation and the "FC series" from Sumitomo 3M Corporation.

[0076] Examples of commercially available siloxane-modified acrylic surfactants include the product "BYK-3550" manufactured by BIC Chemie Japan.

[0077] One type of surfactant may be used alone, or two or more types may be used in combination.

[0078] <Composition and properties of resin compositions> The solid content concentration of the resin composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, even more preferably 1 to 30% by mass, particularly preferably 2 to 20% by mass, and most preferably 3 to 10% by mass. If the solid content concentration is above the lower limit of the above range, the resin composition can be uniformly coated over the entire substrate. If the solid content concentration is below the upper limit of the above range, in-plane variations in film thickness can be reduced.

[0079] The viscosity of the resin composition at 25°C is preferably 0.1 mPa·s to 10 Pa·s, more preferably 0.5 mPa·s to 1 Pa·s, and even more preferably 1 mPa·s to 0.5 Pa·s. If the viscosity is above the lower limit of the above range, the film can be uniformly coated onto the entire substrate. If the viscosity is below the upper limit of the above range, the film can be uniformly formed by spin coating or the like.

[0080] The content of fluorine atoms relative to the total mass of the resin composition is preferably 7% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

[0081] The content of compound A relative to the total mass of the resin composition is preferably 0.02 to 40% by mass, more preferably 0.1 to 30% by mass, and even more preferably 0.2 to 20% by mass. The content of compound A relative to the total mass of solids in the resin composition is preferably 10 to 90% by mass, more preferably 20 to 70% by mass, and even more preferably 30 to 60% by mass. When the content of compound A is above the lower limit of the above range, coating properties tend to improve. When the content of compound A is below the upper limit of the above range, moldability tends to improve.

[0082] The content of (meth)acrylate compound B relative to the total mass of the resin composition is preferably 0.02 to 40% by mass, more preferably 0.1 to 30% by mass, and even more preferably 0.2 to 20% by mass. The content of (meth)acrylate compound B relative to the total mass of solids in the resin composition is preferably 5 to 80% by mass, more preferably 15 to 60% by mass, and even more preferably 25 to 50% by mass. When the content of (meth)acrylate compound B is above the lower limit of the above range, moldability tends to improve. When the content of (meth)acrylate compound B is below the upper limit of the above range, coating properties tend to improve.

[0083] The content of photopolymerization initiator C relative to the total mass of the resin composition is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, and even more preferably 0.2 to 5% by mass. The content of photopolymerization initiator C relative to the total mass of solids in the resin composition is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and even more preferably 1 to 15% by mass. If the content of photopolymerization initiator C is above the lower limit of the above range, the resin will cure easily by UV irradiation. If the content of photopolymerization initiator C is below the upper limit of the above range, the coating properties of the resin composition will improve.

[0084] The content of solvent D relative to the total mass of the resin composition is preferably 30 to 99.9% by mass, more preferably 60 to 99.5% by mass, and even more preferably 70 to 99% by mass. If the content of solvent D is above the lower limit of the above range, the viscosity of the resin composition is reduced. If the content of solvent D is below the upper limit of the above range, the resin composition is easier to form a uniform film.

[0085] When the resin composition contains (meth)acrylate compound E, the content of (meth)acrylate compound E relative to the total mass of the resin composition is preferably 0.01 to 30% by mass, more preferably 0.05 to 20% by mass, and even more preferably 0.1 to 10% by mass. When the resin composition contains (meth)acrylate compound E, the content of (meth)acrylate compound E relative to the total mass of solids in the resin composition is preferably 0.5 to 50% by mass, more preferably 1 to 30% by mass, and even more preferably 3 to 15% by mass. When the content of (meth)acrylate compound E is above the lower limit of the above range, moldability tends to improve. When the content of (meth)acrylate compound E is below the upper limit of the above range, coating properties tend to improve.

[0086] If the resin composition contains any component other than (meth)acrylate compound E, the content of the optional component relative to the total mass of the resin composition is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 1% by mass or less. If the resin composition contains any component other than (meth)acrylate compound E, the content of the optional component relative to the total mass of solids in the resin composition is preferably 15% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less.

