Method for producing resin cured product with pattern structure

Abstract

To provide a method for producing a resin cured product with a pattern structure which can form a pattern structure by a new method.SOLUTION: A curable composition 2 contains a curable component and an active energy ray polymerization initiator. A first curing step irradiates a part of the curable composition 2 with active energy rays, through a photomask 14. In a part irradiated with the active energy rays, gas caused by the active energy ray polymerization initiator is generated. In the remainder to the part irradiated with the active energy rays, a recess 20 caused by the gas is formed. A protrusion 4 is formed by curing a curable component in the part irradiated with the active energy rays. A second curing step removes the photomask 14, irradiates the remainder with active energy rays to cure a curable component and form a recess 5. As a result, an uneven structure 6 is formed in the cured product of the curable component.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a method for producing a pattern-structured cured resin product. [Background technology]

[0002] Conventionally, cured resin products having a pattern structure have been known. For example, a concavo-convex structure having a concavo-convex pattern is known as the pattern structure. Cured resin products having a pattern structure are used in, for example, the optical field, the water repellent field, the heat dissipation field, and the cushion field.

[0003] A resin composition having a pattern structure is produced, for example, by the following method. That is, in this method, an active energy ray-curable polyurethane resin as a flowable substance, 1-hexene as a compatible substance, a plasticizer, a reactive diluent, and a polymerization initiator are mixed to obtain a composition. The composition is then formed into a film to obtain a coating film. Next, the coating film is irradiated with active energy rays through a photomask to cure the active energy ray-curable polyurethane resin and reduce the compatibility of 1-hexene. Thereafter, the 1-hexene is volatilized, and the portions where 1-hexene was present become recessed. In this way, a patterned molded product is obtained (see, for example, Patent Document 1 (Example 2)). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2022 / 041787 Summary of the Invention [Problem to be solved by the invention]

[0005] On the other hand, a new method for forming a pattern structure in a cured resin is required.

[0006] The present invention provides a method for producing a patterned structure-bearing cured resin product, which is capable of forming a patterned structure by a novel method. [Means for solving the problem]

[0007] The present invention [1] comprises a preparation step of preparing a curable composition that can be cured by irradiation with at least active energy rays, a disposing step of the curable composition, a coating step of covering at least one surface of the curable composition with an active energy ray-transparent coating material, a masking step of disposing a photomask on the one surface of the active energy ray-transparent coating material, a first curing step of irradiating a part of the curable composition with active energy rays through the photomask, and a second curing step of irradiating a remaining part of the curable composition with active energy rays and / or heating the remaining part after the first curing step, wherein the curable composition contains at least a curable component that can be cured by irradiation with active energy rays and an active energy ray polymerization initiator, and the first curing step the curing step includes: generating a gas resulting from the active energy ray polymerization initiator in the portion irradiated with the active energy rays, forming a space resulting from the gas in the remaining portion relative to the portion irradiated with the active energy rays, and curing the curable component in the portion irradiated with the active energy rays to form a first cured portion without the space; and removing the photomask, irradiating the remaining portion with active energy rays and / or heating the remaining portion to curing the curable component to form a second cured portion having the space, thereby forming a pattern structure comprising the first cured portion and the second cured portion in the cured product of the curable component.

[0008] The present invention [2] includes the method for producing a cured resin product having a pattern structure according to the above [1], wherein the pattern structure is a concave-convex structure and the aspect ratio (depth / width) of the concave-convex structure is 5 or more.

[0009] The present invention [3] includes the method for producing a patterned cured resin product according to the above [1] or [2], wherein the photomask has a plurality of light-transmitting portions and light-shielding portions, the light-transmitting portions and the light-shielding portions have a line-and-space pattern, the line width in the line-and-space pattern is less than 100 μm, and the space width in the line-and-space pattern is less than 100 μm.

[0010] The present invention [4] includes the method for producing a pattern-structured cured resin product according to any one of the above [1] to [3], wherein the active energy ray polymerization initiator is a cleavage-type active energy ray radical polymerization initiator, and the content of the active energy ray polymerization initiator is 1 part by mass or more and 10 parts by mass or less per 100 parts by mass of the curable component. [Effects of the Invention]

[0011] According to the method for producing a patterned cured resin product of the present invention, a patterned structure can be formed by a novel method.

[0012] More specifically, in the above-described method for producing a pattern-structured cured resin product, the curable composition contains a curable component and an active energy ray polymerization initiator.

[0013] In the method for producing a patterned cured resin product, the first curing step involves irradiating the curable composition with active energy rays through a photomask. That is, a gas resulting from the active energy ray polymerization initiator is generated in a portion of the curable composition. Furthermore, a space resulting from the gas is formed in the remaining portion of the curable composition, which is different from the portion irradiated with the active energy rays. Furthermore, in the portion irradiated with the active energy rays, the curable component is cured to form a first cured portion that does not have the space.

[0014] Then, in the second curing step, the photomask is removed, and the remaining portion is irradiated with active energy rays and / or heated to cure the curable component, thereby forming a second cured portion having the space, resulting in a pattern structure comprising the first cured portion and the second cured portion in the cured product of the curable component.

[0015] Therefore, the above-described method for producing a patterned cured resin product allows a patterned structure to be formed in a cured product of a curable component by a novel method. In other words, the above-described method allows a patterned cured resin product having a patterned structure to be produced by a novel method. [Brief explanation of the drawings]

[0016] [Figure 1] Figure 1A is a schematic side cross-sectional view showing the step of preparing a molding die, Figure 1B is a schematic side cross-sectional view showing the step of placing a curable composition, Figure 1C is a schematic side cross-sectional view showing the step of coating one side of the curable composition with an active energy ray-transparent coating material, and Figure 1D is a schematic side cross-sectional view showing the step of placing a photomask on one side of the active energy ray-transparent coating material. [Figure 2] FIG. 2E is a schematic side cross-sectional view showing a process of irradiating the curable composition with active energy rays from one side of the photomask, FIG. 2F is a schematic side cross-sectional view showing a process of generating gas due to the active energy ray polymerization initiator and forming depressions due to the gas, FIG. 2G is a schematic side cross-sectional view showing a process of removing the photomask and irradiating the curable composition with active energy rays, and FIG. 2H is a schematic side cross-sectional view showing a process of demolding the patterned cured resin material. [Figure 3] FIG. 3 is a schematic side cross-sectional view showing an embodiment in which a photomask also serves as an active energy ray-transmitting covering material. [Figure 4] FIG. 4 is a schematic cross-sectional side view showing a form in which internal voids caused by gas are formed. DETAILED DESCRIPTION OF THE INVENTION

[0017] 1. Method for manufacturing a patterned structured cured resin 1) Preparation process [Curable composition] A patterned cured resin product is a cured resin product having a patterned structure on its surface and / or inside. Examples of the patterned structure include a concave-convex structure formed on the surface of the cured resin product (hereinafter referred to as the concave-convex structure) and a porous structure formed inside the cured resin product (hereinafter referred to as the porous structure). Below, a patterned cured resin product having a concave-convex structure as a patterned structure on its surface (cured resin product with a concave-convex structure) will be described.

[0018] In the method for producing a patterned cured resin product, first, a curable composition that can be cured by irradiation with at least active energy rays is prepared (preparation step).

[0019] The curable composition is, for example, a raw material component of a patterned-structured cured resin product 1 (described later). That is, the curable composition is a molding material. The curable composition contains, as essential components, at least a curable component and an active energy ray polymerization initiator.

[0020] [Curable component] The curable component contains, for example, a curable resin.

[0021] [Curable resin] The curable resin is a resin that can be cured at least by irradiation with active energy rays (i.e., an active energy ray-curable resin). In other words, the curable resin can be polymerized and cured by irradiation with active energy rays. The curable resin may also be polymerized and cured by heating. That is, the curable resin may be both an active energy ray-curable resin and a thermosetting resin.

[0022] Examples of the curable resin include an active energy ray radical polymerizable resin and an active energy ray cationically polymerizable resin. That is, the curable resin contains, for example, an active energy ray radical polymerizable resin and / or an active energy ray cationically polymerizable resin. The curable resin is preferably made of an active energy ray radical polymerizable resin and / or an active energy ray cationically polymerizable resin.

[0023] [Active energy ray radical polymerizable resin] Examples of the active energy ray-polymerizable resin include an active energy ray-polymerizable polyurethane resin. That is, the active energy ray-polymerizable resin contains, for example, an active energy ray-polymerizable polyurethane resin, and is preferably made of an active energy ray-polymerizable polyurethane resin.

[0024] Examples of active energy ray-polymerizable polyurethane resins include polyurethane resins capable of radical polymerization. The active energy ray-polymerizable polyurethane resin contains, for example, a reaction product of a polyisocyanate component, an alcohol component, and an active energy ray-polymerizable group-containing component. The active energy ray-polymerizable polyurethane resin is preferably composed of a reaction product of a polyisocyanate component, an alcohol component, and an active energy ray-polymerizable group-containing component.

[0025] The polyisocyanate component includes, for example, a polyisocyanate monomer and a polyisocyanate derivative.

[0026] Examples of polyisocyanate monomers include linear aliphatic polyisocyanate monomers, alicyclic polyisocyanate monomers, aromatic polyisocyanate monomers, and araliphatic polyisocyanate monomers. Examples of linear aliphatic polyisocyanate monomers include linear aliphatic diisocyanates. Examples of linear aliphatic diisocyanates include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate (PDI), and hexamethylene diisocyanate (HDI). Examples of alicyclic polyisocyanate monomers include alicyclic diisocyanates. Examples of alicyclic diisocyanates include cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane (H6XDI), isophorone diisocyanate (IPDI), norbornene diisocyanate (NBDI), and methylenebis(cyclohexylisocyanate) (H 12 Examples of aromatic polyisocyanate monomers include aromatic diisocyanates. Examples of aromatic diisocyanates include diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), toluidine diisocyanate (TODI), paraphenylene diisocyanate, and naphthalene diisocyanate (NDI). Examples of araliphatic polyisocyanate monomers include araliphatic diisocyanates. Examples of araliphatic diisocyanates include xylylene diisocyanate (XDI) and tetramethylxylylene diisocyanate (TMXDI). These can be used alone or in combination of two or more types.

[0027] Examples of polyisocyanate derivatives include modified products obtained by modifying the above-mentioned polyisocyanate monomers using known methods. More specifically, examples of polyisocyanate derivatives include polymers, isocyanurate modified products, allophanate modified products, polyol modified products, biuret modified products, urea modified products, oxadiazinetrione modified products, and carbodiimide modified products. Further, examples of polyisocyanate derivatives include polymethylene polyphenylene polyisocyanate. These can be used alone or in combination of two or more types.

[0028] These may be used alone or in combination of two or more. As the polyisocyanate component, preferably, a polyisocyanate monomer is used, more preferably, an alicyclic polyisocyanate monomer is used, and even more preferably, bis(isocyanatomethyl)cyclohexane (H6XDI) is used.

[0029] Examples of bis(isocyanatomethyl)cyclohexane (H6XDI) include 1,2-bis(isocyanatomethyl)cyclohexane (1,2-H6XDI), 1,3-bis(isocyanatomethyl)cyclohexane (1,3-H6XDI), and 1,4-bis(isocyanatomethyl)cyclohexane (1,4-H6XDI). These can be used alone or in combination of two or more. Preferably, 1,3-bis(isocyanatomethyl)cyclohexane (1,3-H6XDI) is used.

[0030] The alcohol component includes, for example, monools and polyols.

[0031] Examples of monools include low-molecular-weight monools (ie, monohydric low-molecular-weight alcohols) and high-molecular-weight monools (ie, monohydric high-molecular-weight alcohols).

