WO2019167461A1 - ポリマーを含むインプリント用光硬化性組成物 - Google Patents
ポリマーを含むインプリント用光硬化性組成物 Download PDFInfo
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- WO2019167461A1 WO2019167461A1 PCT/JP2019/001392 JP2019001392W WO2019167461A1 WO 2019167461 A1 WO2019167461 A1 WO 2019167461A1 JP 2019001392 W JP2019001392 W JP 2019001392W WO 2019167461 A1 WO2019167461 A1 WO 2019167461A1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00009—Production of simple or compound lenses
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B3/00—Simple or compound lenses
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
Definitions
- the present invention includes an alicyclic (meth) acrylate monomer, a urethane (meth) acrylate compound or an epoxy (meth) acrylate compound, a surface-modified silica particle, a polymer having a radical polymerizable group, and an optical radical initiator.
- the present invention relates to a photocurable composition for printing.
- the optical properties are excellent, and after forming an antireflection layer (AR layer) on the upper layer of the cured product and the molded body, the antireflection layer is formed even after heat treatment.
- the present invention relates to a photocurable composition that does not generate cracks and that does not generate cracks in a cured product even after washing or development with an organic solvent.
- Resin lenses are used in electronic devices such as mobile phones, digital cameras, and in-vehicle cameras, and are required to have excellent optical characteristics according to the purpose of the electronic device. Moreover, high durability, for example, heat resistance and weather resistance, and high productivity that can be molded with a high yield are required in accordance with the usage mode.
- a thermoplastic transparent resin such as a polycarbonate resin, a cycloolefin polymer, and a methacrylic resin has been used.
- a plurality of lenses are used in the high resolution camera module, but lenses having low wavelength dispersion, that is, lenses having a high Abbe number are mainly used, and an optical material for forming them is required.
- lenses having low wavelength dispersion that is, lenses having a high Abbe number are mainly used, and an optical material for forming them is required.
- resin lenses in order to improve yield and production efficiency, and to suppress optical axis misalignment during lens lamination, from injection molding of thermoplastic resin to pressing molding using liquid curable resin at room temperature The transition to wafer level molding by means of is being actively studied.
- wafer level molding from the viewpoint of productivity, a hybrid lens system in which a lens is formed on a support such as a glass substrate is generally used.
- a radically curable resin composition As a photocurable resin capable of wafer level molding, a radically curable resin composition has been conventionally used from the viewpoints of high transparency, heat-resistant yellowing and mold releasability (Patent Document 1). ).
- a curable composition capable of obtaining a cured product having a high Abbe number by containing surface-modified oxide particles such as silica particles surface-modified with a silane compound and zirconium oxide particles surface-modified with a dispersant.
- surface-modified oxide particles such as silica particles surface-modified with a silane compound and zirconium oxide particles surface-modified with a dispersant.
- Patent No. 5281710 International Publication No. 2011/105473
- JP 2014-234458 A International Publication No. 2016/104039
- the molded body is a lens
- an antireflection layer made of an inorganic material such as silicon oxide or titanium oxide is formed thereon. Therefore, there is a problem that cracking occurs in the antireflection layer by heat-treating the lens covered with the antireflection layer.
- the curable composition containing the surface-modified oxide particles is a development step of washing an uncured portion such as an outer peripheral portion of a wafer-shaped molded body on which a plurality of lens patterns are formed after imprinting with an organic solvent.
- erosion of the organic solvent into the wafer-shaped molded body becomes remarkable, and there is a problem that cracks are generated in the wafer-shaped molded body.
- the development process in which cracks do not occur and the uncured portion such as the outer periphery of the wafer-shaped molded body is washed with an organic solvent there is still no curable resin material in which cracks do not occur in the wafer-shaped molded body.
- the development was desired.
- the present invention has been made in view of such circumstances, and can form a molded body exhibiting a high Abbe number, a high refractive index, high transparency and heat-resistant yellowing, and heat-treating the molded body. It is an object of the present invention to provide a photocurable composition capable of forming a molded article having high crack resistance in which cracks do not occur in the upper antireflection layer and cracks do not occur even when exposed to a development process.
- the inventors of the present invention blend the surface-modified silica particles and the polymer having a radical polymerizable group, respectively, into the photocurable composition at a predetermined ratio.