[0087] If the resin composition contains other (meth)acrylate compounds other than (meth)acrylate compound B and (meth)acrylate compound E, the content of the other (meth)acrylate compounds relative to the total mass of the resin composition is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 1% by mass or less. If the resin composition contains other (meth)acrylate compounds other than (meth)acrylate compound B and (meth)acrylate compound E, the content of the other (meth)acrylate compounds relative to the total mass of solids in the resin composition is preferably 15% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less.

[0088] The total content of compound A and (meth)acrylate compound B relative to the total mass of the resin composition is preferably 0.02 to 40% by mass, more preferably 0.1 to 30% by mass, and even more preferably 0.2 to 20% by mass. The total content of compound A and (meth)acrylate compound B relative to the total mass of solids in the resin composition is preferably 40 to 99% by mass, more preferably 60 to 98% by mass, and even more preferably 80 to 97% by mass.

[0089] The content of compound A relative to 100 parts by mass of the total of compound A and (meth)acrylate compound B is preferably 30 to 75 parts by mass, more preferably 40 to 70 parts by mass, and even more preferably 45 to 65 parts by mass. When the content of compound A is above the lower limit of the above range, coating properties tend to improve. When the content of compound A is below the upper limit of the above range, moldability tends to improve.

[0090] When the resin composition contains (meth)acrylate compound E, the content of (meth)acrylate compound E relative to 100 parts by mass of the total of (meth)acrylate compound B and (meth)acrylate compound E is preferably 10 to 30 parts by mass, more preferably 12 to 25 parts by mass, and even more preferably 14 to 20 parts by mass. When the content of (meth)acrylate compound E is above the lower limit of the above range, moldability tends to improve. When the content of (meth)acrylate compound E is below the upper limit of the above range, coating properties tend to improve.

[0091] The resin composition has no particular applications, but examples include imprint molding, 3D printing, and photoresist applications, with imprint molding being preferred. In other words, an imprint agent made from a resin composition is preferred.

[0092] ≪Cured product≫ The cured product of this embodiment is a cured product of the above-mentioned resin composition. The curing conditions and other details will be described later.

[0093] ≪Laminated structure≫ The laminate of this embodiment has a thin film made of a cured product of the above resin composition on one surface of the substrate. Figure 1 is a schematic cross-sectional view showing an example of a laminate according to this embodiment. The laminate 1A has a substrate 10 and a thin film 20 on one surface of the substrate 10. An inorganic oxide layer, such as tantalum oxide, may be provided between the substrate 10 and the thin film 20. Figure 2 is a schematic cross-sectional view showing yet another example of the laminate of this embodiment. The laminate 1B has a substrate 10 and a thin film 20 on one surface of the substrate 10. The thin film 20 has a fine pattern 22 on its surface. An inorganic oxide layer, such as tantalum oxide, may be provided between the substrate 10 and the thin film 20.

[0094] (substrate) Examples of substrate 10 include substrates made of inorganic materials or substrates made of organic materials. Inorganic materials include glass (including tempered glass, crystallized glass, and quartz glass), silicon wafers, metals (aluminum, nickel, copper, etc.), metal oxides (sapphire, indium tin oxide (ITO), etc.), silicon nitride, aluminum nitride, lithium niobate, etc. Organic materials include fluororesins, silicone resins, acrylic resins, polycarbonates, polyesters (polyethylene terephthalate, etc.), polyamides, polyimides, polypropylene, polyethylene, nylon resins, polyphenylene sulfide, triacetylcellulose, and cyclic polyolefins. As the substrate 10, glass is preferred in terms of transparency, surface flatness, and optical isotropy, and a surface-treated substrate 10 may also be used in order to have excellent adhesion to the thin film. Examples of surface treatments include UV ozone treatment and plasma etching. The substrate 10 may be one layer or two layers. The substrate 10 may be of one type or two or more types may be used in combination. The thickness of the substrate 10 is preferably 0.1 to 10 mm, more preferably 0.2 to 7 mm, and even more preferably 0.3 to 5 mm. The refractive index of the substrate 10 at a wavelength of 589 nm is preferably 1.75 to 2.3, more preferably 1.8 to 2.2, even more preferably 1.85 to 2.1, and particularly preferably 1.9 to 2.05. When the refractive index is within the above range, the substrate can be made into a thin film.