[0032] Examples of low-molecular-weight monools include organic compounds having one hydroxyl group in the molecule and a relatively low molecular weight. Here, "relatively low molecular weight" means a number-average molecular weight of less than 400, preferably 300 or less (the same applies hereinafter). Examples of low-molecular-weight monools include low-molecular-weight monools having 1 to 50 carbon atoms. Examples of low-molecular-weight monools include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, s-butanol, t-butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, lauryl alcohol, myristyl alcohol (tetradecanol), pentadecanol, cetyl alcohol (hexadecanol), heptadecanol, stearyl alcohol (octadecanol), nonadecanol, oleyl alcohol, polyethylene ether monool, polybutylene ether monool, cyclohexanol, methylcyclohexanol, and benzyl alcohol. These may be used alone or in combination of two or more.

[0033] Examples of high-molecular-weight monools include organic compounds having one hydroxyl group in the molecule and a relatively high molecular weight. Here, a relatively high molecular weight means a number-average molecular weight of 400 or more, preferably 500 or more (the same applies hereinafter). More specifically, examples of high-molecular-weight monools include single-end-capped macrodiols. Examples of single-end-capped macrodiols include single-end-capped macrodiols containing a nonionic group. The nonionic group is, for example, a polyoxyethylene group having one end capped with an alkoxy group. Examples of single-end-capped macrodiols containing a nonionic group include single-end-capped polyoxyethylene glycols. Examples of single-end-capped polyoxyethylene glycols include alkoxyethylene glycols (monoalkoxypolyethylene glycols) having one end capped with an alkyl group. Examples of the alkyl group include alkyl groups having 1 to 20 carbon atoms, preferably alkyl groups having 1 to 10 carbon atoms, and more preferably alkyl groups having 1 to 4 carbon atoms. More specifically, alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, and t-butyl, and preferably methyl and ethyl. More specifically, single-end-capped polyoxyethylene glycols include methoxypolyoxyethylene glycol (MPEG) and ethoxypolyoxyethylene glycol. These can be used alone or in combination of two or more types.

[0034] The number average molecular weight of the high molecular weight monool is, for example, 400 to 20,000, preferably 500 to 20,000, more preferably 1,000 to 10,000, and even more preferably 2,000 to 10,000. The number average molecular weight can be calculated by a known method from the hydroxyl group equivalent weight and the average number of hydroxyl groups. The number average molecular weight can also be measured as a polystyrene-equivalent molecular weight by gel permeation chromatography (the same applies hereinafter).

[0035] Polyols include, for example, low molecular weight polyols (ie, polyhydric low molecular weight alcohols) and high molecular weight polyols (ie, polyhydric high molecular weight alcohols).

[0036] Examples of low-molecular-weight polyols include organic compounds with two or more hydroxyl groups in the molecule and a relatively low molecular weight. Examples of low-molecular-weight polyols include dihydric alcohols, trihydric alcohols, and tetrahydric or higher alcohols. Examples of dihydric alcohols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, and dipropylene glycol. Examples of trihydric alcohols include glycerin and trimethylolpropane. Examples of tetrahydric or higher alcohols include pentaerythritol and diglycerin. Examples of low-molecular-weight polyols include polymers obtained by addition polymerization of alkylene (C2-C3) oxide with dihydric to tetrahydric alcohols to obtain a number-average molecular weight of less than 400. These can be used alone or in combination of two or more types.

[0037] Examples of high molecular weight polyols include organic compounds having two or more hydroxyl groups in the molecule and having a relatively high molecular weight. Examples of high molecular weight polyols include polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, and vinyl monomer-modified polyols. These can be used alone or in combination of two or more. A preferred example of high molecular weight polyol is polyether polyol.

[0038] Examples of polyether polyols include polyoxyalkylene (carbon number 2-3) polyols and polytetramethylene ether polyols. Examples of polyoxyalkylene (carbon number 2-3) polyols include polyoxyethylene polyols, polyoxypropylene polyols, and polyoxyethylene-polyoxypropylene polyols (random copolymers and block copolymers). These polyether polyols can be used alone or in combination of two or more. A preferred example of the polyether polyol is polyoxyethylene polyol.

[0039] The high molecular weight polyol has an average number of functional groups (average number of hydroxyl groups) of, for example, 2 to 6, preferably 2 to 4, more preferably 2 to 3, and particularly preferably 2.

[0040] The number average molecular weight of the high molecular weight polyol is, for example, 400 to 20,000, preferably 500 to 20,000, more preferably 1,000 to 10,000, and still more preferably 2,000 to 10,000.

[0041] The alcohol component can be used alone or in combination of two or more kinds. The alcohol component preferably contains a polyol, more preferably consists of a polyol. The alcohol component further preferably contains a high molecular weight polyol, particularly preferably consists of a high molecular weight polyol.

[0042] Examples of the active energy ray-polymerizable group-containing component include a component that contains an active energy ray-polymerizable group and is capable of reacting with a polyisocyanate component and / or an alcohol component. Examples of the active energy ray-polymerizable group include a photopolymerizable group, and more specifically, an ethylenically unsaturated group.

[0043] Examples of the active energy ray-polymerizable group-containing component include a hydroxyl group-containing unsaturated compound. That is, the active energy ray-polymerizable group-containing component contains, for example, a hydroxyl group-containing unsaturated compound. The active energy ray-polymerizable group-containing component is preferably composed of a hydroxyl group-containing unsaturated compound.

[0044] Examples of hydroxyl group-containing unsaturated compounds include compounds having one or more ethylenically unsaturated groups and one or more hydroxyl groups. Examples of ethylenically unsaturated groups include (meth)acryloyl groups, vinylphenyl groups, propenyl ether groups, allyl ether groups, and vinyl ether groups. Note that (meth)acryloyl refers to acryloyl and / or methacryloyl. Furthermore, (meth)acrylic refers to acrylic and / or methacrylic, and (meth)acrylate refers to acrylate and / or methacrylate. A preferred ethylenically unsaturated group is a (meth)acryloyl group, and more preferably an acryloyl group. When the ethylenically unsaturated group is a (meth)acryloyl group, examples of hydroxyl group-containing unsaturated compounds include hydroxyl group-containing (meth)acrylates.

[0045] Examples of hydroxyl group-containing (meth)acrylates include monohydroxyl mono(meth)acrylate, polyhydroxyl mono(meth)acrylate, monohydroxyl poly(meth)acrylate, and polyhydroxyl poly(meth)acrylate.

[0046] Monohydroxyl mono(meth)acrylate is a compound having one hydroxyl group and one (meth)acryloyl group in one molecule. Examples of monohydroxyl mono(meth)acrylates include 2-hydroxyethyl(meth)acrylate (HE(M)A), 2-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 2-phenoxypropyl(meth)acrylate, 4-hydroxycyclohexyl(meth)acrylate, 3-chloro-2-hydroxypropyl(meth)acrylate, 2-hydroxy-3-phenyloxypropyl(meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethylphthalate, 2-hydroxyalkyl(meth)acryloylphosphate, pentanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate.

[0047] Polyhydroxyl mono(meth)acrylate is a compound having multiple hydroxyl groups and one (meth)acryloyl group in one molecule. Examples of polyhydroxyl mono(meth)acrylate include trimethylolpropane mono(meth)acrylate, glycerin mono(meth)acrylate, and pentaerythritol mono(meth)acrylate.

[0048] Monohydroxyl poly(meth)acrylate is a compound having one hydroxyl group and multiple (meth)acryloyl groups in one molecule. Examples of monohydroxyl poly(meth)acrylate include trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate.

[0049] Polyhydroxyl poly(meth)acrylate is a compound having multiple hydroxyl groups and multiple (meth)acryloyl groups in one molecule. Examples of polyhydroxyl poly(meth)acrylate include pentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, and dipentaerythritol tetra(meth)acrylate.

[0050] These hydroxyl group-containing unsaturated compounds can be used alone or in combination of two or more. As the hydroxyl group-containing unsaturated compound, preferably, a hydroxyl group-containing (meth)acrylate, more preferably, a monohydroxyl mono(meth)acrylate, a monohydroxyl poly(meth)acrylate, even more preferably, a monohydroxyl mono(meth)acrylate, even more preferably, a hydroxyalkyl (meth)acrylate, and particularly preferably, 2-hydroxyethyl (meth)acrylate (HE(M)A).

[0051] The method for reacting the polyisocyanate component, the alcohol component, and the active energy ray-polymerizable group-containing component is not particularly limited. For example, the polyisocyanate component, the alcohol component, and the active energy ray-polymerizable group-containing component may be reacted all at once. Alternatively, the polyisocyanate component, the alcohol component, and the active energy ray-polymerizable group-containing component may be reacted sequentially. Preferably, the polyisocyanate component and the alcohol component are reacted first, and then the reaction product is reacted with the active energy ray-polymerizable group-containing component.

[0052] More specifically, in this method, a polyisocyanate component and an alcohol component are first mixed in a predetermined ratio and subjected to a urethane reaction, thereby producing a modified product (hereinafter referred to as alcohol-added isocyanate) in which the alcohol component is added to the polyisocyanate component (alcohol addition step).

[0053] In the alcohol addition step, the equivalent ratio of the isocyanate groups in the polyisocyanate component to the hydroxyl groups in the alcohol component (isocyanate groups / hydroxyl groups) is, for example, greater than 1. More specifically, the equivalent ratio of the isocyanate groups in the polyisocyanate component to the hydroxyl groups in the alcohol component (isocyanate groups / hydroxyl groups) is preferably 1.1 to 20, more preferably 3 to 15, and even more preferably 6 to 10.

[0054] In the alcohol addition step, a known reaction method is employed. Examples of the reaction method include bulk reaction and solution reaction. In the bulk reaction, for example, the above components are blended under a nitrogen atmosphere and reacted at a reaction temperature of 75 to 85°C for about 1 to 20 hours. In the solution reaction, for example, the above components are added to a known organic solvent under a nitrogen atmosphere and reacted at a reaction temperature of 20 to 80°C for about 1 to 20 hours. In addition, in the alcohol addition step, a known urethane catalyst is added in an appropriate ratio as needed.

[0055] This results in the production of an alcohol-added isocyanate as the reaction product of the alcohol addition step. The alcohol-added isocyanate is purified by a known method, if necessary. Examples of the purification method include distillation and extraction, and preferably distillation. The distillation method is not particularly limited, but examples include batch distillation and continuous distillation, and preferably continuous distillation. Examples of the continuous distillation method include thin film distillation (Smith thin film distillation). The distillation conditions are set according to the purpose and application.

[0056] The isocyanate group concentration of the alcohol-adducted isocyanate is, for example, 0.3 to 15 mass %, preferably 0.5 to 12 mass %, and more preferably 1.0 to 10 mass %, relative to the total amount of the alcohol-adducted isocyanate (converted into solid content).

[0057] Next, in this method, the alcohol-added isocyanate is reacted with an active energy ray-polymerizable group-containing component in a predetermined ratio (polymerizable group addition step), thereby producing an active energy ray-polymerizable polyurethane resin.

[0058] More specifically, in the polymerizable group addition step, for example, the above-mentioned isocyanate group-terminated prepolymer and an active energy ray-polymerizable group-containing component (hydroxyl group-containing unsaturated compound) are blended in a predetermined equivalent ratio under an inert gas atmosphere, and a urethane reaction is carried out.

[0059] The equivalent ratio (isocyanate group / hydroxyl group) of the isocyanate group in the isocyanate group-terminated prepolymer to the hydroxyl group in the active energy ray-polymerizable group-containing component (hydroxyl group-containing unsaturated compound) is, for example, 0.7 to 1.5, or preferably 0.9 to 1.2.