- the molded product obtained from the photocurable composition has a high refractive index n D (1.50 or more) and a high Abbe number ⁇ D (53 or more), and a high transmittance of 90% or more at a wavelength of 410 nm.
- n D refractive index
- ⁇ D 53 or more
- a high transmittance of 90% or more at a wavelength of 410 nm it was found that the heat treatment at 175 ° C. did not cause any cracks or wrinkles in the upper antireflection layer of the molded article, and furthermore, no cracks occurred in the development process using an organic solvent. It came to be completed.
- the first aspect of the present invention includes the following component (a), the following component (b), the following component (c), the following component (d), and the following component (e).
- Component 100 parts by mass of the component (c) and the component (d), the component (a) is 10 to 40 parts by mass, the component (b) is 10 to 50 parts by mass, The component (c) is 10 to 50 parts by weight, the component (d) is 1 to 10 parts by weight, and the component (e) is 0.1 to 5 parts by weight. It is a photocurable composition.
- R 1 and R 2 each independently represent a methyl group or a hydrogen atom
- a 1 represents an alkyl group having 1 to 8 carbon atoms
- a 2 represents a single bond or an alkylene having 1 to 4 carbon atoms.
- X represents a polymerizable group having one or more (meth) acryloyloxy groups
- the photocurable composition for imprints of the present invention further comprises 1 part by mass to 15 parts by mass with respect to 100 parts by mass of the sum of the component (a), the component (b), the component (c) and the component (d).
- the following component (f) may be contained.
- the bond represents ——O—
- Q represents an organic group having 2 to 12 carbon atoms containing at least one heteroatom or no heteroatom, or a heteroatom, and r represents an integer of 2 to 6.
- a hetero atom represents atoms other than a carbon atom and a hydrogen atom, for example, a nitrogen atom, an oxygen atom, and a sulfur atom are mentioned.
- the photocurable composition for imprints of the present invention further comprises 0.05 parts by mass to 100 parts by mass of the sum of the component (a), the component (b), the component (c), and the component (d). 3 parts by mass of the following component (g) and / or the component (a), the component (b), the component (c), and the component (d) are 0.1 parts by mass to 3 parts by mass. You may contain the following (h) component of a mass part.
- h Sulfide antioxidant
- the divalent linking group is, for example, an alkylene group having 1 to 5 carbon atoms, preferably an alkylene group having 2 or 3 carbon atoms.
- the urethane (meth) acrylate compound or epoxy (meth) acrylate compound as the component (c) is a compound having, for example, two or three (meth) acryloyloxy groups in one molecule.
- the polymer of the component (d) may further have a repeating structural unit represented by the following formula (4).
- R 3 represents a methyl group or a hydrogen atom
- Z 3 represents a single bond or an ethyleneoxy group
- a 4 represents an alicyclic hydrocarbon group having 5 to 13 carbon atoms.
- Z 3 represents an ethyleneoxy group (—CH 2 CH 2 O— group)
- the O atom of the ethyleneoxy group is bonded to A 4 representing the alicyclic hydrocarbon group.
- the alicyclic hydrocarbon group having 5 to 13 carbon atoms is substituted with, for example, a cyclopentyl group, cyclohexyl group, isobornyl group, dicyclopentanyl group, dicyclopentenyl group, or an alkyl group having 1 to 3 carbon atoms.
- An adamantyl group which may be present as a group.
- Examples of the polymerizable group having one or more (meth) acryloyloxy groups include the following formula (X0), formula (X1), formula (X2), formula (X3), formula (X4), formula (X X5) or a group represented by formula (X6), or a group obtained by substituting part or all of the acryloyloxy group of these groups with a methacryloyloxy group.
- the cured product has a refractive index n D at a wavelength of 589 nm of 1.50 or more, and the cured product has an Abbe number ⁇ D of 53 or more.
- the second aspect of the present invention is a cured product of the photocurable composition for imprints.
- the 3rd aspect of this invention is a manufacturing method of the resin lens including the process of imprint-molding the said photocurable composition for imprints.
- a method for producing a molded product of a photocurable composition for imprints wherein the imprinted photocurable composition has a space between a support and a mold in contact with each other, or It is a method for producing a molded body, which includes a filling step of filling a space inside a mold that can be divided, and a photocuring step of exposing and photocuring the photocurable composition for imprint filled in the space.