[0095] (Thin film) The thin film consists of a cured product of the above-mentioned resin composition. The thickness of the thin film 20 in Figure 1 and the thickness of the thickest part of the thin film 20 in Figure 2 are preferably 10 to 500 nm, more preferably 20 to 400 nm, and even more preferably 30 to 300 nm. The refractive index of the thin film 20 at a wavelength of 589 nm is preferably 1.4 to 2.0, more preferably 1.5 to 2.0, and even more preferably 1.6 to 2.0. When the refractive index is within the above range, the optical performance when used as a light guide member is improved. The absolute value of the refractive index difference between the substrate 10 and the thin film 20 at a wavelength of 589 nm is preferably 0 to 1, more preferably 0 to 0.7, and even more preferably 0 to 0.5. When the absolute value of the refractive index difference is within the above range, the optical performance when used as a light guide member is improved.

[0096] As shown in Figure 2, the thin film 20 may have a fine pattern 22 on its surface having either or both of a plurality of protrusions and a plurality of recesses. The fine pattern is an inverted pattern corresponding to the fine pattern of the mold described later. Examples of protrusions include long ridges extending from the surface of the thin film 20 and protrusions scattered on the surface. Examples of recesses include long grooves extending from the surface of the thin film 20 and holes scattered on the surface.

[0097] The shape of the protrusions or grooves can be straight, curved, or bent. Multiple protrusions or grooves may be present in parallel or without intersecting to form a striped pattern. Examples of cross-sectional shapes of the protrusions or grooves in the direction perpendicular to the longitudinal direction include rectangles, trapezoids, triangles, and semicircles. Examples of shapes for protrusions or holes include triangular prisms, square prisms, hexagonal prisms, cylinders, triangular pyramids, square pyramids, hexagonal pyramids, cones, hemispheres, and polyhedra.

[0098] The width of the ridges or grooves is preferably 1 nm to 500 μm, more preferably 10 nm to 100 μm, and even more preferably 15 nm to 10 μm. The width of the ridges refers to the length of the base in a cross-section perpendicular to the longitudinal direction. The width of the grooves refers to the length of the top in a cross-section perpendicular to the longitudinal direction. The width of the protrusion or pore is preferably 1 nm to 500 μm, more preferably 10 nm to 100 μm, and even more preferably 15 nm to 10 μm. The width of the protrusion refers to the length of the base in a cross-section perpendicular to the longitudinal direction if the base is elongated, or to the maximum length at the base of the protrusion if it is not. The width of the pore refers to the length of the top in a cross-section perpendicular to the longitudinal direction if the opening is elongated, or to the maximum length at the opening of the pore if it is not.

[0099] The height of the protrusions is preferably 1 nm to 500 μm, more preferably 10 nm to 100 μm, and even more preferably 15 nm to 10 μm. The depth of the recesses is preferably 1 nm to 500 μm, more preferably 10 nm to 100 μm, and even more preferably 15 nm to 10 μm. In regions where fine patterns are densely packed, the pitch (center-to-center distance) between adjacent protrusions (or recesses) is preferably 1 nm to 500 μm, more preferably 10 nm to 100 μm, and even more preferably 15 nm to 10 μm.

[0100] (Method of manufacturing a laminate) The manufacturing method of the laminate according to this embodiment includes, for example, the following steps 1 to 5. Step 1: As shown in S1 to S2 of Figure 3, the step of sandwiching the resin composition 21 between the mold 30 having a fine pattern 33 on its surface and the substrate 10 such that the fine pattern 33 of the mold 30 is in contact with the resin composition 21. Step 2: As shown in S2 of Figure 3, the step of curing the resin composition 21 to form a thin film 20. Step 3: A step to separate the thin film 20 and the mold 30, as shown in S3 of Figure 3.

[0101] (Mold) The mold 30 may have a fine pattern 33 on its surface. The fine pattern 33 is an inverted pattern corresponding to the fine pattern of the thin film 20. As the mold 30, a replica mold may be used which has a layer of cured material on which an inverted pattern of the fine pattern 33 has been transferred to the surface by an imprint method using a master mold having a fine pattern 33 on its surface. Examples of mold 30 include molds made of non-transparent material or molds made of translucent material. Examples of molds made from non-transparent materials include silicon wafers, nickel, copper, stainless steel, titanium, SiC, and mica. Examples of translucent material molds include glass such as quartz glass, polydimethylsiloxane, cyclic polyolefin, polycarbonate, polyethylene terephthalate, and transparent fluororesin. Translucent material molds may be composed of multiple materials. Preferably, at least one of the substrate 10 and the mold 30 is made of a material that transmits 40% or more of the light at the wavelength on which initiator B and initiator B' act.

