Photosensitive resin composition for imprint, hardened product, and optical element

Abstract

The present invention provides a photoreactive resin composition for imprinting, a hardened product, and an optical element, which have high transmittance, low thermal expansion coefficient, low water absorption, high hardness, and high Young's modulus. The photoreactive resin composition for imprinting includes resin (A) having a weight average molecular weight of 1,000 to 50,000 and two or more ethylenic polymerizable groups, ethylenic unsaturated monomer (B), photoinitiator (C), solvent (D), and hydrophobic oligomer (E).

Description

TECHNICAL FIELD

[0001] The present application relates to a photosensitive resin composition, a hardened product, and an optical element, and particularly relates to a photosensitive resin composition for imprint, a hardened product, and an optical element. BACKGROUND

[0002] Imprint technology includes imprinting a mold insert (also referred to as "mold", "stamper", or "template") having a pattern formed on a surface onto a resin, and accurately transferring the pattern to the resin via deformation of the resin.

[0003] Currently, there are various imprint technologies such as hot embossing lithography (HEL), step and flash imprint lithography, and soft lithography. In hot embossing lithography, a mold is pressed against a resin that has been heated to a temperature higher than the glass transition temperature, and then the resin is cooled and thereafter peeled from the mold, thereby transferring the structure of the mold to the resin on the substrate. In step and flash imprint lithography, a photocurable composition is cured by ultraviolet light irradiation through a transparent mold or a transparent substrate at room temperature. In soft lithography, a flexible imprinting mold made of a soft polymer material is used, and after a monomer having self-assembly properties (SAM) is coated on the mold, the mold is pressed against a thin film substrate, and the monomer having self-assembly properties on the protruding portion of the mold is printed on the thin film substrate like ink.

[0004] However, the coefficient of thermal expansion, water absorption, and hardness of the photocurable composition (photosensitive resin composition) used in imprint technology have not been discussed much. SUMMARY

[0005] Therefore, the present application provides a photosensitive resin composition for imprint having a high transmittance, a low coefficient of thermal expansion, a low water absorption, a high hardness, and a high Young's modulus, a hardened product formed therefrom, and an optical element comprising the hardened product.

[0006] High transmittance means that the hardened product has high transparency, and thus is suitable for optical elements. Low thermal expansion coefficient means that the amount of thermal expansion deformation of the optical element under a high temperature environment can be reduced. High hardness means that the optical element can be less damaged or deformed by external force. High Young's modulus means that the optical element is less likely to be deformed. Low water absorption means that the optical element is less likely to be affected by water, which can affect the transmittance, refractive index, and physical properties of the optical element.

[0007] The present application provides a photosensitive resin composition for imprint, comprising a resin (A), an ethylenically unsaturated monomer (B), a photoinitiator (C), a solvent (D), and a hydrophobic oligomer (E), wherein the resin (A) has a weight average molecular weight of 1,000 to 50,000 and has two or more ethylenically polymerizable groups.

[0008] According to an embodiment of the present application, the above-mentioned hydrophobic oligomer (E) comprises a fluorine-based acrylic-based oligomer (E-1).

[0009] According to an embodiment of the present application, the above-mentioned hydrophobic oligomer (E) comprises a siloxane-based acrylic-based oligomer (E-2).

[0010] According to an embodiment of the present application, the above-mentioned resin (A) comprises a resin (A-1) having a fluorene ring and two or more ethylenically polymerizable groups, a polyurethane acrylate (A-2), or a combination thereof.

[0011] According to an embodiment of the present application, the above-mentioned ethylenically unsaturated monomer (B) comprises a compound represented by the following formula (I-1), a compound represented by the following formula (I-2), or a combination thereof.

[0012] Formula (I-1)

[0013] In formula (I-1), X 1 ~X 6 respectively represent a hydrogen atom, an acryloyl group, or a methacryloyl group, wherein at least two of X 1 ~X 6 are acryloyl groups or methacryloyl groups,

[0014] Formula (I-2)

[0015] In formula (I-2), X 7 ~X 16 respectively represent a hydrogen atom, an acryloyl group, or a methacryloyl group, wherein at least two of X 7 ~X 16 are acryloyl groups or methacryloyl groups.

[0016] According to an embodiment of the present application, the photoinitiator (C) described above includes an acylphosphine oxide compound (C-1).

[0017] According to an embodiment of the present application, the acylphosphine oxide compound (C-1) is 50 to 100% by weight, based on 100% by weight of the photoinitiator (C).

[0018] According to an embodiment of the present application, the solvent (D) described above includes propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, cyclopentanone, cyclohexanone, or a combination thereof.

[0019] According to an embodiment of the present application, the photoresist composition for imprint described above further includes a surfactant (F), wherein the surfactant (F) includes a fluorine-based surfactant (F-1), a siloxane-based surfactant (F-2), a non-ionic surfactant (F-3), or a combination thereof.

[0020] The present application provides a hardened product, which is hardened from the photoresist composition for imprint described above.

[0021] According to an embodiment of the present application, the thickness of the hardened product described above is 1 to 5 μm.

[0022] According to an embodiment of the present application, the transmittance of the hardened product described above at a wavelength of 365 nm is greater than 94%, at a wavelength of 400 nm is greater than 98%, and at a wavelength of 500 to 1100 nm is greater than 99%.