- the mold is also called a mold.
- a mold releasing step of taking out the obtained photocured product after the photocuring step, a mold releasing step of taking out the obtained photocured product, and heating the photocured product before, during or after the mold releasing step.
- a heating step may be further included.
- You may further include the image development process which wash
- the photocured product after the development step may be exposed again and photocured.
- the molded body is, for example, a camera module lens.
- the photocurable composition for imprints of the present invention includes the component (a) to the component (e), and optionally, the component (f), the component (g), and / or the component (h).
- the cured product and the molded product obtained from the photocurable composition contain the components, so that the optical properties desirable as a lens for an optical device, for example, a high-resolution camera module, that is, a high Abbe number, a high refractive index, and a high transparency. And heat yellowing.
- the cured product and the molded product obtained from the photocurable composition of the present invention are such that the antireflective layer on the upper layer of the cured product and the molded product is free from cracks and wrinkles due to heat treatment at 175 ° C. Cracks do not occur in the development process using an organic solvent.
- the surface-modified silica particles that can be used as the component (a) of the photocurable composition for imprints of the present invention have a primary particle diameter of 1 nm to 100 nm.
- the primary particles are particles constituting the powder, and the particles in which the primary particles are aggregated are referred to as secondary particles.
- the primary particle diameter calculated from the relational expression is an average particle diameter and is a diameter of the primary particles.
- the surface-modified silica particles are surface-modified with, for example, a (meth) acryloyloxy group bonded to a silicon atom via a divalent linking group.
- the surface-modified silica particles may be used as they are, and the surface-modified silica particles are in a colloidal state in which the surface-modified silica particles are previously dispersed in an organic solvent as a dispersion medium. (A sol in which colloidal particles are dispersed in a dispersion medium) may be used.
- a sol having a solid content in the range of 10% by mass to 60% by mass can be used.
- sol containing the surface-modified silica particles examples include MEK-AC-2140Z, MEK-AC-4130Y, MEK-AC-5140Z, PGM-AC-2140Y, PGM-AC-4130Y, MIBK-AC-2140Z, MIBK-SD-L (manufactured by Nissan Chemical Co., Ltd.), ELCOM (registered trademark) V-8802, and V-8804 (manufactured by JGC Catalysts & Chemicals Co., Ltd.) can be employed.
- the content of the component (a) in the photocurable composition for imprints of the present invention is the sum 100 of the component (a), the component (b) described later, the component (c) described later, and the component (d) described later. It is 10 to 40 parts by mass, preferably 15 to 35 parts by mass with respect to parts by mass. If the content of the component (a) is less than 10 parts by mass, the cured product obtained from the photocurable composition for imprints and the crack of the antireflection layer formed on the upper layer of the molded product may not be suppressed. There is. When there is more content of this (a) component than 40 mass parts, there exists a possibility that haze will arise in this hardened
- the surface-modified silica particles of the component (a) can be used singly or in combination of two or more.
- the alicyclic (meth) acrylate monomer that can be used as the component (b) of the photocurable composition for imprints of the present invention has at least one (meth) acryloyloxy group, for example, one in one molecule of the monomer. Or it is a monomer compound which has two and one alicyclic hydrocarbon, and remove
- Examples of the alicyclic (meth) acrylate monomer include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, menthyl (Meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, 2-methyladamantan-2-yl (meth) acrylate, 2-ethyladamantane -2-yl (meth) acrylate, tricyclo [5.2.1.0 (2,6)] decanyl (meth) acrylate, tricyclo [5.2.1.0 (2,6)] decanyl (meth) acrylate 1,4-cyclohexanedimethanol
- alicyclic (meth) acrylate monomer for example, Biscoat # 155, IBXA, ADMA (manufactured by Osaka Organic Chemical Industry Co., Ltd.), NK Ester A-IB, IB, A-DCP, DCP (above, manufactured by Shin-Nakamura Chemical Co., Ltd.), and FANCLIL (registered trademark) FA-511AS, FA-512AS, FA-513AS, FA-512M, FA-512MT, FA-513M (made by Hitachi Chemical Co., Ltd.).
- the content of the component (b) in the photocurable composition for imprints of the present invention is 100 mass of the sum of the component (a), the component (b), the component (c) described later, and the component (d) described later. Parts by weight to 10 parts by weight to 50 parts by weight, preferably 20 parts by weight to 45 parts by weight.