[0102] (Process 1) Methods for placing the resin composition 21 on the surface of the substrate 10 shown in S1 of Figure 1 include inkjet method, potting method (dispense method), spin coating method, roll coating method, casting method, dip coating method, die coating method, Langmuller Projet method, and vacuum deposition method. The resin composition 21 may be placed over the entire surface of the substrate 10, or it may be placed over a portion of the surface of the substrate 10.

[0103] It is preferable to heat the resin composition 21 after placing it on the surface of the substrate 10 to evaporate the solvent C. The heating temperature is preferably, for example, 50 to 150°C, and more preferably 70 to 130°C. The heating time is preferably, for example, 0.5 to 10 minutes, and more preferably 1 to 5 minutes.

[0104] The pressing pressure when pressing the mold 20 onto the resin composition 21 is preferably greater than 0 MPa and less than or equal to 100 MPa, and more preferably between 0.01 and 80 MPa. The temperature at which the mold 30 is pressed onto the resin composition 21 is preferably 0 to 120°C, and more preferably 15 to 60°C. In step 1, the position of the mold 30 and the substrate 10 may be adjusted using alignment marks.

[0105] (Process 2) The resin composition 21 is cured by irradiating it with light to form a thin film 20. Methods of irradiating with light include irradiating from the mold side using a mold made of light-transmitting material, irradiating from the substrate side using a substrate made of light-transmitting material, and irradiating with light through the gap between the mold 30 and the substrate 10. The wavelength of the light is preferably 200 to 500 nm. When irradiating with light, the resin composition 21 may be heated to accelerate curing. The temperature when irradiating with light is preferably between 0 and 120°C, and more preferably between 15 and 60°C.

[0106] (Step 3) The temperature at which the thin film 20 and the mold 30 are separated is preferably 0 to 100°C, and more preferably 15 to 60°C. As for the method of separating the mold 30, it may be by dissolving the mold 30, but from the viewpoint of reusing the mold 30, it is preferable to remove the mold 30 from the thin film 20.

[0107] <Optical Components> The laminate manufactured by the above-described method can be used as an optical component. This optical component can be used, for example, as a light guide member or diffuser for AR / VR applications. [Examples]

[0108] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Examples 1-11 are examples of actual cases, and Examples 12-18 are comparative examples.

[0109] <Mw、Mn> The results were obtained by measuring using the following equipment under the following conditions. GPC system: HLC-8220GPC (manufactured by Tosoh Corporation) Columns: TSKGuard Column Super MZ-L, TSK gel HZ4000, TSK gel HZ3000, TSK gel HZ2500, TSK gel HZ2000 (used in this order, concatenated together). Column oven temperature: 40℃, Solvent: tetrahydrofuran, flow rate: 0.35 mL / min, standard sample: polystyrene.

[0110] <Viscosity> Compound A, comparative compound a, (meth)acrylate compound B, comparative compound b, or (meth)acrylate compound E was mixed with propylene glycol monomethyl ether acetate to a concentration of 50% by mass. The viscosity of the resulting liquid was measured at 25 ± 0.2°C using a rotational viscometer (TV-25, manufactured by Toki Sangyo Co., Ltd.). The rotational speed during measurement was set according to the viscosity as shown in Table 1 below. Even when the viscosity exceeded 3000 mPa·s, the rotational speed was set to 0.3 rpm.

[0111] [Table 1]

[0112] <(meth)acrylic equivalent> The (meth)acrylic equivalent was calculated by dividing the molecular weight of compound A, comparative compound a, (meth)acrylate compound B, comparative compound b, or (meth)acrylate compound E by the number of monovalent groups represented by formula 1-1 above. For (meth)acrylate compound B, comparative compound b, and (meth)acrylate compound E, the formula weight was used as the molecular weight. For compound A and comparative compound a, since they are compounds consisting of only one type of unit, the (meth)acrylic equivalent was calculated using the above unit.

[0113] <Carbon atom mass ratio> The carbon atom mass ratio was calculated using the following formula f3. Carbon atom mass ratio = (A C ×12) / (A C ×12+A H ×1+A O ×16)×100 formula f3 In the above formula f3, A C This is the number of carbon atoms contained in compound A, comparative compound a, (meth)acrylate compound B, comparative compound b, or (meth)acrylate compound E, and A H This is the number of hydrogen atoms contained in compound A, comparative compound a, (meth)acrylate compound B, comparative compound b, or (meth)acrylate compound E, and A O This is the number of oxygen atoms contained in compound A, comparative compound a, (meth)acrylate compound B, comparative compound a, or (meth)acrylate compound E.