[0023] According to an embodiment of the present application, the Young's modulus of the hardened product described above is greater than 1 Gpa.

[0024] According to an embodiment of the present application, the water absorption of the hardened product described above is less than 0.5%.

[0025] According to an embodiment of the present application, the Shore D hardness of the hardened product described above is greater than 70.

[0026] According to an embodiment of the present application, the coefficient of thermal expansion of the hardened product described above is less than 100 ppm / °C.

[0027] According to an embodiment of the present application, the refractive index of the hardened product described above is greater than 1.5.

[0028] The present application provides an optical element, which includes the hardened product described above.

[0029] Based on the above, the photosensitive resin composition for imprint of the present application includes resin (A), ethylenically unsaturated monomer (B), photoinitiator (C), solvent (D), and hydrophobic oligomer (E), and the hardened product thereof has high transmittance, low thermal expansion coefficient, low water absorption, high hardness, and high Young's modulus, and is thus suitable for optical elements. DETAILED DESCRIPTION

[0030] <Photosensitive resin composition>

[0031] The present embodiment provides a photosensitive resin composition for imprint, including resin (A), ethylenically unsaturated monomer (B), photoinitiator (C), solvent (D), and hydrophobic oligomer (E). In addition, if necessary, the photosensitive resin composition can further include other additives (G), surfactant (F), or a combination thereof. Each component of the photosensitive resin composition for imprint (hereinafter, also simply referred to as "photosensitive resin composition") will be described in detail below.

[0032] In the present specification, "(meth)acrylic acid" indicates "acrylic acid" and / or "methacrylic acid"; "(meth)acrylate" indicates "acrylate" and / or "methacrylate"; "(meth)acryloyl" indicates "acryloyl" and / or "methacryloyl"; and "(meth)acrylamide" indicates "acrylamide" and / or "methacrylamide".

[0033] In the present specification, "hardened product" refers to a hardened film or a block material formed after the photosensitive resin composition is hardened.

[0034] Resin (A)

[0035] The weight average molecular weight of resin (A) is 1,000 to 50,000, and it has two or more ethylenically polymerizable groups.

[0036] Resin (A) includes resin (A-1) having a fluorene ring and two or more ethylenically polymerizable groups (hereinafter, simply referred to as "resin (A-1)"), polyamine ester acrylate (A-2), or a combination thereof.

[0037] Resin (A-1)

[0038] Resin (A-1) includes a structural unit having a fluorene ring and two or more ethylenically polymerizable groups. The weight average molecular weight of resin (A-1) can be 1,000 to 50,000, preferably 2,000 to 20,000, more preferably 3,000 to 7,000, and still more preferably 4,500 to 5,000.

[0039] Specifically, the structural unit having a fluorene ring and two or more ethylenically polymerizable groups is preferably a structural unit represented by the following formula (1):

[0040] Formula (1)

[0041] In Formula (1), * indicates a bonding position.

[0042] Further, the structural unit shown in Formula (1) is derived from a monomer shown in Formula (1-1) below.

[0043] Formula (1-1)

[0044] The resin (A-1) is a cardo resin formed by polymerizing a monomer having a fluorene ring and two or more vinyl polymerizable groups, a tetracarboxylic dianhydride, and a dicarboxylic acid, and the monomer having a fluorene ring and two or more vinyl polymerizable groups is preferably the monomer shown in Formula (1-1) above. The tetracarboxylic dianhydride and the dicarboxylic acid are not particularly limited, and an appropriate tetracarboxylic dianhydride and dicarboxylic acid can be selected as needed.

[0045] Further, the method for synthesizing the resin (A-1) is not particularly limited, and the monomer having a fluorene ring and two or more vinyl polymerizable groups, the tetracarboxylic dianhydride, and the dicarboxylic acid can be polymerized into a structural unit having a fluorene ring and two or more vinyl polymerizable groups using an existing organic synthesis method.

[0046] Specific examples of the resin (A-1) include cardo resins (trade name: KBR series, manufactured by KISCO Ltd.).

[0047] Based on 100 parts by weight of the resin (A), the resin (A-1) is 0 to 100 parts by weight.

[0048] When the photosensitive resin composition includes the resin (A-1), the hardened product formed from the photosensitive resin composition can have preferable adhesion.

[0049] Polyurethane acrylate (A-2)

[0050] The polyurethane acrylate is not particularly limited, and can be (1) a reaction product of a hydroxyl-containing methacrylate and an isocyanate compound; (2) a reaction product of a hydroxyl-containing methacrylate and a polyurethane prepolymer having an isocyanate group at the tail; or a mixture of the above (1) and (2).

[0051] (1) In the reaction product of the hydroxyl-containing methacrylate and the isocyanate compound, specific examples of the hydroxyl-containing methacrylate are not particularly limited and can include a hydroxyalkyl methacrylate. Specific examples of the hydroxyalkyl methacrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, or 8-hydroxyoctyl (meth) acrylate, or a combination thereof.

[0052] (1) In the reaction product of the hydroxyl-containing methacrylate and the isocyanate compound, the isocyanate compound is a compound including at least two isocyanate groups. The isocyanate compound is not particularly limited and can include an aliphatic polyisocyanate, a cycloaliphatic polyisocyanate, an aromatic polyisocyanate, or a combination thereof. Specific examples of the isocyanate compound can include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylenediisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate, and isophorone diisocyanate, or a combination thereof.