- the content of the component (b) is less than 10 parts by mass, the refractive index of the cured product and the molded product obtained from the photocurable composition for imprints may be lowered to less than 1.50.
- there is more content of this (b) component than 50 mass parts there exists a possibility that the curvature amount of the support body in which this hardened
- the alicyclic (meth) acrylate monomer of the component (b) can be used alone or in combination of two or more.
- urethane (meth) acrylate compound examples include EBECRYL (registered trademark) 230, 270, 280 / 15IB, 284, 4491, 4683, 4858, 8307, 8402, 8411, 8804, 8807, 9270, 8800, 294 / 25HD, 4100, 4220, 4220, 4513, 4738, 4740, 4820, 8311, 8465, 9260, 8701, KRM7735, 8667, 8296 (manufactured by Daicel Ornex Co., Ltd.), UV-2000B, UV-2750B, UV-3000B, UV-3200B, UV-3210EA, UV-3300B, UV-3310B, UV-3500B, UV-3520EA, UV -3700B, UV-6640B, V-6630B, UV-7000B, UV-7510B, UV-7461TE (above, manufactured by Nippon Synthetic Chemical Co., Ltd.), UA-306H, UA
- the epoxy (meth) acrylate compound that can be used as the component (c) of the photocurable composition for imprints of the present invention is obtained by reacting a compound having at least two epoxy rings in one molecule with (meth) acrylic acid. And a compound excluding the polymer of component (d) described later.
- the epoxy (meth) acrylate compound include EBECRYL (registered trademark) 645, 648, 860, 3500, 3608, 3702, 3708 (above, Daicel Ornex Co., Ltd.), DA-911M.
- DA-920, DA-931, DA-314, DA-212 above, manufactured by Nagase ChemteX Corporation), HPEA-100 (manufactured by KS Corporation), and Unidic (registered trademark) V-5500, V-5502 and V-5508 (manufactured by DIC Corporation).
- the content of the component (c) in the photocurable composition for imprints of the present invention is 100 parts by mass of the component (a), the component (b), the component (c) and the component (d) described later.
- the component (c) is 10 to 50 parts by mass, preferably 30 to 50 parts by mass.
- the content of the component (c) is less than 10 parts by mass, the cured product and the molded product obtained from the photocurable composition for imprints become brittle, so that the resistance of the cured product and the molded product during heating is increased. There is a possibility that the cracking property is lowered.
- there is more content of this (b) component than 50 mass parts there exists a possibility that the shape change of this hardened
- the urethane (meth) acrylate compound or epoxy (meth) acrylate compound as the component (c) can be used alone or in combination of two or more.
- the polymer that can be used as the component (d) of the photocurable composition for imprints of the present invention is a copolymer containing a polymerizable group, and the repeating structural unit represented by the formula (1) and the formula (1) It may have at least a repeating structural unit represented by 2) and may further have a repeating structural unit represented by the formula (4).
- Examples of the repeating structural unit represented by the formula (1) include repeating structural units represented by the following formulas (1-1) to (1-6).
- Examples of the repeating structural unit represented by the formula (2) include repeating structural units represented by the following formulas (2-1) to (2-44).
- Examples of the repeating structural unit represented by the formula (4) include repeating structural units represented by the following formulas (4-1) to (4-22).
- Examples of the polymer of the component (d) include, for example, Hitaloid (registered trademark) 7975, 7975D, 7988 (above, manufactured by Hitachi Chemical Co., Ltd.), RP-274S, RP-310 (above, made by KSM Co., Ltd.) Artcure (registered trademark) RA-3602MI, OPA-5000, OPA-2511, RA-341 (above, Negami Kogyo Co., Ltd.).
- the content of the component (d) of the photocurable composition for imprints of the present invention is 100 parts by mass of the sum of the component (a), the component (b), the component (c), and the component (d). On the other hand, it is 1 to 10 parts by mass, preferably 3 to 7 parts by mass.
- the content of the component (d) is less than 1 part by mass, the effect of suppressing the occurrence of cracks in the cured product in the development process using a solvent becomes insufficient.
- the content of the component (d) is more than 10 parts by mass, the viscosity of the photocurable composition for imprints is significantly increased, so that workability is remarkably lowered.