[0114] <Evaluation of applicability> Examples 1 to 18 of the resin compositions were applied to one surface of a glass substrate (base material) with a thickness of 0.7 mm, a wavelength of 589 nm, and a refractive index of 2.0, by spin coating. The coatability of the resin compositions was evaluated according to the following criteria. ◎, ○, and △ were considered pass, and × was considered fail. ◎: The resin composition is applied evenly to the entire surface of the substrate without any unevenness in the coating. ○: The resin composition is applied to the entire surface of the substrate, but there are inconsistencies in the application. △: There are areas on the substrate where the resin composition is not applied, and the area of ​​these uncoated areas is less than 10% of the substrate area. ×: There are areas on the substrate where the resin composition is not applied, and the area of ​​these uncoated areas is 10% or more of the substrate area.

[0115] <Evaluation of moldability> <Evaluation of Coatability> The resin composition obtained in the <Evaluation of Coatability> was applied to a substrate, and the resin composition was heated at 100°C for 3 minutes to evaporate the solvent. A resin mold with a line and space pattern spaced 100 nm apart and 100 nm deep was used as the mold. The resin composition was sandwiched between the substrate and the mold so that the fine pattern of the mold was in contact with the resin composition, and pressed at 2 MPa and 25°C. After that, ultraviolet light was exposed from a high-pressure mercury lamp at an exposure dose of 1000 mJ / cm². 2 The resin composition was cured by irradiating it from the substrate side to form a thin film of cured material. Subsequently, the mold was separated from the thin film to obtain a laminate of a glass substrate and a thin film with a fine pattern on its surface, as shown in Figure 2. The thickness of the thickest part of the thin film was 170 nm, and the thickness of the thinnest part was 70 nm. The surface of the thin film was observed with a scanning electron microscope, and its moldability was evaluated according to the following criteria. ◎ and ○ are considered pass, and × is considered fail. ◎: The pattern shape is transferred exactly as it appears in the mold. ○: There are some missing parts in the pattern, but it has been transferred without any distortion. ×: There are gaps and unevenness in the pattern.

[0116] <Evaluation of defects at pattern edges> The surface of the thin film of the laminate obtained in the <Moldability Evaluation> was observed with an optical microscope, and pattern edge defects were evaluated according to the following criteria. ○ and △ are considered pass, and × is considered fail. In this specification, the evaluation of pattern edge defects constitutes the evaluation of moldability. ○: No unfilled areas (areas where cured resin composition does not exist) have occurred at the edges of the imprint area. △: There is one unfilled area at the edge of the imprint area. ×: Two or more unfilled areas have occurred at the edge of the imprint area.

[0117] <Solvent resistance> The laminate obtained in the <Moldability Evaluation> was immersed in toluene for 30 seconds. After that, the laminate was removed from the toluene and heated at 100°C for 3 minutes to evaporate the solvent. Subsequently, the surface of the thin film was observed with a scanning electron microscope and the solvent resistance was evaluated according to the following criteria. ◎ and ○ are considered pass, and × is considered fail. Note that the line and space pattern refers to the width of the protrusions of the fine pattern 22 in S3 of Figure 3. ◎: The rate of change in the line width of the line and space pattern before and after toluene immersion is less than 5%. ○: The rate of change in the line width of the line and space pattern before and after toluene immersion is 5% or more and less than 10%. ×: The change in line width of the line and space pattern before and after toluene immersion is 10% or more.