[0060] The reaction conditions are not particularly limited and are appropriately set depending on the purpose and application. For example, the reaction temperature is, for example, 40 to 120°C, preferably 50 to 100°C, and more preferably 60 to 80°C. The reaction time is, for example, 0.5 to 24 hours, preferably 1.0 to 10 hours. In the polymerizable group addition step, a known urethane catalyst is added in an appropriate ratio, if necessary.

[0061] This results in an active energy ray-polymerizable polyurethane resin. In the above method, the active energy ray-polymerizable polyurethane resin is obtained by a urethane reaction between the isocyanate group of the alcohol-added isocyanate and the hydroxyl group of the active energy ray-polymerizable group-containing component (hydroxyl group-containing unsaturated compound). That is, the active energy ray-polymerizable polyurethane resin is, for example, a reaction product between the alcohol-added isocyanate and the active energy ray-polymerizable group-containing component. In addition, the active energy ray-polymerizable polyurethane resin is, for example, a polyurethane resin having an unsaturated bond derived from the active energy ray-polymerizable group-containing component (hydroxyl group-containing unsaturated compound).

[0062] These can be used alone or in combination of two or more. The composition (type) and number average molecular weight of the active energy ray anionically polymerizable resin are not particularly limited and can be selected appropriately.

[0063] [Active energy ray cationic polymerizable resin] Examples of the active energy ray cationically polymerizable resin include active energy ray polymerizable epoxy resin, active energy ray polymerizable oxetane resin, active energy ray polymerizable maleimide resin, and active energy ray polymerizable vinyl ether resin. These can be used alone or in combination of two or more. A preferred example of the active energy ray cationically polymerizable resin is active energy ray polymerizable epoxy resin.

[0064] Examples of active energy ray-polymerizable epoxy resins include polyfunctional epoxy compounds, more specifically, bisphenol-type epoxy resins, biphenyl-type epoxy resins, fluorene-type epoxy resins, and alicyclic epoxy resins. These can be used alone or in combination of two or more. Preferred are alicyclic epoxy resins. Examples of alicyclic epoxy resins include tetrahydroindene diepoxide, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloxirane, and 3,4-epoxy-6-methylcyclohexylmethyl-3',4'-epoxy-6-methylcyclohexanecarboxylate. These can be used alone or in combination of two or more. Preferred is tetrahydroindene diepoxide.

[0065] The curable resin can be used alone or in combination of two or more kinds. As the curable resin, preferably, an active energy ray radical polymerizable resin is used alone, and an active energy ray cationically polymerizable resin is used alone. That is, the curable resin is preferably made of an active energy ray radical polymerizable resin or an active energy ray cationically polymerizable resin.

[0066] More preferably, the curable resin is an active energy ray radical polymerizable polyurethane resin used alone, or an active energy ray cationically polymerizable epoxy resin used alone. That is, the curable resin is more preferably made of an active energy ray radical polymerizable polyurethane resin or an active energy ray cationically polymerizable epoxy resin.

[0067] More preferably, the curable resin is an active energy ray radical polymerizable polyurethane resin used alone, that is, the curable resin is more preferably made of an active energy ray radical polymerizable polyurethane resin.

[0068] [Hardening resin content] The lower limit of the content of the curable resin is, for example, 10% by mass or more, preferably 20% by mass or more, and more preferably 40% by mass or more, relative to the total amount of the active energy ray-polymerizable composition. The upper limit of the content of the curable resin is, for example, 100% by mass or less, preferably 90% by mass or less, and more preferably 70% by mass or less, relative to the total amount of the curable composition. That is, the content of the curable resin is, for example, 10 to 100% by mass, preferably 20 to 90% by mass, and more preferably 40 to 70% by mass, relative to the total amount of the curable composition.

[0069] The lower limit of the content of the curable resin relative to the total amount of the curable components is, for example, 10% by mass or more, preferably 20% by mass or more, and more preferably 40% by mass or more. The upper limit of the content of the curable resin relative to the total amount of the curable components is, for example, 100% by mass or less, preferably 90% by mass or less, and more preferably 70% by mass or less. That is, the content of the curable resin relative to the total amount of the curable components is, for example, 10 to 100% by mass, preferably 20 to 90% by mass, and more preferably 40 to 70% by mass.

[0070] [Polymerizable diluent] The curable component may optionally contain a polymerizable diluent, if desired. The curable component preferably contains a polymerizable diluent.

[0071] Examples of polymerizable diluents include polymerizable compounds having an aromatic hydrocarbon skeleton, polymerizable compounds having an alicyclic hydrocarbon skeleton, polymerizable compounds having a chain aliphatic hydrocarbon skeleton, polymerizable compounds having a chain ether skeleton, polymerizable compounds having an alicyclic ether skeleton, polymerizable compounds having an amide skeleton, polymerizable compounds having an oxyalkylene skeleton, compounds having both a (meth)acryloyl group and a vinyl group, poly(meth)acrylate, hydroxyl group-containing (meth)acrylate, and unsaturated carboxylic acid allyl ester. Examples of polymerizable compounds having an aromatic hydrocarbon skeleton include 3-phenoxybenzyl (meth)acrylate, styrene, vinyltoluene, divinylbenzene, and α-methylstyrene. Examples of polymerizable compounds having an alicyclic hydrocarbon skeleton include cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, and dicyclopentanyl (meth)acrylate. Examples of polymerizable compounds having a chain aliphatic hydrocarbon skeleton include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate. Examples of polymerizable compounds having a chain ether skeleton include 2-ethylhexyl-diglycol (meth)acrylate. Examples of polymerizable compounds having an alicyclic ether skeleton include cyclic trimethylolpropane formal (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate, and 4-(meth)acryloylmorpholine. Examples of polymerizable compounds having an amide skeleton include N,N-diethyl(meth)acrylamide. Examples of polymerizable compounds having an oxyalkylene skeleton include 2-ethylhexyl-diglycol (meth)acrylate.Examples of compounds having both a (meth)acryloyl group and a vinyl group include methyl 2-(allyloxymethyl)acrylate, 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 5-vinyloxypentyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, p-vinyloxymethylphenylmethyl (meth)acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, and 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate. Examples of polyol poly(meth)acrylates include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, pentanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hexanediol di(meth)acrylate, nonanediol di(meth)acrylate, decanediol di(meth)acrylate, oligoethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Examples of hydroxyl group-containing (meth)acrylates include the above-mentioned monohydroxyl mono(meth)acrylates (e.g., 4-hydroxybutyl (meth)acrylate). Examples of unsaturated carboxylic acid allyl esters include allyl (meth)acrylate, diallyl maleate, diallyl fumarate, and diallyl itaconate. These can be used alone or in combination of two or more.

[0072] The lower limit of the content of the polymerizable diluent relative to the total amount of the curable composition is, for example, 0% by mass or more, preferably 10% by mass or more, and more preferably 30% by mass or more. The upper limit of the content of the polymerizable diluent relative to the total amount of the curable composition is, for example, 90% by mass or less, preferably 80% by mass or less, and more preferably 60% by mass or less. That is, the content of the polymerizable diluent relative to the total amount of the curable composition is, for example, 0 to 90% by mass, preferably 10 to 80% by mass, and more preferably 30 to 60% by mass.

[0073] The type and content of the polymerizable diluent are not particularly limited and are selected appropriately. For example, the lower limit of the content of the polymerizable diluent is, for example, 0% by mass or more, preferably 10% by mass or more, and more preferably 30% by mass or more, relative to the total amount of the curable components. The upper limit of the content of the polymerizable diluent is, for example, 90% by mass or less, preferably 80% by mass or less, and more preferably 60% by mass or less, relative to the total amount of the curable components. In other words, the content of the polymerizable diluent is, for example, 0 to 90% by mass, preferably 10 to 80% by mass, and more preferably 30 to 60% by mass, relative to the total amount of the curable components.

[0074] The lower limit of the content of the polymerizable diluent is, for example, 0 parts by mass or more, preferably 20 parts by mass or more, and more preferably 50 parts by mass or more, relative to 100 parts by mass of the curable resin. The upper limit of the content of the polymerizable diluent is, for example, 300 parts by mass or less, preferably 200 parts by mass or less, and more preferably 150 parts by mass or less, relative to 100 parts by mass of the curable resin. The content of the polymerizable diluent is, for example, 0 to 300 parts by mass, preferably 20 to 200 parts by mass, and more preferably 50 to 150 parts by mass, relative to 100 parts by mass of the curable resin.

[0075] [Content of hardening component] The content of the curable component (the total amount of the curable resin and the polymerizable diluent (hereinafter the same)) is appropriately selected depending on the purpose and application. For example, from the viewpoint of obtaining a pattern structure (relief structure) having a relatively high aspect ratio, the lower limit of the content of the curable component is, for example, 30% by mass or more, preferably 50% by mass or more, and more preferably 70% by mass or more, based on the total amount of the curable composition. Furthermore, from the viewpoint of obtaining a pattern structure (relief structure) having a relatively high aspect ratio, the upper limit of the content of the curable component is, for example, 99.5% by mass or less, preferably 99% by mass or less, and more preferably 98% by mass or less, based on the total amount of the curable composition. In other words, from the viewpoint of obtaining a pattern structure (relief structure) having a relatively high aspect ratio, the content of the curable component is, for example, 50 to 99.5% by mass, preferably 70 to 99% by mass, and more preferably 90 to 98% by mass, based on the total amount of the active energy ray-polymerizable composition.

[0076] [Active energy ray polymerization initiator] Examples of the active energy ray polymerization initiator include an active energy ray radical polymerization initiator and an active energy ray cationic polymerization initiator, and preferably an active energy ray radical polymerization initiator. Examples of the active energy ray radical polymerization initiator include a cleavage-type active energy ray radical polymerization initiator and a hydrogen abstraction-type active energy ray radical polymerization initiator, and preferably a cleavage-type active energy ray radical polymerization initiator. In other words, the curable composition preferably contains a cleavage-type active energy ray radical polymerization initiator, and more preferably consists of a cleavage-type active energy ray radical polymerization initiator.

[0077] Examples of the cleavage-type active energy ray radical polymerization initiator include diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one, and bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titano. Examples of suitable benzoyl esters include benzophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone, ethyl (2,4,6-trimethylbenzoyl)-phenylphosphinate, 1,1'-[methylenebis(4,1-phenylene)]bis(2-methyl-2-hydroxy-1-propanone), 2,2-dimethoxy-2-phenylacetophenone, bis[4-(2-hydroxy-2-methylpropanoyl)phenyl]ether, 1-[4-(phenylthio)phenyl]octane-1,2-dione = 2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime). These can be used alone or in combination.

[0078] The cleavage-type active energy ray radical polymerization initiator is commercially available. Examples of commercially available cleavage-type active energy ray radical polymerization initiators include Omnirad TPO, Omnirad 819, Omnirad 380, Omnirad 907, Omnirad 369, Omnirad 2959, Omnirad 379, Omnirad 784, Omnirad 651, Omnirad 184, Omnirad 1173, Omnirad TPO-L, Omnirad 127, ESACURE KIP150, Omnirad 601, Omnirad 1314, and Omnirad 1315 (all trade names, manufactured by IGM resins B.V.). These can be used alone or in combination of two or more types.

[0079] [Active energy ray polymerization initiator content] The content of the active energy ray polymerization initiator is appropriately selected depending on the type of the active energy ray polymerization initiator.