- the polymer of the said (d) component can be used individually by 1 type or in combination of 2 or more types.
- photo-radical initiator examples include alkylphenones, benzophenones, Michler's ketones, acylphosphine oxides, and benzoylbenzoates. , Oxime esters, tetramethylthiuram monosulfides, and thioxanthones, with photocleavable photoradical polymerization initiators being particularly preferred.
- the content of the component (e) in the photocurable composition for imprints of the present invention is 100 parts by mass of the sum of the component (a), the component (b), the component (c), and the component (d).
- the amount is 0.1 to 5 parts by mass, preferably 0.5 to 3 parts by mass.
- content of this (e) component is less than 0.1 mass part, there exists a possibility that the intensity
- there is more content of this (e) component than 5 mass parts there exists a possibility that the heat-resistant yellowing of this hardened
- the photoradical initiator of the component (e) can be used alone or in combination of two or more.
- the polyfunctional thiol compound that can be used as the component (f) of the photocurable composition for imprints of the present invention is a polyfunctional thiol compound represented by the formula (3).
- the polyfunctional thiol compound represented by the formula (3) include 1,2-ethanedithiol, 1,3-propanedithiol, bis (2-mercaptoethyl) ether, trimethylolpropane tris (3-mercaptopropio Nate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mer
- polyfunctional thiol compound represented by the formula (3) commercially available products such as Karenz MT (registered trademark) PE1, NR1, BD1, TPMB, TEMB (above, manufactured by Showa Denko KK), and TMMP TEMPIC, PEMP, EGMP-4, DPMP, TMMP II-20P, PEMP II-20P, PEPT (above, SC Organic Chemical Co., Ltd.) can be employed.
- the photocurable composition for imprints of the present invention contains the component (f), the content of the component (a), the component (b), the component (c), and the component (d) It is 1 to 15 parts by mass, preferably 3 to 10 parts by mass with respect to 100 parts by mass of the sum.
- the content of the component (f) is more than 15 parts by mass, the cured product and the molded body obtained from the photocurable composition for imprints are deteriorated in mechanical properties. The cured product and the molded product may be deformed.
- the polyfunctional thiol compound of the component (f) can be used alone or in combination of two or more.
- phenolic antioxidant examples include, for example, IRGANOX (registered trademark) 245, 1010, 1035, 1076, and 1135 (above, BASF Japan Co., Ltd.), SUMILIZER (registered trademark) GA-80, GP, MDP-S, BBM-S, WX-R (above, manufactured by Sumitomo Chemical Co., Ltd.), and ADK STAB (registered trademark) AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330 (above, manufactured by ADEKA Corporation).
- IRGANOX registered trademark
- SUMILIZER registered trademark
- GA-80 GP
- MDP-S MDP-S
- BBM-S BBM-S
- WX-R aboveve, manufactured by Sumitomo Chemical Co., Ltd.
- ADK STAB registered trademark
- the content thereof is that of the component (a), the component (b), the component (c), and the component (d).
- the amount is 0.05 to 3 parts by mass, preferably 0.1 to 1 part by mass, based on 100 parts by mass of the sum.
- the phenolic antioxidant as the component (g) can be used alone or in combination of two or more.
- sulfide type antioxidant examples include ADK STAB (registered trademark) AO-412S and AO-503 (above, manufactured by ADEKA Corporation). ), IRGANOX (registered trademark) PS802, PS800 (above, manufactured by BASF), and SUMILIZER (registered trademark) TP-D (manufactured by Sumitomo Chemical Co., Ltd.).
- the content thereof is that of the component (a), the component (b), the component (c), and the component (d).
- the amount is 0.1 to 3 parts by mass, preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the sum.
- the sulfide antioxidant of the component (h) can be used alone or in combination of two or more.
- the preparation method of the photocurable composition for imprints of the present invention is not particularly limited.
- the preparation method include (a) component, (b) component, (c) component, (d) component and (e) component, and (f) component, (g) component and / or (h) as desired.
- the method of mixing a component by a predetermined ratio and making it into a uniform solution is mentioned.
- the photocurable composition for imprints of the present invention prepared in a solution is preferably used after being filtered using a filter having a pore size of 0.1 ⁇ m to 5 ⁇ m.