[0118] <Raw materials, etc.> The raw materials used in Examples 1-18 are as follows: [Compound A] Compound A-1: ​​A compound consisting solely of phenol novolac type epoxy acrylate units represented by formula 3 below (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product name "EA-6320"). Mw: 1100, Mn: 620, where n1 is an integer corresponding to the above Mw and Mn. [ka] Compound A-2: A compound consisting solely of cresol novolac type epoxy acrylate units represented by formula 4 below (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product name "EA-7420"). Mw: 5483, Mn: 3082, where n2 is an integer corresponding to the above Mw and Mn. [ka]

[0119] [Comparative compound a compared to compound A] Compound a-1: An epoxy ester compound represented by formula 5 below (manufactured by Kyoeisha Chemical Co., Ltd., product name "Epoxy Ester 3002A"). Mw: 601. [ka] Compound a-2: A compound represented by formula 6 below (manufactured by Arakawa Chemical Co., Ltd., product name "Beamset DK1"). Mw: 20000, and n3 is an integer corresponding to the above Mw. [ka]

[0120] [(meth)acrylate compound B] • (Meth)acrylate compound B-1: A bifunctional methacrylate compound represented by formula 7 below (manufactured by Tokyo Chemical Industry Co., Ltd., product name "Bisphenol A dimethacrylate"). [ka] • (Meth)acrylate compound B-2: A bifunctional acrylate compound represented by formula 8 below (manufactured by Tokyo Chemical Industry Co., Ltd., product name "Bisphenol A polyethylene glycol diether diacrylate"). In the formula below, n4 + n5 is 3. [ka] • (Meth)acrylate compound B-3: A bifunctional acrylate compound represented by formula 9 below (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product name "A-DCP"). [ka]

[0121] [Comparative compound b compared to (meth)acrylate compound B] • (Meth)acrylate compound b-1: Monofunctional benzyl acrylate represented by formula 10 below (manufactured by Tokyo Chemical Industry Co., Ltd., product name "Benzyl Acrylate"). [ka]

[0122] [Photopolymerization initiator C] • Photopolymerization initiator C-1: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by IGM Resins, product name "Omnirad TPO N"). • Photopolymerization initiator C-2: Ethyl (2,4,6-trimethylbenzoyl)-phenylphosphine oxide (manufactured by IGM Resins, product name "Omnirad TPO-L"). • Photopolymerization initiator C-3: Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (manufactured by IGM Resins, product name "Omnirad 819").

[0123] [Solvent D] Solvent D-1: A mixed solvent with a mass ratio of propylene glycol monomethyl ether acetate:propylene glycol monomethyl ether = 90:10.

[0124] [Optional ingredients] ((meth)acrylate compound E) • (Meth)acrylate compound E: A hexafunctional acrylate compound represented by formula 11 below (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product name "A-DPH"). [ka] • Surfactant: 0-function acrylic polymer (manufactured by BYK, product name "BYK-361N").

[0125] Table 2 shows the (meth)acrylic equivalent, viscosity at a solid content concentration of 50% at 25°C, and carbon atom mass ratio for compound A, comparative compound a, (meth)acrylate compound B, comparative compound b, and (meth)acrylate compound E.

[0126] [Table 2]

[0127] (Examples 1-18) A resin composition was obtained by mixing compound A (comparative compound a), (meth)acrylate compound B (comparative compound b), photopolymerization initiator C, (meth)acrylate compound E, and surfactant according to the formulations shown in Table 3. A blank space in Table 3 indicates that the component was not included, and the unit of the amount included is mass% (the sum of components excluding solvent D is 100% by mass). Although not shown in Table 3, solvent D was also added. The amount of solvent D added was adjusted so that the solid content concentration of the resin composition was 5.5% by mass. The obtained resin composition was evaluated for coatability, moldability, pattern edge defects, and solvent resistance. The results are shown in Table 3. A "-" in the evaluation indicates that the evaluation was not performed.

[0128] [Table 3]

[0129] Examples 1 to 11, which contain compound A, (meth)acrylate compound B, photopolymerization initiator C, and solvent D of the present invention, were found to be excellent in terms of coatability, moldability, and solvent resistance. Example 12, which contains comparative compound a-1 instead of compound A, showed poor moldability. Example 13, which contains comparative compound a-2 instead of compound A, showed poor solvent resistance. Example 14, which does not contain compound A or comparative compound a, showed poor coatability. Examples 15 to 17, which do not contain (meth)acrylate compound B, showed poor moldability or solvent resistance. In Example 17, although a monofunctional (meth)acrylate compound was included instead of (meth)acrylate compound B, the result was poor moldability. Furthermore, Example 18, which contains a monofunctional (meth)acrylate compound instead of (meth)acrylate compound B and also contains (meth)acrylate compound (E), also showed poor moldability. [Explanation of symbols]

[0130] 1A, 1B...Laminate, 10...Substrate, 20...Thin film, 21...Resin composition, 22...Fine pattern, 30...Mold, 33...Fine pattern