[0053] (2) The reactant of the hydroxyl-containing methacrylate and the isocyanate-tailed polyamine ester prepolymer, for example, includes a reactant of a polyisocyanate and a polyol ester.

[0054] The hydroxyl-containing methacrylate and the polyisocyanate are as described above for the hydroxyl-containing methacrylate and the isocyanate compound in the reaction product of the hydroxyl-containing methacrylate and the isocyanate compound, and are not repeated here.

[0055] The polyol ester can include a polyol, a polyol ether, or a reactant of the acid composition that is esterified. Specific examples of the polyol can include ethylene glycol, propylene glycol, cyclohexane dimethanol, 3-methyl-1,5-pentanediol, or a combination thereof.

[0056] Specific examples of the polyol ester can include a polyalkylene glycol such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, a block polymer or a random polymer such as a polyethylenepolypropoxy block polymer diol, or a combination thereof.

[0057] The acid composition is not particularly limited and can include a dibasic acid or an anhydride such as adipic acid, succinic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and terephthalic acid.

[0058] Specific examples of the polyamine ester acrylate (A-2) include a polyamine ester acrylate "Art Cure" RA series (weight average molecular weight 40,000, glass transition point 190°C, acid value 90 mgKOH / g; manufactured by Shin-Etsu Chemical Co., Ltd.).

[0059] The polyamine ester acrylate (A-2) is 0 to 100 parts by weight based on 100 parts by weight of the resin (A).

[0060] When the photosensitive resin composition includes the polyamine ester acrylate (A-2), the photosensitive resin composition can have preferable adhesion.

[0061] Furthermore, the present embodiment is not limited thereto, and the resin (A) can also include other resins other than the resin (A-1) and the polyamine ester acrylate (A-2) without affecting the efficacy of the present embodiment.

[0062] Ethyleneically unsaturated monomer (B)

[0063] The ethyleneically unsaturated monomer (B) in the photosensitive resin composition can promote the cross-linking reaction of the polymer in the photosensitive resin composition.

[0064] The ethylenically unsaturated monomer (B) includes a compound represented by the following formula (I-1), a compound represented by the following formula (I-2), or a combination thereof. In addition, the ethylenically unsaturated monomer (B) can further include an acryl monomer having a cyclic structure.

[0065] Formula (I-1)

[0066] In formula (I-1), X 1 ~X 6 respectively represent a hydrogen atom, an acryl group, or a methacryl group, wherein at least two of X 1 ~X 6 are an acryl group or a methacryl group.

[0067] In formula (I-1), X 1 ~X 6 is preferably five or more, and more preferably six or more.

[0068] When the number of acryl groups or methacryl groups contained in formula (I-1) is two or more, the hardness and Young's modulus of the hardened material formed from the photosensitive resin composition can be further increased, and the thermal expansion coefficient of the hardened material formed from the photosensitive resin composition can be decreased. In addition, when the number of acryl groups or methacryl groups contained in formula (I-1) is five or more, or even six or more, the hardness and Young's modulus of the hardened material formed from the photosensitive resin composition are more preferably increased, and the thermal expansion coefficient is more preferably decreased. When the thermal expansion coefficient of the hardened material formed from the photosensitive resin composition is low, the hardened film as an optical element is less likely to be deformed due to the ambient temperature, and the effect of the optical element is less likely to change due to the ambient temperature.

[0069] Specific examples of the compound represented by formula (I-1) are preferably dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate (DPHA), dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, or a combination thereof; and more preferably dipentaerythritol hexaacrylate.

[0070] Formula (I-2)

[0071] In formula (I-2), X 7 ~X 16 respectively represent a hydrogen atom, an acryl group, or a methacryl group, wherein at least two of X 7 ~X 16 are an acryl group or a methacryl group.

[0072] In formula (I-2), X 7 ~X 16 More preferably, five or more acryl groups or methacryl groups are present, and even more preferably, six or more acryl groups or methacryl groups are present.

[0073] When the number of acryl groups or methacryl groups contained in formula (I-2) is two or more, the hardness and Young's modulus of the hardened product formed from the photosensitive resin composition can be further increased, and the thermal expansion coefficient of the hardened product formed from the photosensitive resin composition can be further decreased. Furthermore, when the number of acryl groups or methacryl groups contained in formula (I-2) is five or more, or even six or more, the hardness and Young's modulus of the hardened product formed from the photosensitive resin composition are even more preferable, and the thermal expansion coefficient is even lower.

[0074] A specific example of the compound represented by formula (I-2) is preferably a multifunctional polyamine ester acrylate (trade name: DPHA-40H, manufactured by Nippon Kayaku Co., LTD.).

[0075] In one embodiment, the ethylenically unsaturated monomer (B) includes the compound represented by formula (I-2) but does not include the compound represented by formula (I-1). In this case, the hardness and Young's modulus of the hardened product formed from the photosensitive resin composition are even higher, and the thermal expansion coefficient of the hardened product formed from the photosensitive resin composition is even lower.

[0076] Based on 100 parts by weight of the resin (A), the total amount of the compound represented by formula (I-1) and the compound represented by formula (I-2) is 100 to 700 parts by weight, preferably 200 to 600 parts by weight, and more preferably 250 to 550 parts by weight.