- the photocurable composition for imprints of the present invention can be exposed (photocured) to obtain a cured product, and the present invention also targets the cured product.
- Examples of light rays to be exposed include ultraviolet rays, electron beams, and X-rays.
- a light source used for ultraviolet irradiation for example, sunlight, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, and a UV-LED can be used.
- the post-baking method is not particularly limited, but is usually performed in a range of 50 ° C. to 260 ° C. and 1 minute to 24 hours using a hot plate, an oven or the like.
- the cured product obtained by photocuring the photocurable composition for imprints of the present invention has a high Abbe number ⁇ D of 53 or more, and a refractive index n D at a wavelength of 589 nm (D line) is 1. It is 50 or more, and yellowing by heating is not seen. Therefore, the photocurable composition for imprints of the present invention can be suitably used for resin lens formation.
- the photocurable composition for imprints of the present invention can easily produce various molded products in parallel with the formation of a cured product, for example, by using an imprint molding method.
- a method for producing a molded body for example, a filling step of filling the space between the contacting support and the mold, or the space inside the mold that can be divided, with the photocurable composition for imprints of the present invention, A photocuring step of exposing and photocuring the photocurable composition for imprint filled in the space, a releasing step of taking out the photocured product obtained by the photocuring step, and the photocured product, Examples thereof include a method including a heating step of heating before, during or after the mold release step.
- the mold release process which takes out the photocured material obtained by the said photocuring process you may further include the image development process which wash
- the method for producing the uncured portion is not particularly limited, but a portion that is not exposed by exposing only a predetermined position by mask exposure, projection exposure, or the like, that is, an uncured portion can be produced. Further, if necessary, the photocured product after the development step may be exposed again and photocured.
- the photocuring step of photocuring by exposure can be performed by applying the conditions for obtaining the above-mentioned cured product.
- the conditions of the heating step for heating the photocured product are not particularly limited, but are usually appropriately selected from the range of 50 ° C. to 260 ° C. and 1 minute to 24 hours. Moreover, it does not specifically limit as a heating means, For example, a hotplate and oven are mentioned.
- the molded body produced by such a method can be suitably used as a lens for a camera module.
- Lens molding Device Nanoimprinter for 6 inches manufactured by Meisho Kiko Co., Ltd.
- Light source High pressure mercury lamp, i-line bandpass filter HB0365 (manufactured by Asahi Spectroscopy) Through exposure Molding conditions: Pressing pressure 100 N, 20 mW / cm 2 ⁇ 300 seconds (10) Lens height measurement Device: Non-contact surface texture measuring device PF-60 manufactured by Mitaka Kogyo Co., Ltd.
- A-DCP Shin-Nakamura Chemical Co., Ltd.
- MEK-AC-2140Z manufactured by Nissan Chemical Co., Ltd.
- Trade name: Organosilica Sol MEK-AC-2140Z AOI Showa Denko Co., Ltd.
- Product name: Karenz AOI (registered trademark) BEI Showa Denko Co., Ltd.
- Product name: Karenz BEI (registered trademark) FA-513AS manufactured by Hitachi Chemical Co., Ltd.
- FANCLIL registered trademark
- FA-513AS UA-4200 Shin-Nakamura Chemical Co., Ltd.
- MEK was distilled off under conditions of 50 ° C. and a reduced pressure of 133.3 Pa or less, and the A-DCP dispersion of the surface-modified silica particles (the content of the surface-modified silica particles was 50 mass). %).
- MEK was distilled off under the conditions of 50 ° C. and a reduced pressure of 133.3 Pa or less, and the A-DCP dispersion of the surface-modified silica particles (the content of the surface-modified silica particles was 55 mass). %).
- the reaction solution was returned to room temperature and reprecipitated and dried using methanol cooled to 10 ° C., thereby obtaining 53.0 g of polymer 1 having a repeating structural unit represented by the following formula (A).
- the weight average molecular weight Mw measured by polystyrene conversion by GPC of the obtained polymer 1 was 12,900.
- Example 1 (A) Solid content of the A-DCP dispersion obtained in Production Example 1 as the surface-modified silica particles, (b) A-DCP as the alicyclic (meth) acrylate monomer, (c) Urethane (meta ) UA-4200 as acrylate compound, (d) polymer 1 obtained in Production Example 3 as the polymer, (e) I184 as photo radical initiator, (g) I245 as phenolic antioxidant, and (h) sulfide AO-503 was added as a system antioxidant in the proportions shown in Table 1 below.