[0080] For example, when the curable composition contains a cleavage-type active energy ray radical polymerization initiator, the content of the active energy ray polymerization initiator relative to the total amount of the curable composition is, for example, 0.5% by mass or more, preferably 1% by mass or more, and more preferably 2% by mass or more, from the viewpoint of obtaining a pattern structure (convexo-concave structure) having a relatively high aspect ratio. When the curable composition contains a cleavage-type active energy ray radical polymerization initiator, the content of the active energy ray polymerization initiator relative to the total amount of the curable composition is, for example, 20% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less, from the viewpoint of obtaining a pattern structure (convexo-concave structure) having a relatively high aspect ratio. That is, when the curable composition contains a cleavage-type active energy ray radical polymerization initiator, the content of the active energy ray polymerization initiator relative to the total amount of the curable composition is, for example, 0.5 to 20% by mass, preferably 1 to 15% by mass, and more preferably 2 to 10% by mass, from the viewpoint of obtaining a pattern structure (convexo-concave structure) having a relatively high aspect ratio.

[0081] When the curable composition is a cleavage-type active energy ray radical polymerization initiator, from the viewpoint of obtaining a pattern structure (relief structure) having a relatively high aspect ratio, the lower limit of the content of the active energy ray polymerization initiator is, for example, 0.1 parts by mass or more, preferably 1 part by mass or more, more preferably 3 parts by mass or more, per 100 parts by mass of the curable component. When the curable composition is a cleavage-type active energy ray radical polymerization initiator, from the viewpoint of obtaining a pattern structure (relief structure) having a relatively high aspect ratio, the upper limit of the content of the active energy ray polymerization initiator is, for example, 20 parts by mass or less, preferably 10 parts by mass or less, more preferably 8 parts by mass or less, per 100 parts by mass of the curable component. That is, when the curable composition contains a cleavage-type active energy ray radical polymerization initiator, from the viewpoint of obtaining a pattern structure (relief structure) having a relatively high aspect ratio, the content of the active energy ray polymerization initiator is, for example, 0.1 to 20 parts by mass, preferably 1 to 10 parts by mass, and more preferably 3 to 8 parts by mass, relative to 100 parts by mass of the curable component.

[0082] When the curable composition is a cleavage-type active energy ray radical polymerization initiator, from the viewpoint of obtaining a pattern structure (relief structure) having a relatively high aspect ratio, the lower limit of the content of the active energy ray polymerization initiator is, for example, 0.1 parts by mass or more, preferably 2 parts by mass or more, more preferably 5 parts by mass or more, relative to 100 parts by mass of the curable resin. When the curable composition is a cleavage-type active energy ray radical polymerization initiator, from the viewpoint of obtaining a pattern structure (relief structure) having a relatively high aspect ratio, the upper limit of the content of the active energy ray polymerization initiator is, for example, 40 parts by mass or less, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, relative to 100 parts by mass of the curable resin. That is, when the curable composition contains a cleavage-type active energy ray radical polymerization initiator, from the viewpoint of obtaining a pattern structure (relief structure) having a relatively high aspect ratio, the content of the active energy ray polymerization initiator is, for example, 0.1 to 40 parts by mass, preferably 2 to 20 parts by mass, and more preferably 5 to 10 parts by mass, relative to 100 parts by mass of the curable resin.

[0083] [Thermal polymerization initiator] When the curable resin is an active energy ray-curable resin and a thermosetting resin, the curable composition may contain a thermal polymerization initiator as an optional component. Examples of the thermal polymerization initiator include a thermal radical polymerization initiator and a thermal cationic polymerization initiator. Examples of the thermal radical polymerization initiator include a known azo compound and a known peroxide. Examples of the thermal cationic polymerization initiator include a known iodonium salt compound and a known sulfonium salt compound. These compounds may be used alone or in combination of two or more. The amount and timing of the thermal polymerization initiator to be added are appropriately determined depending on the purpose and application.

[0084] [Additives] The curable composition may contain additives as optional components. Examples of additives include plasticizers, antioxidants, volatile substances (e.g., olefins), thixotropic agents, UV absorbers, fluorescent brighteners, internal mold release agents, lubricants, sensitizers, antiblocking agents, heat stabilizers, active energy ray stabilizers, light stabilizers, catalysts, pigments, dyes, lubricants, fillers, and hydrolysis inhibitors. The amounts and timing of addition of these additives are appropriately determined depending on the purpose and application.

[0085] [Preparation of Curable Composition] The method for preparing the curable composition is not particularly limited. For example, the curable component, the active energy ray polymerization initiator, the optional thermal polymerization initiator, and the optional additives are mixed by a known method. As a result, the curable composition is obtained as a mixture.

[0086] A method for producing a pattern-structured cured resin product using a curable composition will be described in detail below with reference to Figures 1 and 2. In Figures 1 and 2, the upper surface (upper side) of the paper is one surface (one side), and the lower surface (lower side) of the paper is the other surface (other side) relative to the one surface (one side).

[0087] 2) Placement process In this method, after the above-mentioned preparation step, as shown in FIGS. 1A and 1B, the curable composition is placed at a desired position (placement step).

[0088] More specifically, in this method, as shown in FIG. 1A, a mold 10 for disposing the curable composition is prepared. The mold 10 includes, for example, a substrate 11 and a spacer 12 disposed on the upper surface of the substrate 11. The substrate 11 has, for example, a flat plate shape. The spacer 12 has, for example, a rectangular frame shape. The spacer 12 is placed on the substrate 11 and defines a space above the substrate 11 for disposing the curable composition. The sizes of the substrate 11 and the spacer 12 are appropriately set depending on the purpose and application.

[0089] Next, in this method, as shown in FIG. 1B, for example, a curable composition 2 is placed on the upper surface of the substrate 11 and within the frame of the spacer 12. The method for placing the curable composition 2 is not particularly limited, and examples thereof include a casting method, a dispensing method, a printing method, a 3D printing method, a bar coating method, a roll coating method, and a spraying method. These methods can be used alone or in combination of two or more.

[0090] The position and amount of the curable composition 2 are appropriately set depending on the purpose and application. For example, the curable composition 2 is placed within the frame of the spacer 12 so that one surface of the coating film (uncured film) of the curable composition 2 and one surface of the spacer 12 (upper surface on the paper) are flush with each other.

[0091] The thickness of the curable composition 2 (that is, the thickness of the uncured film) is, for example, 1 to 100,000 μm, preferably 10 to 10,000 μm, more preferably 50 to 1,000 μm, and still more preferably 50 to 200 μm.

[0092] 3) Coating process In this method, after the disposing step, for example, as shown in FIG. 1C, at least one surface of the curable composition 2 is covered with an active energy ray-transmitting covering material 13 (covering step).

[0093] The active energy ray-transmitting covering material 13 contains, for example, a material that is transmissive to active energy rays, and is preferably made of a material that is transmissive to active energy rays. Examples of materials that are transmissive to active energy rays include active energy ray-transmitting resins (translucent resins), glass, ceramics, and paper. From the viewpoint of preventing gas (described later) from being released into the atmosphere, active energy ray-transmitting resins are preferred. These materials can be used alone or in combination of two or more types.

[0094] Examples of the active energy ray-transmitting resin include known transparent resins, more specifically, polyester, polyolefin, polycarbonate, polystyrene, polyamide, polyamideimide, polyvinyl chloride, and cellulose acetate. These can be used alone or in combination of two or more. Polyester is preferred.

[0095] The shape of the active energy ray-transmittable covering material 13 is not particularly limited and may be appropriately determined depending on the purpose and application. Examples of the shape include a film, a sheet, and a plate, and a film is preferred.

[0096] The active energy ray-transmittable covering material 13 is preferably a film made of an active energy ray-transmittable resin, more preferably a polyester film.

[0097] The size of the active energy ray-transmittable covering material 13 is not particularly limited and is set appropriately depending on the purpose and application. For example, the thickness of the active energy ray-transmittable covering material 13 is, for example, 5 to 500 μm, preferably 10 to 100 μm.

[0098] The active energy ray-transparent coating material 13 covers, for example, one surface in the thickness direction (upper surface in the drawing) of the curable composition 2. The active energy ray-transparent coating material 13 can also cover, for example, the other surface (lower surface in the drawing) opposite to the one surface in the thickness direction of the curable composition 2. More specifically, for example, the substrate 11 of the molding die 10 may be the active energy ray-transparent coating material 13.

[0099] There are no particular limitations on the method for covering the curable composition 2 with the active energy ray-transparent covering material 13. For example, the active energy ray-transparent covering material 13 is arranged so that it is in close contact with one surface of the curable composition 2 in the thickness direction (the upper surface in the drawing).

[0100] More specifically, as described above, the curable composition 2 is placed so that one surface in the thickness direction of the curable composition 2 (the upper surface of the paper) is flush with one surface of the spacer 12 (the upper surface of the paper). Then, the active energy ray-transparent covering material 13 is placed on one surface (the upper surface of the paper) of the spacer 12. In this way, the active energy ray-transparent covering material 13 and the curable composition 2 are brought into close contact with each other.

[0101] 4) Masking process In this method, after the above-described coating step, for example, as shown in FIG. 1D, a photomask 14 is placed on one surface of the active energy ray-transmittable coating material 13 (masking step).

[0102] The photomask 14 has, for example, a plurality of light-transmitting portions 15 and a plurality of light-shielding portions 16. The light-transmitting portions 15 and the light-shielding portions 16 are arbitrarily arranged to form a pattern. Examples of the pattern include a line-and-space pattern, a dot pattern, and a checkerboard pattern, and preferably a line-and-space pattern. In other words, the light-transmitting portions 15 and the light-shielding portions 16 preferably have a line-and-space pattern.

[0103] The line and space pattern has, for example, lines made of light-shielding portions 16 and spaces made of light-transmitting portions 15 arranged alternately.

[0104] From the viewpoint of forming a pattern structure (relief structure) having a relatively high aspect ratio, the line width in the line and space pattern is, for example, less than 100 μm, preferably 50 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. Furthermore, from the viewpoint of forming a pattern structure (relief structure) having a relatively high aspect ratio, the line width in the line and space pattern is, for example, 0.01 μm or more, preferably 0.05 μm or more, more preferably 0.1 μm or more, and even more preferably 0.5 μm or more. That is, from the viewpoint of forming a pattern structure (relief structure) having a relatively high aspect ratio, the line width in the line and space pattern is, for example, 0.01 μm or more and less than 100 μm, preferably 0.05 to 50 μm, more preferably 0.1 to 10 μm, and even more preferably 0.5 to 5 μm.

[0105] From the viewpoint of forming a pattern structure (relief structure) having a relatively high aspect ratio, the space width in the line and space pattern is, for example, less than 100 μm, preferably 50 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. Furthermore, from the viewpoint of forming a pattern structure (relief structure) having a relatively high aspect ratio, the space width in the line and space pattern is, for example, 0.01 μm or more, preferably 0.05 μm or more, more preferably 0.1 μm or more, and even more preferably 0.5 μm or more. That is, from the viewpoint of forming a pattern structure (relief structure) having a relatively high aspect ratio, the space width in the line and space pattern is, for example, 0.01 μm or more and less than 100 μm, preferably 0.05 to 50 μm, more preferably 0.1 to 10 μm, and even more preferably 0.5 to 5 μm.

[0106] The ratio of the line width to the space width (line width / space width) is 0.01 to 100, preferably 0.05 to 50, more preferably 0.1 to 10, and even more preferably 0.5 to 5. The ratio of the line width to the space width (line width / space width) is particularly preferably 1. That is, the space width and the line width are particularly preferably the same.

[0107] There are no particular limitations on the method for placing the photomask 14 on one surface of the active energy ray-transparent covering material 13. For example, the photomask 14 is placed on one surface (the upper surface in the drawing) of the active energy ray-transparent covering material 13, and the light-shielding portion 16 of the photomask 14 and the active energy ray-transparent covering material 13 are brought into close contact.