[0077] The cyclic structure contained in the acryl monomer having a cyclic structure is not particularly limited, and is, for example, an aliphatic ring, an aromatic ring, or a heterocyclic ring. The number of acryl groups contained in the acryl monomer having a cyclic structure is not particularly limited, and is preferably two or more. Specific examples of the acryl monomer having a cyclic structure include tricyclo[5.2.1.0 2,6 ]decane dimethanol diacrylate, 1,3-adamantane dimethanol diacrylate, trimethylolpropane benzoate diacrylate, 1,3-cyclohexane dimethanol diacrylate, 1,4-cyclohexane dimethanol diacrylate, tris(2-acryloyloxyethyl) isocyanurate, or a combination thereof.

[0078] When the photosensitive resin composition includes the acryl monomer having a cyclic structure, the hardness and Young's modulus of the hardened product formed from the photosensitive resin composition can be further effectively improved without affecting the ultraviolet transmittance, and the thermal expansion coefficient of the hardened product formed from the photosensitive resin composition can be reduced.

[0079] The acryl monomer having a cyclic structure is preferably 10 to 400 parts by weight, more preferably 20 to 350 parts by weight, and even more preferably 30 to 300 parts by weight, based on 100 parts by weight of the resin (A).

[0080] In addition, the ethylenically unsaturated monomer (B) can further include other ethylenically unsaturated monomers. Specifically, the other ethylenically unsaturated monomers include a compound represented by the following formula (II-1), a compound represented by the following formula (II-2), trimethylolpropane tri(meth)acrylate, glycerol di(meth)acrylate, glycerol triacrylate, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxy polyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerol polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate, a reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, and 2-hydroxyethyl (meth)acrylate, methylene bis(meth)acrylamide, a condensate of a polyol and N-methylol (meth)acrylamide, and the like multifunctional monomers, or a combination thereof.

[0081] Formula (II-1)

[0082] In formula (II-1), R 1 and R 2 respectively represent a hydrogen atom or a methyl group, Y 1 represents a linear or branched alkyl group having a carbon number of 1 to 6, and m represents an integer of 1 to 8.

[0083] Specific examples of the compound represented by formula (II-1) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, or a combination thereof.

[0084] Formula (II-2)

[0085] In formula (II-2), X17 20 X17to X20respectively represent a hydrogen atom, an acryloyl group, or a methacryloyl group, wherein at least two of X17to X20are an acryloyl group or a methacryloyl group.

[0086] Specific examples of the compound represented by formula (II-2) include pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, or a combination thereof.

[0087] The ethylenically unsaturated monomer (B) can be used alone or in combination with a plurality of monomers.

[0088] The ethylenically unsaturated monomer (B) is preferably 100 to 800 parts by weight, more preferably 200 to 700 parts by weight, and even more preferably 250 to 600 parts by weight, based on 100 parts by weight of the resin (A).

[0089] The photoinitiator (C)

[0090] The photoinitiator (C) in the photosensitive resin composition generates radicals and causes a polymerization reaction to form a hardened product in the exposure step.

[0091] The photoinitiator (C) includes an acylphosphine oxide compound (C-1). In addition, the photoinitiator (C) can further include an oxime ester compound (C-2), a benzophenone compound (C-3), or a combination thereof, without affecting the efficacy of the present application. Furthermore, the photoinitiator (C) can also include other photopolymerization initiators (C-4), without affecting the efficacy of the present application.

[0092] The acylphosphine oxide compound (C-1)

[0093] The acylphosphine oxide compound (C-1) is an acylphosphine oxide compound represented by formula (IV-1).

[0094] Formula (IV-1)

[0095] In formula (IV-1),

[0096] Y 2 , Y 3 , and Y 4 respectively represent a single bond or a carbonyl group, at least one of Y 2 , Y 3 , and Y 4 is a carbonyl group;

[0097] R 3 , R 4 , and R 5 respectively represent an alkyl group;​

[0098] p, q and r each represent an integer of 0 to 5.

[0099] Specific examples of the acylphosphine oxide compound (C-1) include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Irgacure 819, manufactured by BASF Corporation, a compound represented by the following formula (IV-1-1)), 2,4,6-trimethylbenzoyl diphenylphosphine oxide (trade name: TPO, manufactured by BASF Corporation, a compound represented by the following formula (IV-1-2)), or a combination thereof. The specific examples of the acylphosphine oxide compound (C-1) preferably include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, or a combination thereof.

[0100] Formula (IV-1-1)

[0101] Formula (IV-1-2)

[0102] The acylphosphine oxide compound (C-1) is 50 to 100% by weight based on 100% by weight of the photoinitiator (C).

[0103] The acylphosphine oxide compound (C-1) is 0.1 parts by weight to 50 parts by weight, preferably 1 part by weight to 40 parts by weight, and more preferably 10 parts by weight to 30 parts by weight, based on 100 parts by weight of the resin (A).

[0104] When the photoinitiator (C) includes the acylphosphine oxide compound (C-1), the speed of curing of the photosensitive resin composition to form a hardened product can be accelerated.

[0105] Oxime ester compound (C-2)

[0106] The oxime ester compound is a compound represented by the following formula (IV-2).

[0107] Formula (IV-2)

[0108] In the formula (IV-2),

[0109] R 6 represents an alkyl group or a cycloalkyl group, and preferably represents a hexyl group or a cyclopentyl group;

[0110] R 7 represents an alkyl group or a phenyl group, and preferably represents a methyl group or a phenyl group.