Claims

1. A resin composition comprising compound A having either or both cresol novolac-type (meth)acrylate units and phenol novolac-type (meth)acrylate units, a 2- to 4-functional (meth)acrylate compound B, a photopolymerization initiator C, and a solvent D, The compound A has units with a (meth)acrylic equivalent of 200 to 290 g / mol, a viscosity of 30 to 3,000 mPa·s at a solid content concentration of 50% by mass at 25°C, and a carbon atom mass ratio of 60 to 84% by mass calculated by the following formula f1. The (meth)acrylate compound B is a resin composition having a (meth)acrylic equivalent of 120 to 290 g / mol, a viscosity of 0.5 to 20 mPa·s at a solid content concentration of 50% by mass at 25°C, and a carbon atom mass ratio calculated by the following formula f1 of 60 to 84% by mass. Carbon atomic mass ratio = (A1) Ｃ ×12) / (A1) Ｃ ×12+A1 Ｈ ×1+A1 Ｏ ×16)×100 Formula f1 In the above formula f1, A1 Ｃ A1 is the number of carbon atoms contained in compound A or (meth)acrylate compound B, Ｈ A1 is the number of hydrogen atoms contained in compound A or (meth)acrylate compound B, and Ｏ This is the number of oxygen atoms contained in compound A or (meth)acrylate compound B.

2. The resin composition according to claim 1, wherein compound A has a unit represented by the following formula 1. 【Chemistry 1】 In the above formula (1), R １ is a hydrogen atom, a monovalent hydrocarbon group, or a halogen atom, R ２ is a hydrogen atom, a monovalent hydrocarbon group, or a halogen atom, R ３ is a divalent hydrocarbon group, R ４ is a divalent hydrocarbon group, R ５ is a single bond or a divalent hydrocarbon group, R ６ is a hydrogen atom or a monovalent hydrocarbon group, and X is a divalent hydrocarbon group.

3. The resin composition according to claim 1, wherein the (meth)acrylate compound B has either an aromatic ring or an alicyclic ring, or both.

4. The resin composition according to claim 1, wherein the content of compound A is 30 to 75 parts by mass relative to 100 parts by mass of the total of compound A and (meth)acrylate compound B.

5. The resin composition according to claim 1, further comprising a 5-15 functional (meth)acrylate compound E, wherein the (meth)acrylate compound E has a (meth)acrylic equivalent of 70-100 g / mol, a viscosity of 0.5-20 mPa·s at a solid content concentration of 50% by mass at 25°C, and a carbon atom mass ratio calculated by the following formula f2 of 45-84% by mass. Carbon atomic mass ratio = (A2) Ｃ ×12) / (A2) Ｃ ×12+A2 Ｈ ×1 + A2 Ｏ (×16)×100 Formula f2 In the above formula f2, A2 Ｃ A2 is the number of carbon atoms contained in the (meth)acrylate compound E. Ｈ A2 is the number of hydrogen atoms contained in the (meth)acrylate compound E. Ｏ This is the number of oxygen atoms contained in the (meth)acrylate compound E.

6. The resin composition according to claim 5, wherein the content of (meth)acrylate compound E is 10 to 30 parts by mass relative to 100 parts by mass of the total of (meth)acrylate compound B and (meth)acrylate compound E.

7. The resin composition according to claim 1, further comprising a surfactant that does not have a fluoroalkyl group.

8. The resin composition according to claim 1, wherein the photopolymerization initiator C comprises an acylphosphine compound.

9. The resin composition according to claim 1, wherein the solid content concentration is 1 to 50% by mass.

10. The resin composition according to claim 1, used for imprint molding.

11. A cured product of the resin composition according to any one of claims 1 to 10.

12. A laminate comprising a substrate and a thin film made of the cured product described in claim 11 on one surface of the substrate, wherein the thickness of the thin film is 10 to 500 nm.

13. The laminate according to claim 12, wherein the thin film has a fine pattern on its surface.

14. A method for manufacturing a laminate comprising a substrate and a thin film having a fine pattern on its surface on one surface of the substrate, A method for manufacturing a laminate, comprising sandwiching a resin composition according to any one of claims 1 to 10 between a mold having a fine pattern on its surface and the substrate, curing the resin composition to form a thin film having a fine pattern on its surface, and separating the thin film from the mold.

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