[0108] Furthermore, the molding die 10, the active energy ray-transparent coating material 13, and the photomask 14 are fixed together, for example, by a jig (e.g., a clip) not shown. As a result, the curable composition 2 is sealed between the molding die 10 and the active energy ray-transparent coating material 13 and the photomask 14. In other words, the curable composition 2 is placed in an enclosed space.

[0109] 5) First curing process In this method, after the masking step, for example, as shown in FIGS. 2E to 2F, a part of the curable composition 2 is irradiated with active energy rays E through a photomask 14 (first curing step).

[0110] More specifically, in the first curing step, as shown in FIG. 2E, the curable composition 2 is irradiated with active energy rays E from one side of the photomask 14 (the upper side of the paper).

[0111] Examples of the active energy rays E include electron beams, ultraviolet rays, and visible light.

[0112] The irradiation conditions of the active energy rays E are appropriately set depending on the type and amount of the curable composition 2. For example, the irradiation amount (integrated light amount) of the active energy rays E is, for example, 10×10-3 ~6J / cm 2 , preferably 15 x 10 -3 ~4J / cm 2 The output of the active energy ray E is, for example, 1.0 to 1000 mW / cm 2 , preferably 10 to 1000 mW / cm 2 , more preferably 100mW / cm to 1000mW / cm 2 The peak wavelength of the active energy ray is adjusted depending on the active energy ray polymerization initiator. The peak wavelength of the active energy ray is, for example, 0.0001 nm to 800 nm. The irradiation with the active energy ray E may be performed once or multiple times.

[0113] The active energy rays E pass through the light-transmitting portion 15 of the photomask 14 and are irradiated toward a part of the curable composition 2. The part of the curable composition 2 indicates, for example, a part of the curable composition 2 that is disposed on the other side of the light-transmitting portion 15 (the lower side of the paper).

[0114] As a result, as shown in the enlarged view in FIG. 2F, the curable composition 2 is exposed to light in the above-mentioned portion, and the curable component polymerizes and cures. As a result, a cured product 3 of the curable component is formed. In addition, gas G is generated due to the active energy ray polymerization initiator. More specifically, when the active energy ray polymerization initiator contains a cleavage-type active energy ray radical polymerization initiator, cleavage of the active energy ray polymerization initiator generates a cleavage product gas. In other words, in the first curing step, gas G (e.g., cleavage product gas) is generated due to the active energy ray polymerization initiator in the above-mentioned portion irradiated with the active energy rays E.

[0115] On the other hand, the active energy rays E do not pass through the light-shielding portion 16 of the photomask 14 and are not irradiated toward the remaining portion of the curable composition 2. The remaining portion of the curable composition 2 refers to, for example, the portion of the curable composition 2 that is disposed on the other side of the light-shielding portion 16 (the lower side of the paper).

[0116] As a result, as shown in the enlarged view of Fig. 2F, in the remaining portion, the curable composition 2 is not exposed to light, and the curable component is not polymerized or cured. In other words, in the remaining portion, gas G is not generated, and the curable composition 2 remains in an uncured state.

[0117] That is, in the first curing step, only a portion of the curable composition 2 is cured to obtain a cured product 3. In addition, gas G is generated in a portion of the curable composition 2.

[0118] In such a case, the gas G cannot remain in the cured product 3 and is released toward the curable composition 2 that remains in an uncured state. That is, the gas G is released from the portion toward the remaining portion, as shown in the enlarged view of FIG. 2F. Then, the gas G moves in the remaining portion, pushing aside the curable composition 2, and remains as bubbles.

[0119] That is, in the remaining portion, the gas G generates a gap between the active energy ray-transmittable coating material 13 and the curable composition 2 , forming a depression 20 as a space on the surface of the curable composition 2 .

[0120] In other words, in the first curing step, the depressions 20 caused by the gas G are formed in the remaining portion relative to the portion irradiated with the active energy rays E.

[0121] As described above, a cured product 3 of the curable component is formed in the portion irradiated with the active energy rays E. The cured product 3 protrudes toward one side (upward in the drawing) relative to the depression 20. That is, in the first curing step, the irradiation with the active energy rays E forms a convex portion 4 as a first cured portion that does not have the depression 20.

[0122] In other words, in the first curing step, the curable component is cured in the part irradiated with the active energy rays E to form a first cured part (protrusion 4) having no space.

[0123] The height (average height (hereinafter the same)) of each protrusion 4 is in the range of, for example, 0.1 to 500 μm, preferably 0.5 to 250 μm, and more preferably 1.0 to 100 μm.

[0124] 6)Second curing process In this method, after the first curing step, for example, as shown in FIG. 2G, the remaining portion of the curable composition 2 is cured by irradiation with active energy rays and / or heating (second curing step).

[0125] More specifically, in the second curing step, the photomask 14 is removed, as shown in FIG. 2G.

[0126] In the second curing step, the active energy ray-transparent covering material 13 is not removed, and the gas G continues to remain between the active energy ray-transparent covering material 13 and the curable composition 2.

[0127] Then, in the second curing step, the remaining part of the curable composition 2 relative to the above-mentioned part is irradiated with active energy rays and / or the remaining part relative to the above-mentioned part is heated.

[0128] More specifically, for example, the curable composition 2 is irradiated with active energy rays E from above the active energy ray-transparent covering material 13 .

[0129] The irradiation conditions of the active energy rays E are appropriately set depending on the type and amount of the curable composition 2. For example, the irradiation amount (integrated light amount) of the active energy rays E is, for example, 10×10 -3 ~6J / cm 2 , preferably 15 x 10 -3 ~4J / cm 2 The output of the active energy ray E is, for example, 1.0 to 1000 mW / cm 2 , preferably 10 to 1000 mW / cm 2 , more preferably 100mW / cm to 1000mW / cm 2The peak wavelength of the active energy ray is adjusted depending on the active energy ray polymerization initiator. The peak wavelength of the active energy ray is, for example, 0.0001 nm to 800 nm. The irradiation with the active energy ray E may be performed once or multiple times.

[0130] The active energy rays E are irradiated, for example, toward the remainder of the curable composition 2. As a result, the curable component in the remainder is polymerized and cured.

[0131] In the second curing step, instead of irradiating the remaining part of the curable composition 2 with the active energy rays E, the remaining part of the curable composition 2 can also be heated.

[0132] More specifically, when the curable resin is an active energy ray-curable resin and a thermosetting resin, and further when the curable composition 2 contains a thermal polymerization initiator, the second curing step can heat the remainder of the curable composition 2 to thermally cure the curable composition 2. That is, the curable component in the remainder can be polymerized and cured.

[0133] The heating method is not particularly limited. For example, the remaining portion of the curable composition 2 is heated before and / or after removing the photomask. During heating, the first cured portion (convex portion 4) may be heated together with the remaining portion of the curable composition 2. The heating conditions in the second curing step are not particularly limited and are set appropriately depending on the type of curable resin and the type of thermal polymerization initiator.

[0134] In the second curing step, the remaining part of the curable composition 2 may be irradiated with active energy rays E and may also be heated.

[0135] In such a case, the order of irradiation with active energy rays E and heating is not particularly limited. For example, first, the remainder of the curable composition 2 can be irradiated with active energy rays E, and then the remainder of the curable composition 2 can be heated. Alternatively, for example, the remainder of the curable composition 2 can be heated, and then the remainder of the curable composition 2 can be irradiated with active energy rays E. Alternatively, for example, the remainder of the curable composition 2 can be irradiated with active energy rays E, and simultaneously the remainder of the curable composition 2 can be heated.

[0136] As described above, in the second curing step, the remaining portion of the curable composition 2 is irradiated with active energy rays and / or the remaining portion of the curable composition 2 is heated to form a cured product 3 of the curable component.

[0137] More specifically, in the second curing step, the curable component is cured in a state in which the curable composition 2 in the remaining portion is recessed relative to the protruding portions 4, thereby forming a cured product 3. In other words, in the remaining portion, the cured product 3 is recessed toward the other side (the lower side of the paper surface) relative to the protruding portions 4. In other words, in the second curing step, depressions 5 having depressions 20 are formed as second cured portions by irradiation with active energy rays E.

[0138] As a result, a concave-convex structure 6 is formed as a pattern structure having convex portions 4 and concave portions 5 in a pattern according to the photomask 14. Also, a cured product 3 having the concave-convex structure 6 is formed.

[0139] In other words, in the second curing step, the remaining portion is irradiated with active energy rays E and / or heated to cure the curable component, thereby forming second cured portions (recesses 5). Also, a concavo-convex structure 6 is formed as a pattern structure comprising first cured portions (recesses 4) and second cured portions (recesses 5) in the cured product 3 of the curable component.

[0140] The depth (average depth (hereinafter the same)) of the concave-convex structure 6 is, for example, the same as the height (average height (hereinafter the same)) of each convex portion 4. More specifically, the depth of the concave-convex structure 6 is, for example, 0.1 to 500 μm, preferably 0.5 to 250 μm, and more preferably 1.0 to 100 μm.

[0141] The width (average width (hereinafter the same)) of the concave-convex structure 6 is, for example, the same as the average value of the width of each convex portion 4 and the width of each concave portion 3. More specifically, the width of the concave-convex structure 6 is, for example, 0.01 μm or more and less than 100 μm, preferably 0.05 to 50 μm, more preferably 0.1 to 10 μm, and even more preferably 0.5 to 5 μm.

[0142] The lower limit of the aspect ratio (depth / width) of the concave-convex structure 6 is, for example, 5 or more, preferably 10 or more, more preferably 15 or more, even more preferably 18 or more, and particularly preferably 20 or more. The upper limit of the aspect ratio (depth / width) of the concave-convex structure 6 is usually 100 or less, preferably 50 or less. That is, the aspect ratio (depth / width) of the concave-convex structure 6 is, for example, 5 to 100, preferably 10 to 100, more preferably 15 to 50, even more preferably 18 to 50, and particularly preferably 20 to 50.

[0143] The cured product 3 having the relief structure 6 is, in other words, a patterned structured cured resin product 1. The patterned structured cured resin product 1 is released from the molding die 10 as needed, as shown in Figure 2H.

[0144] The shape and size of the patterned cured resin material 1 are appropriately set depending on the purpose and application. Examples of the shape of the patterned cured resin material 1 include a film, a sheet, and a plate. The thickness (average thickness (hereinafter the same)) of the patterned cured resin material 1 is, for example, 10 to 1000 μm, preferably 50 to 500 μm, and more preferably 100 μm to 200 μm.

[0145] 2. Action and Effects According to the above-described method for producing the patterned cured resin material 1, the relief structure 6 can be formed by a novel method.

[0146] More specifically, in the above-mentioned method for producing a pattern-structured cured resin product 1, the curable composition 2 contains a curable component and an active energy ray polymerization initiator.

[0147] In the method for producing the patterned cured resin material 1, the first curing step involves irradiating the curable composition 2 with active energy rays E through a photomask 14. That is, gas G is generated in a portion of the curable composition 2 due to the active energy ray polymerization initiator. In addition, depressions 20 are formed as spaces due to the gas G in the remaining portions of the curable composition 2 that are not irradiated with the active energy rays E. Furthermore, in the portions irradiated with the active energy rays E, the curable component is cured to form protrusions 4 as first cured portions that do not have the spaces.

[0148] Thereafter, in the second curing step, the photomask 14 is removed, and the remaining portion is irradiated with active energy rays and / or heated to cure the curable component, thereby forming the recesses 5 as the second cured portion having the spaces. As a result, a relief structure 6 is formed as a pattern structure in the cured product of the curable component.