[0111] Specific examples of the oxime ester-based compound include a compound represented by formula (IV-2-1) (1,2-octanedione, 1-[4-(phenylsulfanyl)phenyl-, 2-(O-benzoyl oxime)], (trade name: Irgacure OXE-01, manufactured by BASF Corporation), a compound represented by formula (IV-2-2) (trade name: PBG-3057, manufactured by Changzhou Qiangli Electronics New Material Co., Ltd.), or a combination thereof.

[0112] Formula (IV-2-1)

[0113] Formula (IV-2-2)

[0114] Benzophenone-based compound (C-3)

[0115] The benzophenone-based compound can include chemcure-BP, chemcure-64 (trade name; manufactured by Hengqiao Industry Co., Ltd.), or other suitable benzophenone-based compounds. The benzophenone-based compound can be used alone or in combination with multiple types.

[0116] Other photopolymerization initiators (C-4)

[0117] The other photopolymerization initiators (C-4) are not particularly limited, and are, for example, triazine-based compounds, phenone-based compounds, dimidazole-based compounds, thioxanthone-based compounds, quinone-based compounds, or a combination thereof.

[0118] The triazine-based compound can include chemcure-PAG-1 (trade name; manufactured by Hengqiao Industry Co., Ltd.), chemcure-PAG-2 (trade name; manufactured by Hengqiao Industry Co., Ltd.), or other suitable triazine-based compounds. The triazine-based compound can be used alone or in combination with multiple types.

[0119] The phenone-based compound can include Irgacure 907, 369E (trade name; manufactured by BASF Corporation), chemcure-96 (trade name; manufactured by Hengqiao Industry Co., Ltd.), or other suitable phenone-based compounds. The phenone-based compound can be used alone or in combination with multiple types.

[0120] The dimidazole-based compound can include Chemcure-BCIM, Chemcure-TCDM (trade name; manufactured by Hengqiao Industry Co., Ltd.), or other suitable dimidazole-based compounds. The dimidazole-based compound can be used alone or in combination with multiple types.

[0121] The thioxanthone compound can include Irgacure ITX (trade name; manufactured by BASF) or other suitable thioxanthone compound. The thioxanthone compound can be used alone or in combination.

[0122] The quinone compound can be selected as appropriate. The quinone compound can be used alone or in combination.

[0123] The photoinitiator (C) is preferably 1 part by weight to 80 parts by weight, more preferably 10 parts by weight to 50 parts by weight, based on 100 parts by weight of the resin (A).

[0124] Solvent (D)

[0125] The solvent (D) includes propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether, propylene glycol monopropyl ether, cyclopentanone, cyclohexanone, or a combination thereof.

[0126] The solvent (D) can be used alone or in combination.

[0127] The solvent (D) is preferably 400 parts by weight to 800 parts by weight, more preferably 450 parts by weight to 750 parts by weight, based on 100 parts by weight of the resin (A).

[0128] Hydrophobic oligomer (E)

[0129] The hydrophobic oligomer (E) is not particularly limited and can be selected as appropriate from among oligomers that can undergo a crosslinking reaction with the resin (A) and the like.

[0130] The hydrophobic oligomer (E) can include a fluorine-based acrylic oligomer (E-1). Specific examples of the fluorine-based acrylic oligomer (E-1) include R-30, R-94, RS-75, RS-72-K, RS-76-NS, DS-21, RS-72-A, RS-75-NS, or a combination thereof, of the Megafac series manufactured by DIC Corporation, and the selection thereof is determined as appropriate, i.e., the fluorine-based acrylic oligomer (E-1) can undergo a crosslinking reaction with the resin (A) and the like. The specific examples of the fluorine-based acrylic oligomer (E-1) are preferably a combination of RS-75, RS-72-A, RS-75-NS, or the like.

[0131] The hydrophobic oligomer (E) can include a silicone-based acrylic oligomer (E-2). Specific examples of the silicone-based acrylic oligomer (E-2) include BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341v344, BYK-345v346, BYK-348, BYK-354, BYK-355, BYK-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380, BYK-390, or a combination thereof, manufactured by BYK-Chemie, which is selected as needed, i.e., which can be crosslinked with the components such as the resin (A). The specific example of the silicone-based acrylic oligomer (E-2) is preferably BYK-370.

[0132] When the photosensitive resin composition contains the hydrophobic oligomer (E) including the fluorine-based acrylic oligomer (E-1), the hydrophobic oligomer (E) can be crosslinked with the components such as the resin (A), whereby the water absorption of the hardened product formed by the photosensitive resin composition can be further reduced.

[0133] Further, the hydrophobic oligomer (E) can further include other hydrophobic oligomers (E-3) without affecting the effects of the present application. The other hydrophobic oligomers (E-3) are not particularly limited and can be appropriately selected as needed.

[0134] The hydrophobic oligomer (E) is 0.1 parts by weight to 50 parts by weight, preferably 1 part by weight to 40 parts by weight, and more preferably 10 parts by weight to 30 parts by weight, based on 100 parts by weight of the resin (A).

[0135] Surfactant (F)

[0136] The photosensitive resin composition can further include a surfactant (F) as needed, in addition to the above components, without affecting the effects of the present application. The surfactant (F) is not particularly limited but is basically not crosslinked with the components such as the resin (A). For example, the surfactant (F) can include at least one selected from the group consisting of a fluorine-based surfactant (F-1), a silicone-based surfactant (F-2), a nonionic surfactant (F-3), or a combination thereof.

[0137] Specific examples of the fluorine-based surfactant (F-1) include Megaface F444, F477, F554, F556, F563, F575 (trade names; manufactured by DIC Corporation) or other suitable fluorine-based surfactants, the selection of which can be determined as desired, i.e., without undergoing a crosslinking reaction with the components such as the resin (A). The fluorine-based surfactant (F-1) can be used alone or in combination with multiple types.

[0138] Specific examples of the silicone-based surfactant (F-2) include polysiloxane-based surfactants. Specifically, the silicone-based surfactant can include BYK-307, BYK-323, BYK-348 (trade names; manufactured by BYK-Chemie GmbH), KP323, KP324, KP340, KP341 (trade names; manufactured by Shin-Etsu Chemical Co., Ltd.), or other suitable silicone-based surfactants, the selection of which can be determined as desired, i.e., without undergoing a crosslinking reaction with the components such as the resin (A). The silicone-based surfactant (F-2) can be used alone or in combination with multiple types.

[0139] Specific examples of the nonionic surfactant (F-3) include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, or other suitable nonionic surfactants, the selection of which can be determined as desired, i.e., without undergoing a crosslinking reaction with the components such as the resin (A). The nonionic surfactant (F-3) can be used alone or in combination with multiple types.

[0140] Based on 100 parts by weight of the resin (A), the surfactant (F) is 0 parts by weight to 20 parts by weight, preferably 0.1 parts by weight to 10 parts by weight, and more preferably 0.5 parts by weight to 5 parts by weight.

[0141] Additive (G)

[0142] Without affecting the effects of the present application, the photosensitive resin composition can also add an additive (G) as necessary in addition to the above components. The additive (G) is not particularly limited, and specifically, the additive (G) can include a photosensitizer, an antioxidant, an ultraviolet absorber, a light stabilizer, an aging inhibitor, a plasticizer, an adhesion promoter, a thermal polymerization initiator, a photo-base generator, a colorant, an inorganic particle, an elastomer particle, an alkaline compound, a photo-acid generator, a photo-acid proliferator, a chain transfer agent, an antistatic agent, a flow modifier, an antifoaming agent, a dispersant, or a combination thereof.

[0143] <Method for preparing the photosensitive resin composition>

[0144] The method for preparing the photosensitive resin composition is not particularly limited, and an appropriate method for mixing the components can be selected as needed. For example, the resin (A), the ethylenically unsaturated monomer (B), the photoinitiator (C), the solvent (D), and the hydrophobic oligomer (E) can be placed in a stirrer and stirred to be uniformly mixed into a solution state. If necessary, the additive (G), the surfactant (F), or a combination of the two can be added, and the photosensitive resin composition in a liquid state can be obtained after uniform mixing.

[0145] <Hardened product>

[0146] The present embodiment provides a hardened product, which is hardened from the embossing photosensitive resin composition described above, and the hardened product can be a hardened film or a block.

[0147] The present embodiment provides a hardened film, which is hardened from the embossing photosensitive resin composition described above.

[0148] The hardened film can be formed by applying the photosensitive resin composition described above on a substrate to form a coating film, and performing prebaking, exposure, and postbaking on the coating film. Specifically, after the photosensitive resin composition is applied on the substrate to form a coating film, prebaking is performed at a temperature of 80-100°C for 3-5 minutes. Then, the prebaked coating film is exposed to an i-line (wavelength: 365 nm) exposure machine for 3000 J / m 2 . Then, postbaking is performed at 150-200°C for 40-60 minutes to form a hardened film on the substrate.

[0149] The substrate can be a glass substrate, a silicon wafer substrate, or a plastic base material (for example, a Polysulfone (PES) plate or a Polycarbonate (PC) plate), and the type thereof is not particularly limited.

[0150] The coating method is not particularly limited, but a spray coating method, a roll coating method, a spin coating method, or the like can be used, and generally, a spin coating method is widely used. In addition, a coating film is formed, and then in some cases, residual solvents can be partially removed under reduced pressure.

[0151] The present embodiment provides a block, which is hardened from the embossing photosensitive resin composition described above.

[0152] The photosensitive resin composition is poured into a block mold, and baking is performed at a temperature of 100-140°C for 24-36 hours. Then, postbaking is performed at 200-240°C for 10-30 minutes to obtain a block.

[0153] In one embodiment, the hardening has a thickness of 1 to 5 μm. In another embodiment, the hardening has a thickness of 3 to 5 μm.

[0154] In one embodiment, the hardening has a thickness of 1 to 5 μm and a transmittance of more than 94% at a wavelength of 365 nm, more than 98% at a wavelength of 400 nm, and more than 99% at a wavelength of 500 to 1100 nm.

[0155] In one embodiment, the hardening has a Young's modulus of more than 1 Gpa, preferably more than 4 Gpa, and more preferably more than 4.5 Gpa.

[0156] In one embodiment, the hardening has a water absorption of less than 0.5%.

[0157] In one embodiment, the hardening has a Shore D hardness of more than 70.