[0149] Therefore, according to the above-described method for producing a patterned-structured cured resin material 1, a novel unevenness structure 6 can be formed in a cured product of a curable component. In other words, according to the above-described method, a patterned-structured cured resin material 1 having an unevenness structure 6 can be produced in a novel manner. Furthermore, when a known liquid substance (such as 1-hexene) is used to produce a patterned-structured cured resin material 1 having an unevenness structure 6, the liquid substance is volatilized and then the patterned-structured cured resin material 1 is washed. In contrast, the above-described method does not use a liquid substance but uses gas G, so that washing of the patterned-structured cured resin material 1 can be omitted.

[0150] Therefore, the above-mentioned method for producing the patterned cured resin product 1 and the above-mentioned patterned cured resin product 1 are suitable for use in, for example, the fields of optics, water repellency, heat dissipation, and impact absorbing cushions.

[0151] 3. Variations (1) Active energy ray polymerization initiator In the above description, a cleavage-type active energy ray radical polymerization initiator is specifically described as the active energy ray polymerization initiator. However, the type of the active energy ray polymerization initiator is not limited to the above.

[0152] For example, the active energy ray polymerization initiator may be a hydrogen abstraction type active energy ray radical polymerization initiator. When a hydrogen abstraction type active energy ray radical polymerization initiator is used, a gas G resulting from the hydrogen abstraction type active energy ray radical polymerization initiator is generated by irradiation with active energy.

[0153] The active energy ray polymerization initiator may be an active energy ray cationic polymerization initiator. Examples of the active energy ray cationic polymerization initiator include an antimony-type active energy ray cationic polymerization initiator, a phosphorus-type active energy ray cationic polymerization initiator, and a boron-type active energy ray cationic polymerization initiator. When an active energy ray cationic polymerization initiator is used, a gas G resulting from the active energy ray cationic polymerization initiator is generated by irradiation with active energy.

[0154] The content ratio of the active energy ray polymerization initiator is appropriately set depending on the type of the active energy ray polymerization initiator so as to generate an amount of gas G that is sufficient to form a pattern structure. Each of these will be described in detail below.

[0155] [Hydrogen abstraction type active energy ray radical polymerization initiator] Examples of hydrogen abstraction type active energy ray radical polymerization initiators include methyl phenylglyoxylate, benzophenone, 4-methylbenzophenone, methyl 2-benzoylbenzoate, bis(benzophenone-2-carboxylic acid) polyethylene glycol ester, 4-benzoyl 4'-methyldiphenyl sulfide, 4,4'bis(diethylamino)benzophenone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, 4-phenylbenzophenone, and methyl o-benzoylbenzoate. These can be used alone or in combination of two or more.

[0156] Hydrogen abstraction type active energy ray radical polymerization initiators are commercially available. Examples of commercially available hydrogen abstraction type active energy ray radical polymerization initiators include Kohshylex-I 3002 (trade name, manufactured by KJ Chemicals), Omnirad MBF, Omnirad BP Flakes, Omnirad 4MBZ Flakes, Omnirad OMBB, Omnipol 2702, Omnirad BMS, Omnirad EMK, Omnirad DETX, Omnirad ITX, ESACURE 1001M, Omnirad 4PBZ, and Omnirad OMBB (all trade names, manufactured by IGM resins B.V.). These can be used alone or in combination of two or more types.

[0157] When the curable composition contains a hydrogen abstraction type active energy ray radical polymerization initiator, the content of the active energy ray polymerization initiator is, for example, 0.5% by mass or more, preferably 1% by mass or more, and more preferably 2% by mass or more, relative to the total amount of the curable composition, from the viewpoint of obtaining a pattern structure (relief structure) having a relatively high aspect ratio. When the curable composition contains a hydrogen abstraction type active energy ray radical polymerization initiator, the content of the active energy ray polymerization initiator is, for example, 20% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less, relative to the total amount of the curable composition, from the viewpoint of obtaining a pattern structure (relief structure) having a relatively high aspect ratio. That is, when the curable composition contains a hydrogen abstraction type active energy ray radical polymerization initiator, the content of the active energy ray polymerization initiator is, for example, 0.5 to 20% by mass, preferably 1 to 15% by mass, and more preferably 2 to 10% by mass, relative to the total amount of the curable composition, from the viewpoint of obtaining a pattern structure (relief structure) having a relatively high aspect ratio.

[0158] When the curable composition contains a hydrogen abstraction type active energy ray radical polymerization initiator, from the viewpoint of obtaining a pattern structure (relief structure) having a relatively high aspect ratio, the lower limit of the content of the active energy ray polymerization initiator is, for example, 1 part by mass or more, preferably 2 parts by mass or more, and more preferably 3 parts by mass or more, per 100 parts by mass of the curable component. When the curable composition contains a hydrogen abstraction type active energy ray radical polymerization initiator, from the viewpoint of obtaining a pattern structure (relief structure) having a relatively high aspect ratio, the upper limit of the content of the active energy ray polymerization initiator is, for example, 20 parts by mass or less, preferably 10 parts by mass or less, and more preferably 8 parts by mass or less, per 100 parts by mass of the curable component. That is, when the curable composition contains a hydrogen abstraction type active energy ray radical polymerization initiator, from the viewpoint of obtaining a pattern structure (relief structure) having a relatively high aspect ratio, the content of the active energy ray polymerization initiator is, for example, 3 to 20 parts by mass, preferably 4 to 10 parts by mass, and more preferably 5 to 8 parts by mass, relative to 100 parts by mass of the curable component.

[0159] Furthermore, when the curable composition is a hydrogen abstraction type active energy ray radical polymerization initiator, from the viewpoint of obtaining a pattern structure having a relatively high aspect ratio, the lower limit of the content of the active energy ray polymerization initiator is, for example, 1 part by mass or more, preferably 2 parts by mass or more, more preferably 3 parts by mass or more, per 100 parts by mass of the curable resin. When the curable composition is a hydrogen abstraction type active energy ray radical polymerization initiator, from the viewpoint of obtaining a pattern structure having a relatively high aspect ratio, the upper limit of the content of the active energy ray polymerization initiator is, for example, 40 parts by mass or less, preferably 20 parts by mass or less, more preferably 8 parts by mass or less, per 100 parts by mass of the curable resin. That is, when the curable composition is a hydrogen abstraction type active energy ray radical polymerization initiator, from the viewpoint of obtaining a pattern structure having a relatively high aspect ratio, the content of the active energy ray polymerization initiator is, for example, 1 to 40 parts by mass, preferably 2 to 20 parts by mass, more preferably 3 to 8 parts by mass, per 100 parts by mass of the curable resin.

[0160] [Antimony-type active energy ray cationic polymerization initiator] Examples of antimony-type active energy ray cationic polymerization initiators include diphenyl[4-(phenylthio)phenyl]sulfonium hexafluoroantimony. These can be used alone or in combination of two or more.

[0161] Antimony-type active energy ray cationic polymerization initiators are available as commercially available products, such as CPI-110A (trade name, manufactured by San-Apro).

[0162] When the curable composition contains an antimony-type active energy ray cationic polymerization initiator, the content of the active energy ray polymerization initiator relative to the total amount of the curable composition is, for example, 0.5% by mass or more, preferably 1% by mass or more, and more preferably 2% by mass or more, from the viewpoint of obtaining a pattern structure (convexo-concave structure) having a relatively high aspect ratio. When the curable composition contains an antimony-type active energy ray cationic polymerization initiator, the content of the active energy ray polymerization initiator relative to the total amount of the curable composition is, for example, 20% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less, from the viewpoint of obtaining a pattern structure (convexo-concave structure) having a relatively high aspect ratio. That is, when the curable composition contains an antimony-type active energy ray cationic polymerization initiator, the content of the active energy ray polymerization initiator relative to the total amount of the curable composition is, for example, 0.5 to 20% by mass, preferably 1 to 15% by mass, and more preferably 2 to 10% by mass, from the viewpoint of obtaining a pattern structure (convexo-concave structure) having a relatively high aspect ratio.

[0163] When the curable composition contains an antimony-type active energy ray cationic polymerization initiator, from the viewpoint of obtaining a pattern structure (uneven structure) having a relatively high aspect ratio, the lower limit of the content of the active energy ray polymerization initiator is, for example, 0.1 parts by mass or more, preferably 1 part by mass or more, and more preferably 3 parts by mass or more, per 100 parts by mass of the curable component. When the curable composition contains an antimony-type active energy ray cationic polymerization initiator, from the viewpoint of obtaining a pattern structure (uneven structure) having a relatively high aspect ratio, the upper limit of the content of the active energy ray polymerization initiator is, for example, 20 parts by mass or less, preferably 10 parts by mass or less, and more preferably 8 parts by mass or less, per 100 parts by mass of the curable component. That is, when the curable composition contains an antimony-type active energy ray cationic polymerization initiator, from the viewpoint of obtaining a pattern structure (relief structure) having a relatively high aspect ratio, the content of the active energy ray polymerization initiator is, for example, 0.1 to 20 parts by mass, preferably 1 to 10 parts by mass, and more preferably 3 to 8 parts by mass, relative to 100 parts by mass of the curable component.

[0164] Furthermore, when the curable composition contains an antimony-type active energy ray cationic polymerization initiator, from the viewpoint of obtaining a pattern structure having a relatively high aspect ratio, the lower limit of the content of the active energy ray polymerization initiator is, for example, 0.1 parts by mass or more, preferably 2 parts by mass or more, and more preferably 5 parts by mass or more, per 100 parts by mass of the curable resin. When the curable composition contains an antimony-type active energy ray cationic polymerization initiator, from the viewpoint of obtaining a pattern structure having a relatively high aspect ratio, the upper limit of the content of the active energy ray polymerization initiator is, for example, 40 parts by mass or less, preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, per 100 parts by mass of the curable resin. That is, when the curable composition contains an antimony-type active energy ray cationic polymerization initiator, from the viewpoint of obtaining a pattern structure having a relatively high aspect ratio, the content of the active energy ray polymerization initiator is, for example, 0.1 to 40 parts by mass, preferably 2 to 20 parts by mass, and more preferably 5 to 10 parts by mass, per 100 parts by mass of the curable resin.

[0165] [Phosphorus-based active energy ray cationic polymerization initiator] Examples of phosphorus-type active energy ray cationic polymerization initiators include diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, diphenyl[4-(phenylsulfanyl)phenyl]sulfonium trifluoride tris(pentafluoroethane-1-ide)phosphate, (4-acetoxyphenyl)benzyl(methyl)sulfonium hexafluorophosphate, 1-naphthylmethylmethyl p-hydroxyphenylsulfonium hexafluorophosphate, and benzyl(4-hydroxyphenyl)(methyl)sulfonium hexafluorophosphate. These can be used alone or in combination of two or more.

[0166] The phosphorus-type active energy ray cationic polymerization initiator is available as a commercially available product, such as CPI-110P, CPI-210S, San-Aid SI-300, San-Aid SI-360, and San-Aid SI-110 (all trade names, manufactured by San-Apro).

[0167] When the curable composition contains a phosphorus-type active energy ray cationic polymerization initiator, from the viewpoint of obtaining a pattern structure (relief structure) having a relatively high aspect ratio, the content of the active energy ray polymerization initiator is, for example, 0.5% by mass or more, preferably 1% by mass or more, and more preferably 2% by mass or more, based on the total amount of the curable composition. When the curable composition contains a phosphorus-type active energy ray cationic polymerization initiator, from the viewpoint of obtaining a pattern structure (relief structure) having a relatively high aspect ratio, the content of the active energy ray polymerization initiator is, for example, 20% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less, based on the total amount of the curable composition. That is, when the curable composition contains a phosphorus-type active energy ray cationic polymerization initiator, from the viewpoint of obtaining a pattern structure (relief structure) having a relatively high aspect ratio, the content of the active energy ray polymerization initiator is, for example, 0.5 to 20% by mass, preferably 1 to 15% by mass, and more preferably 2 to 10% by mass, based on the total amount of the curable composition.