[0158] In one embodiment, the hardening has a thermal expansion coefficient of less than 100 ppm / °C, and preferably less than 70 ppm / °C.

[0159] In one embodiment, the hardening has a refractive index of more than 1.5.

[0160] <Optical element>

[0161] The present application provides an optical element comprising the hardening as described above.

[0162] The optical element is, for example, an optical lens, an optical element, a transparent back light panel, an encapsulating material in a micro light emitting diode display (Micro LED), a semiconductor integrated circuit, a flat screen, a micro electromechanical system (MEMS), a sensor element, an optical disk, a magnetic storage media such as a high density memory disk, an optical part such as a diffraction grating or a relief hologram, a nano device, an optical element, an optical film or a polarizing element for manufacturing a flat panel display.

[0163] Hereinafter, the present application will be described in detail with reference to experimental examples. The following experimental examples are provided to describe the present application, and the scope of the present application includes the scope described in the following claims and its substitutes and modifications, and is not limited to the scope of the experiments.

[0164] <Experimental examples and comparative examples of photosensitive resin composition and hardening>

[0165] Experimental Examples 1 to 7 and Comparative Example 1 of the photosensitive resin composition and the hardened film are described below:

[0166] Experimental Example 1

[0167] I. Photosensitive resin composition

[0168] 100 parts by weight of a cadion resin (molecular weight: 5300; manufactured by Gohsen Co., Ltd.), 498 parts by weight of a multifunctional polyamine ester acrylate (trade name: DPHA-40H, manufactured by Nippon Kayaku Co., LTD.), 55 parts by weight of an acryloyl monomer having a cyclic structure, 5.48 parts by weight of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Irgacure 819, manufactured by BASF), 22.2 parts by weight of 2,4,6-trimethylbenzoyl diphenylphosphine oxide (trade name: TPO, manufactured by BASF), and 20.1 parts by weight of a fluorine-based acrylic oligomer 1 were added to 634 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and after stirring with a stirrer until uniform, the photosensitive resin composition of Experimental Example 1 was prepared.

[0169] II. Hardened film

[0170] Each of the photosensitive resin compositions prepared in the Experimental Examples or the Comparative Example was coated on a glass substrate of 8 inches by a spin coating method (spin coater model TEL-MK8, manufactured by Tokyo Eprex Co., Ltd., rotation speed: about 1800 rpm). Next, pre-baking was performed at a temperature of 90°C for 3 minutes. Then, exposure was performed with an i-line (i-line) exposure machine (wavelength: 365 nm) (exposure machine model FPA-5500 iZa, manufactured by Cannon Inc.) at 3000 J / m 2 to form a semi-finished product. Finally, post-baking was performed at 150°C for 60 minutes to obtain a hardened film.

[0171] II. Block

[0172] Each of the photosensitive resin compositions prepared in the Experimental Examples or the Comparative Example was poured into a block mold, and baking was performed at a temperature of 120°C for 24 hours. Then, post-baking was performed at 220°C for 20 minutes to obtain a block.

[0173] The prepared hardened film or block was evaluated in the following evaluation methods, and the results are shown in Table 1.

[0174] Experimental Examples 2 to 7 and Comparative Example 1

[0175] The photosensitive resin compositions of Experimental Examples 2 to 7 and Comparative Example 1 were prepared in the same procedure as Experimental Example 1, and the difference was that the kind and amount of the components of the photosensitive resin composition were changed (as shown in Table 1). The hardened films or blocks prepared from the photosensitive resin compositions were evaluated in the following evaluation methods, and the results are shown in Table 1.

[0176] [Table 1]

[0177]

[0178] The trade names of the components / compounds in Table 1 are as shown in Table 2.

[0179] [Table 2]

[0180]

[0181] [Evaluation methods]

[0182] a. Transmittance

[0183] The transmittance of the hardened films (5 μm in thickness) prepared was measured at a wavelength of 190-1100 nm using a UV-Vis spectrophotometer (model U2900, manufactured by Hitachi High-technologies). Specifically, after scanning the full-range spectrum using the UV-Vis spectrophotometer, the transmittance at a wavelength of 365 nm, 400 nm and 500 nm was recorded, respectively.

[0184] b. Refractive index

[0185] The refractive index of the hardened films (5 μm in thickness) prepared was measured at a wavelength of 940 nm using an ellipsometer (model M2000, manufactured by J. A. Woollam Co. Inc.).

[0186] c. Coefficient of thermal expansion

[0187] The coefficient of thermal expansion (CTE) of the blocks prepared was measured at a temperature of 25°C or higher to 200°C or lower using a thermal mechanical analyzer (model TMA Q400, manufactured by TA instruments Inc.).

[0188] d. Water absorption

[0189] The prepared block was placed in an oven for drying, and then the dried block was placed in a dry box at 25°C and 30% relative humidity for 30 to 60 hours, and weighed to obtain the weight Wd of the dried block. After the block was placed in water at 25°C for 24 hours, it was taken out to obtain the weight W of the block after water absorption. Then, the water absorption rate was calculated according to the following mathematical formula (1).

[0190] Water absorption rate (%) = (W - Wd) / Wd x 100 (%)

[0191] e. Shore hardness

[0192] The Shore hardness of the block was measured using a Shore D hardness tester.

[0193] f. Young's modulus

[0194] The Young's modulus of the prepared block was measured using a micro hardness tester (model Hm2000, manufactured by Fischer Instruments).