[0168] When the curable composition contains a phosphorus-type active energy ray cationic polymerization initiator, from the viewpoint of obtaining a pattern structure (uneven structure) having a relatively high aspect ratio, the lower limit of the content of the active energy ray polymerization initiator is, for example, 0.1 parts by mass or more, preferably 1 part by mass or more, and more preferably 3 parts by mass or more, per 100 parts by mass of the curable component. When the curable composition contains a phosphorus-type active energy ray cationic polymerization initiator, from the viewpoint of obtaining a pattern structure (uneven structure) having a relatively high aspect ratio, the upper limit of the content of the active energy ray polymerization initiator is, for example, 20 parts by mass or less, preferably 10 parts by mass or less, and more preferably 8 parts by mass or less, per 100 parts by mass of the curable component. That is, when the curable composition contains a phosphorus-type active energy ray cationic polymerization initiator, from the viewpoint of obtaining a pattern structure (relief structure) having a relatively high aspect ratio, the content of the active energy ray polymerization initiator is, for example, 0.1 to 20 parts by mass, preferably 1 to 10 parts by mass, and more preferably 3 to 8 parts by mass, relative to 100 parts by mass of the curable component.

[0169] Furthermore, when the curable composition contains a phosphorus-type active energy ray cationic polymerization initiator, from the viewpoint of obtaining a pattern structure having a relatively high aspect ratio, the lower limit of the content of the active energy ray polymerization initiator is, for example, 0.1 parts by mass or more, preferably 2 parts by mass or more, and more preferably 5 parts by mass or more, per 100 parts by mass of the curable resin. When the curable composition contains a phosphorus-type active energy ray cationic polymerization initiator, from the viewpoint of obtaining a pattern structure having a relatively high aspect ratio, the upper limit of the content of the active energy ray polymerization initiator is, for example, 40 parts by mass or less, preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, per 100 parts by mass of the curable resin. That is, when the curable composition contains a phosphorus-type active energy ray cationic polymerization initiator, from the viewpoint of obtaining a pattern structure having a relatively high aspect ratio, the content of the active energy ray polymerization initiator is, for example, 0.1 to 40 parts by mass, preferably 2 to 20 parts by mass, and more preferably 5 to 10 parts by mass, per 100 parts by mass of the curable resin.

[0170] [Boron-type active energy ray cationic polymerization initiator] Examples of boron-type active energy ray cationic polymerization initiators include diphenyl[4-(phenylthio)phenyl]sulfonium tetrakis(pentafluorophenyl)borate, (4-acetoxyphenyl)methyl(2-methylbenzyl)sulfonium tetrakis(pentafluorophenyl)borate, benzyl(4-hydroxyphenyl)(methyl)sulfonium tetrakis(pentafluorophenyl)borate, and (4-hydroxyphenyl)(dimethyl)sulfonium tetrakis(pentafluorophenyl)borate. These can be used alone or in combination of two or more.

[0171] The boron-type active energy ray cationic polymerization initiator is available as a commercially available product. Examples of commercially available boron-type active energy ray cationic polymerization initiators include CPI-110B (trade name, manufactured by San-Apro), San-Aid SI-B2A, San-Aid SI-B3, and San-Aid SI-B4 (all trade names, manufactured by Sanshin Chemical Industry Co., Ltd.).

[0172] When the curable composition contains a boron-type active energy ray cationic polymerization initiator, the content of the active energy ray polymerization initiator is, for example, 0.5% by mass or more, preferably 1% by mass or more, and more preferably 2% by mass or more, relative to the total amount of the curable composition, from the viewpoint of obtaining a pattern structure (convexo-concave structure) having a relatively high aspect ratio. When the curable composition contains a boron-type active energy ray cationic polymerization initiator, the content of the active energy ray polymerization initiator is, for example, 20% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less, relative to the total amount of the curable composition, from the viewpoint of obtaining a pattern structure (convexo-concave structure) having a relatively high aspect ratio. That is, when the curable composition contains a boron-type active energy ray cationic polymerization initiator, the content of the active energy ray polymerization initiator is, for example, 0.5 to 20% by mass, preferably 1 to 15% by mass, and more preferably 2 to 10% by mass, relative to the total amount of the curable composition, from the viewpoint of obtaining a pattern structure (convexo-concave structure) having a relatively high aspect ratio.

[0173] When the curable composition contains a boron-type active energy ray cationic polymerization initiator, from the viewpoint of obtaining a pattern structure (uneven structure) having a relatively high aspect ratio, the lower limit of the content of the active energy ray polymerization initiator is, for example, 1 part by mass or more, preferably 2 parts by mass or more, and more preferably 3 parts by mass or more, per 100 parts by mass of the curable component. When the curable composition contains a boron-type active energy ray cationic polymerization initiator, from the viewpoint of obtaining a pattern structure (uneven structure) having a relatively high aspect ratio, the upper limit of the content of the active energy ray polymerization initiator is, for example, 20 parts by mass or less, preferably 10 parts by mass or less, and more preferably 8 parts by mass or less, per 100 parts by mass of the curable component. That is, when the curable composition contains a boron-type active energy ray cationic polymerization initiator, from the viewpoint of obtaining a pattern structure (relief structure) having a relatively high aspect ratio, the content of the active energy ray polymerization initiator is, for example, 3 to 20 parts by mass, preferably 4 to 10 parts by mass, and more preferably 5 to 8 parts by mass, relative to 100 parts by mass of the curable component.

[0174] Furthermore, when the curable composition contains a boron-type active energy ray cationic polymerization initiator, from the viewpoint of obtaining a pattern structure having a relatively high aspect ratio, the lower limit of the content of the active energy ray polymerization initiator is, for example, 1 part by mass or more, preferably 2 parts by mass or more, and more preferably 3 parts by mass or more, per 100 parts by mass of the curable resin. When the curable composition contains a boron-type active energy ray cationic polymerization initiator, from the viewpoint of obtaining a pattern structure having a relatively high aspect ratio, the upper limit of the content of the active energy ray polymerization initiator is, for example, 40 parts by mass or less, preferably 20 parts by mass or less, and more preferably 8 parts by mass or less, per 100 parts by mass of the curable resin. That is, when the curable composition contains a boron-type active energy ray cationic polymerization initiator, from the viewpoint of obtaining a pattern structure having a relatively high aspect ratio, the content of the active energy ray polymerization initiator is, for example, 1 to 40 parts by mass, preferably 2 to 20 parts by mass, and more preferably 3 to 8 parts by mass, per 100 parts by mass of the curable resin.

[0175] As described above, a pattern structure can be formed by a novel method using various active energy polymerization initiators. In other words, the above method allows a pattern-structured cured resin product having a pattern structure to be produced by a novel method.

[0176] (2) Covering masking process In the above description, the coating process (FIG. 1C) of coating the curable composition with an active energy ray-transparent coating material and the masking process (FIG. 1D) of placing a photomask on one side of the active energy ray-transparent coating material are carried out separately.

[0177] However, in the production of a pattern-structured cured resin material, the coating step and the masking step may be performed simultaneously. Hereinafter, the step in which the coating step and the masking step are performed simultaneously (i.e., the step of coating the curable composition with an active energy ray-transparent coating material and arranging a photomask on one side of the active energy ray-transparent coating material) will be referred to as the coating masking step.

[0178] In the coating masking step, as shown in FIG. 3, the active energy ray-transmitting coating material 13 is also used as a photomask 14 .

[0179] More specifically, in this method, the photomask 14 is also used (shared) as the active energy ray-transmittable coating material 13. That is, the photomask 14 is made of a material capable of covering at least one surface of the curable composition 2, and has a plurality of light-transmitting portions 15 and a plurality of light-shielding portions 16.

[0180] In this method, the curable composition is placed at a desired position, as shown in FIGS. 1A and 1B.

[0181] Next, in this method, as shown in FIG. 3 instead of FIG. 1C and FIG. 1D, a photomask 14 is placed on one side of the active energy ray-transmittable coating material 13, and at least one side of the curable composition 2 is coated with the photomask 14 (coating masking process).

[0182] Next, in this method, as shown in FIG. 2E, the curable composition is irradiated with active energy rays from one side of the photomask 14. Next, in this method, as shown in FIG. 2F, depressions 20 caused by the gas are formed. Next, in this method, as shown in FIG. 2G, the photomask 14 is removed. Then, the curable composition is irradiated with active energy rays without passing through the photomask 14 and the active energy ray-transparent coating material 13. Thereafter, as shown in FIG. 2H, the pattern-structured cured resin product is demolded.

[0183] As a result, a concave-convex structure 6 is formed, which has convex portions 4 and concave portions 5 in a pattern according to the photomask 14. Also, a cured product 3 having the concave-convex structure 6 is formed (see FIG. 3).

[0184] 3, a pattern structure can be formed by a novel method even when the photomask 14 is also used as the active energy ray-transparent coating material 13. In other words, the above method makes it possible to produce a pattern-structured cured resin material 1 having a pattern structure by a novel method.

[0185] (3) Internal voids In the above description, the gas G is used to form depressions 20 as spaces on the surface of the curable composition 2, and the curable composition 2 is cured to form the relief structure 6 as a pattern structure.

[0186] However, the spaces and pattern structure are not limited to those described above. For example, a plurality of internal pores 22 as spaces can be formed inside the curable composition 2 by gas G, and a porous structure 26 as a pattern structure can be formed.

[0187] More specifically, in the first curing step (FIGS. 2E to 2F), when a part of the curable composition 2 is irradiated with active energy rays E through a photomask 14, gas G resulting from the active energy ray polymerization initiator is generated. At this time, depending on the formulation of the curable resin and the polymerizable diluent, part or all of the gas G remains inside the curable composition 2 that is maintained in an uncured state, forming internal voids 22 as spaces.

[0188] That is, in the first curing step, the irradiation with the active energy rays E forms a pore-free portion 24 as a first cured portion that does not have internal pores 22.

[0189] Next, in the second curing step (FIG. 2G), the remaining portion of the curable composition 2 is irradiated with active energy rays E. That is, the active energy rays are irradiated toward the uncured curable composition 2. As a result, a porous portion 25 having internal pores 22 is formed as a second cured portion.

[0190] As a result of the above, a porous structure 26 is formed as a pattern structure having non-porous portions 24 and porous portions 25 in a pattern according to the photomask 14. Furthermore, a cured product 3 having the porous structure 26 is formed (see FIG. 4).

[0191] 4, a pattern structure can be formed by a novel method even when gas G is allowed to remain in the curable composition 2. In other words, according to the above method, a pattern-structured cured resin product 1 having a pattern structure can be produced by a novel method. [Example]

[0192] Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited to the following examples. Note that "parts" and "%" are by mass unless otherwise specified. Furthermore, specific numerical values ​​such as blending ratios (content ratios), physical property values, and parameters used in the following description can be substituted with the corresponding upper limit values ​​(numeric values ​​defined as "equal to or less than") or lower limit values ​​(numeric values ​​defined as "equal to or more than" or "exceeding") of the blending ratios (content ratios), physical property values, parameters, etc. described in the above "Description of the Invention."

[0193] 1.Curing resin Preparation Example 1 (Active Energy Ray Polymerizable Polyurethane Resin) Under a nitrogen atmosphere, polyoxyethylene glycol (trade name Actocol DL-10000, manufactured by Mitsui Chemicals) having a number average molecular weight of 10,000 and 1,3-bis(isocyanatomethyl)cyclohexane (1,3-H6XDI) were placed in a separable glass flask. The amounts placed were adjusted so that the equivalent ratio (NCO / OH) of the isocyanate groups of 1,3-bis(isocyanatomethyl)cyclohexane to the hydroxyl groups of the polyoxyethylene glycol was 8.0.