[0195] <Results of evaluation>

[0196] As shown in Table 1, when the photosensitive resin composition contains the resin (A), the ethylenically unsaturated monomer (B), the photoinitiator (C), the solvent (D), and the hydrophobic oligomer (E) (experimental examples 1 to 7), the prepared hardened material (hardened film or block) not only meets the requirement of high transmittance at each wavelength, but also simultaneously has low thermal expansion coefficient, low water absorption rate, high hardness, and high Young's modulus, so that the prepared hardened material is suitable for optical elements.

[0197] In contrast, when the photosensitive resin composition does not contain the hydrophobic oligomer (comparative example 1), the water absorption rate of the prepared hardened material is high, so that it cannot simultaneously have high transmittance, low thermal expansion coefficient, low water absorption rate, high hardness, and high Young's modulus, and thus the prepared hardened material is not suitable for optical elements.

[0198] In addition, experimental examples 1 to 7 and comparative example 1 show that experimental examples 1 to 7 using the multifunctional polyurethane acrylate as the ethylenically unsaturated monomer (B) have higher hardness, Young's modulus, and lower water absorption rate than comparative example 1 using dipentaerythritol hexaacrylate as the ethylenically unsaturated monomer (B).

[0199] In summary, the photosensitive resin composition of the present application contains the resin (A), the ethylenically unsaturated monomer (B), the photoinitiator (C), the solvent (D), and the hydrophobic oligomer (E), so that the formed hardened material has high transmittance, low thermal expansion coefficient, low water absorption rate, high hardness, and high Young's modulus, and thus is suitable for optical elements.

[0200] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, and are not intended to limit the present application; although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that the technical solutions described in the foregoing embodiments can still be modified, or some or all of the technical features can be replaced by equivalents; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A photosensitive resin composition for embossing, characterized by comprising: comprises: a resin A, wherein the resin A has a weight average molecular weight of 1,000 to 50,000 and has two or more ethylenic polymerizable groups; an ethylenic unsaturated monomer B, wherein the ethylenic unsaturated monomer B comprises an acryloyl monomer having a cyclic structure and a compound represented by formula (I-2), but does not comprise a compound represented by formula (I-1); a photoinitiator C; a solvent D; and a hydrophobic oligomer E, wherein the hydrophobic oligomer E comprises a fluorine-based acrylic oligomer E-1, wherein, based on 100 parts by weight of the resin A, 100 parts by weight to 800 parts by weight of the ethylenic unsaturated monomer B, 0.1 parts by weight to 100 parts by weight of the photoinitiator C, 300 parts by weight to 900 parts by weight of the solvent D, and 0.1 parts by weight to 50 parts by weight of the hydrophobic oligomer E, the hydrophobic oligomer E further comprises a siloxane-based acrylic oligomer E-2. Formula (I-1) In formula (I-1), X 1 X 6 respectively represent a hydrogen atom, an acryloyl group or a methacryloyl group, wherein at least two of X 1 X 6 are an acryloyl group or a methacryloyl group, Formula (I-2) In formula (I-2), X 7 X 16 respectively represent a hydrogen atom, an acryloyl group or a methacryloyl group, wherein at least two of X 7 X 16 are acryloyl groups or methacryloyl groups.

2. The embossing photosensitive resin composition according to claim 1, characterized by the resin A comprises a resin A-1 having a fluorene ring and two or more ethylenic polymerizable groups, a polyamine ester acrylate A-2, or a combination thereof.

3. The photosensitive resin composition for embossing according to claim 1, characterized by the photoinitiator C comprises an acylphosphine oxide compound C-1.

4. The embossing photosensitive resin composition according to claim 1, characterized by based on 100% by weight of the photoinitiator C, the acylphosphine oxide compound C-1 is 50 to 100% by weight.

5. The embossing photosensitive resin composition according to claim 4, characterized by the solvent D comprises propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, cyclopentanone, cyclohexanone, or a combination thereof.

6. The photosensitive resin composition for imprint according to claim 1, wherein further comprises a surfactant F, which comprises a fluorine-based surfactant F-1, a siloxane-based surfactant F-2, a nonionic surfactant F-3, or a combination thereof.

7. The embossing photosensitive resin composition according to claim 1, characterized by is hardened from the photosensitive resin composition for imprint as claimed in any one of claims 1 to 7.

8. A hardened material, characterized by, the hardened product has a thickness of 1 to 5 μm.

9. The hardened material of claim 8, wherein the hardened product has a transmittance of greater than 94% at a wavelength of 365 nm, a transmittance of greater than 98% at a wavelength of 400 nm, and a transmittance of greater than 99% at a wavelength of 500 to 1100 nm.

10. The hardened material of claim 9, wherein the hardened product has a Young's modulus of greater than 1 Gpa.

11. The hardened material of claim 8, wherein the hardened product has a water absorption of less than 0.5%.

12. The hardened material of claim 8, wherein the hardened product has a Shore D hardness of greater than 70.

13. The hardened material of claim 8, wherein the hardened product has a coefficient of thermal expansion of less than 100 ppm / °C.

14. The hardened material of claim 8, wherein the hardened product has a refractive index of greater than 1.

5.

15. The hardened article of claim 8, wherein comprises the hardened product as claimed in any one of claims 8 to 15.

16. An optical element, characterized by, ​

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