[0194] Next, the mixture of polyoxyethylene glycol and 1,3-bis(isocyanatomethyl)cyclohexane was heated to 80°C. A urethane-forming catalyst (tin(II) ethylhexanoate) was then added to the mixture. The amount of the catalyst added was adjusted so that the urethane-forming catalyst was 10 ppm relative to the mixture. The mixture was then reacted at 80°C for 4 hours. This resulted in a polyoxyethylene glycol adduct of 1,3-bis(isocyanatomethyl)cyclohexane (hereinafter referred to as alcohol-adducted isocyanate). More specifically, a crude product containing the alcohol-adducted isocyanate and unreacted 1,3-bis(isocyanatomethyl)cyclohexane was obtained. The crude product was then subjected to thin-film distillation (160-170°C, 70-100 Pa) to purify the alcohol-adducted isocyanate.

[0195] Next, the alcohol-added isocyanate and 2-hydroxyethyl acrylate (HEA) were added to the separable flask, with the amount adjusted so that the equivalent ratio (NCO / OH) of the isocyanate groups of the alcohol-added isocyanate to the hydroxyl groups of the 2-hydroxyethyl acrylate was 1.0.

[0196] Next, the mixture of alcohol-added isocyanate and 2-hydroxyethyl acrylate was heated to 70°C. Next, a urethane catalyst (tin(II) ethylhexanoate) was added to the mixture. The amount of the urethane catalyst added was adjusted so that the amount of the urethane catalyst relative to the mixture was 200 ppm. Thereafter, the mixture was reacted at 70°C for 4 hours.

[0197] As a result of the above, urethane acrylate (abbreviated as UA) was obtained as an active energy ray-polymerizable polyurethane resin.

[0198] Preparation Example 2 (Active Energy Ray Polymerizable Epoxy Resin) Tetrahydroindene diepoxide (abbreviated as THI-DE, manufactured by ENEOS) was prepared as an active energy ray-polymerizable epoxy resin.

[0199] 2. Polymerizable diluents The following polymerizable diluents were prepared: (1) IBXA: Isobornyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. (2) 4-HBA: 4-hydroxybutyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. (3) Product name: FX-AO-MA: 2-(allyloxymethyl)methyl acrylate, a compound containing both (meth)acryloyl and vinyl groups, manufactured by Nippon Shokubai

[0200] 3. Active energy ray polymerization initiator The following active energy ray polymerization initiators were prepared. [Cleavage-type active energy ray radical polymerization initiator] (1) Product name: OmniradD TPO: Photoradical polymerization initiator, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, manufactured by IGM resins B.V. (2) Product name: Omnirad 819: Photoradical polymerization initiator, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, manufactured by IGM resins B.V.

[0201] [Hydrogen abstraction type active energy ray radical polymerization initiator] (3) Product name Kohshylex-I 3002: Photoradical polymerization initiator, manufactured by KJ Chemicals (4) Product name: Omnirad MBF: Photoradical polymerization initiator, Methylbenzoylformate, manufactured by IGM resins B.V. [Antimony-type active energy ray cationic polymerization initiator] (5) Product name CPI-110A: Antimony type photoacid generator, manufactured by San-Apro [Phosphorus-based active energy ray cationic polymerization initiator] (6) Product name: CPI-110P: Phosphorus-type photoacid generator, manufactured by San-Apro

[0202] 4. Additives The following additives were prepared: (1) Benzoflex 9-98: Plasticizer, dipropylene glycol dibenzoate, manufactured by CBC (2) 1-Hexene: Olefin, manufactured by Tokyo Chemical Industry Co., Ltd. (3) Trade name Irganox 245: antioxidant, Ethylene bis(oxyethylene) bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate), manufactured by BASF

[0203] 5. Patterned structured cured resin Examples 1 to 11 and Comparative Examples 1 to 3 1) Preparation process According to the formulations shown in Tables 1 to 4, active energy ray-curable compositions were prepared.

[0204] More specifically, the curable component, the active energy ray polymerization initiator, and additives to be blended as necessary were placed in a brown bottle, and these were heated to 50°C and mixed to obtain an active energy ray curable composition as a mixture.

[0205] 2) Placement process Next, a rectangular spacer was placed on a polyester film (manufactured by Toyobo Co., Ltd., trade name Purex A3100) as a substrate to obtain a molding die (see FIG. 1A). Next, an active energy ray-curable composition was poured into the frame of the spacer to obtain an uncured film of the active energy ray-curable composition (see FIG. 1B).

[0206] The height of the spacers was adjusted so as to obtain an uncured film having the average film thickness shown in Tables 1 to 4. In Comparative Examples 2 to 4, the height of the spacers was set higher than the film thickness to prevent contact between the active energy ray-transparent coating material and / or photomask described below and the uncured film of the active energy ray-curable composition.

[0207] 3) Coating process Next, a polyester film (manufactured by Toyobo Co., Ltd., product name Purex A3100) was placed as an active energy ray-transmitting coating material on the uncured film of the active energy ray-curable composition (see FIG. 1C ). At this time, the uncured film of the active energy ray-curable composition and the polyester film were in close contact with each other.

[0208] In Example 10 and Comparative Examples 2 and 3, no active energy ray-transmitting covering material was placed.

[0209] In Comparative Example 4, the active energy ray-transmittable coating material was placed on the spacer, and a gap was formed between the uncured film of the active energy ray-curable composition and the photomask.

[0210] 4) Masking process Next, a photomask (manufactured by Nippon Filcon Co., Ltd.) was placed on the polyester film serving as the active energy ray-transmitting covering material (see FIG. 1D). The photomask had a line and space pattern. The line and space pattern had the line width / space width (L / S) shown in Tables 1 to 4.

[0211] In Comparative Example 1, no photomask was placed.

[0212] In Example 10, no active energy ray-transparent coating material was placed in the coating step, and the uncured film of the active energy ray-curable composition was covered with the photomask in the masking step, while the uncured film of the active energy ray-curable composition was not attached to the photomask (coating masking step).

[0213] In Comparative Examples 2 and 3, no active energy ray-transmittable coating material was placed in the coating step, and the photomask was placed on the spacer in the masking step, leaving a gap between the uncured film of the active energy ray-curable composition and the photomask.

[0214] Thereafter, the mold, the active energy ray-curable composition, the polyester film as the active energy ray-transmitting covering material (except for Example 10 and Comparative Examples 2 to 3), and the photomask were fixed using clips.

[0215] That is, the curable composition was sealed in a mold.

[0216] However, as described above, in Comparative Examples 2 and 3, no active energy ray-transparent coating material was used, and a gap was formed between the active energy ray-curable composition and the photomask, and the active energy ray-curable composition was not sealed in the mold.

[0217] In addition, in Comparative Example 4, an active energy ray-transparent coating material was used, but a gap was formed between the active energy ray-curable composition and the active energy ray-transparent coating material, and the active energy ray-curable composition was not sealed in the mold.

[0218] 5) First curing process Next, using a UV curing device (a tabletop batch-type UV curing device manufactured by ITEC Systems Co., Ltd.), the active energy ray curable composition was irradiated with active energy rays having peak wavelengths listed in Tables 1 to 4 from above the polyester film and the photomask (see FIG. 2E).

[0219] Tables 1 to 4 show the illuminance of the active energy rays (measured with an illuminance meter Ushio Inc. UIT-250 (measurement wavelength 365 nm or 405 nm)).

[0220] Then, by irradiating the active energy rays, the active energy ray-curable composition was cured in a part of the active energy ray-curable composition, thereby forming convex portions (see FIG. 2F).

[0221] 6)Second curing process Next, the photomask was removed, and the active energy ray-curable composition was irradiated with active energy rays having a peak wavelength shown in Tables 1 to 4 from above the polyester film (see FIG. 2G).

[0222] Tables 1 to 4 show the illuminance of the active energy rays (measured with an illuminance meter Ushio Inc. UIT-250 (measurement wavelength 365 nm or 405 nm)).

[0223] Then, the remaining portion of the active energy ray-curable composition was cured by irradiation with the active energy ray, thereby forming recesses. In this way, a cured resin product having a concavo-convex structure was produced as a cured resin product having a pattern structure.

[0224] Thereafter, the cured resin having the textured structure was released from the mold (see FIG. 2H).

[0225] 6. Evaluation Aspect Ratio The cured resin with the concave-convex structure was cut with a sample cutter, and the cross section was observed. A digital microscope (Keyence Corporation, VHX-6000) was used for the observation. The depth (μm) and width (μm) of the concave-convex structure in the cross section were measured, and the aspect ratio of the concave-convex structure was calculated according to the following formula.

[0226] Aspect ratio = (depth of uneven structure (μm)) / (width of uneven structure (μm))

[0227] The evaluation criteria for the aspect ratio are as follows: ◎: The aspect ratio was 20 or more. ◯: The aspect ratio was 10 or more and less than 20. △: The aspect ratio was 5 or more and less than 10. ×: The aspect ratio was less than 5.

[0228] [Table 1]

[0229] [Table 2]

[0230] [Table 3]

[0231] [Table 4] [Explanation of symbols]

[0232] 1. Patterned structured cured resin 2 Curable composition 3 Cured product 4 Convex part 5 recess 6 Uneven structure 10 mold 11 Base material 12 spacer 13 Active energy ray-transmitting coating material 14 Photomask 15 Translucent part 16 Light blocking section 20 depression 22 Internal voids 24 Non-perforated section 25 Perforated part 26 Porous structure

Claims

1. a preparation step of preparing a curable composition that can be cured by irradiation with at least active energy rays; a disposing step of disposing the curable composition; a coating step of coating at least one surface of the curable composition with an active energy ray-transmitting coating material; a masking step of placing a photomask on the one surface of the active energy ray-transparent covering material; a first curing step of irradiating a part of the curable composition with active energy rays through the photomask; a second curing step of irradiating the remaining portion of the curable composition with active energy rays and / or heating the remaining portion after the first curing step; Equipped with The curable composition comprises The composition contains at least a curable component that can be cured by irradiation with active energy rays and an active energy ray polymerization initiator, In the first curing step, generating a gas resulting from the active energy ray polymerization initiator in the portion irradiated with the active energy ray; A space caused by the gas is formed in the remaining portion relative to the portion irradiated with the active energy rays, In the portion irradiated with the active energy rays, the curable component is cured to form a first cured portion having no space; In the second curing step, removing the photomask; the remaining portion is irradiated with active energy rays and / or the remaining portion is heated to cure the curable component and form a second cured portion having the space, thereby forming a pattern structure including the first cured portion and the second cured portion in the cured product of the curable component. A method for producing a patterned structured cured resin product.

2. the pattern structure is a relief structure, 2. The method for producing a patterned cured resin product according to claim 1, wherein the concave-convex structure has an aspect ratio (depth / width) of 5 or more.

3. the photomask has a plurality of light-transmitting portions and light-shielding portions; the light-transmitting portion and the light-shielding portion have a line-and-space pattern, the line width in the line and space pattern is less than 100 μm, The method for producing a patterned cured resin product according to claim 1 , wherein the line and space pattern has a space width of less than 100 μm.

4. the active energy ray polymerization initiator is a cleavage-type active energy ray radical polymerization initiator, The content ratio of the active energy ray polymerization initiator is The method for producing a pattern-structured cured resin product according to claim 1 , wherein the amount of the curing agent is 1 part by mass or more and 10 parts by mass or less per 100 parts by mass of the curable component.

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