- the proportion of A-DCP shown in Table 1 below includes the A-DCP component contained in the A-DCP dispersion.
- the blend was shaken at 50 ° C. for 3 hours and mixed, and then (f) NR1 was added as the polyfunctional thiol compound, and the mixture was stirred and mixed for 30 minutes using the stirring and deaerator. Furthermore, the photocurable composition 1 for imprinting was prepared by carrying out stirring deaeration for 10 minutes using the same apparatus.
- “part” represents “part by mass”.
- Example 2 to Example 8 Comparative Example 1 to Comparative Example 3
- the components (a) to (h) were mixed at the ratios shown in Table 1 to prepare photocurable compositions 2 to 11 for imprinting.
- Example 4 does not use the component (f)
- Comparative Example 1 does not use the components (a), (d), and (f)
- Comparative Example 2 uses the components (a) and (f).
- No component is used
- Comparative Example 3 does not use the component (d) and the component (f).
- the transmittance at a wavelength of 410 nm of the cured film produced by the above method was measured using the ultraviolet visible near infrared spectrophotometer. The results are shown in Table 2 below. Further, the cured film was placed on a silicon wafer, and heated for 2 minutes and 30 seconds on a hot plate heated to 175 ° C. through the silicon wafer to perform a heat resistance test. The transmittance at a wavelength of 410 nm of the cured film after the heat resistance test was measured using the ultraviolet-visible-near infrared spectrophotometer, and heat yellowing was evaluated from the transmittance change before and after heating. The results are shown in Table 2 below.
- This sandwiched photocurable composition was subjected to UV exposure at 62 mW / cm 2 for 5 seconds through an i-line bandpass filter (manufactured by Asahi Spectroscopy) using the UV irradiation apparatus.
- the cured product obtained after the exposure is peeled off from the release-treated glass substrate, then immersed (developed) in stirred PGMEA, and further rinsed with PGMEA to remove the unexposed portion, whereby the adhesion A cured film having a size of 1 cm square and a thickness of 0.5 mm was produced on the treated 4-inch glass wafer.
- NOVEC registered trademark 1720 (manufactured by 3M Japan) was applied to 0.020 g of the photocurable composition for imprints prepared in Examples 1 to 8 and Comparative Examples 1 to 3, and dried. It weighed on the glass substrate which carried out the mold release process. Then, through a 300 ⁇ m thick silicone rubber spacer, a coating solution obtained by diluting 5% by mass of PGMEA with an adhesion aid (product name: KBM-5103) manufactured by Shin-Etsu Chemical Co., Ltd. is applied and dried. The imprinted photocurable composition on the glass substrate was sandwiched between the quartz substrates (6 cm square, 1 mm thickness).
- This sandwiched photocurable composition was subjected to UV exposure at 20 mW / cm 2 for 300 seconds through an i-line bandpass filter (manufactured by Asahi Spectroscopy) using the UV irradiation apparatus.
- the cured product obtained after the exposure is peeled off from the glass substrate, and then heated on a hot plate at 100 ° C. for 10 minutes, so that the quartz substrate has a diameter of 1 cm, a thickness of 0.3 mm, and a mass of 0.020 g.
- a cured film was produced.
- a 200 nm-thick silicon oxide layer was formed as an antireflection layer under the film formation conditions using the RF sputtering apparatus.
- the antireflection layer on the cured film was observed to confirm the presence or absence of cracks, and then the quartz substrate was heated on a hot plate at 175 ° C. for 2 minutes 30 seconds. A sex test was performed.
- the quartz substrate after the heat resistance test the presence or absence of cracks in the antireflection layer on the cured film was observed using the optical microscope manufactured by Keyence Co., Ltd., and the crack resistance of the antireflection layer was determined.
- the antireflection layer formed on the cured film prepared from the photocurable composition for imprints of Comparative Example 1 not containing the component (a) and the component (d) and Comparative Example 2 not containing the component (a) As a result, cracks occurred after the heat resistance test. Furthermore, the cured film produced from the photocurable composition for imprints of Comparative Example 3 containing the component (a) but not the component (d) is subjected to a development step of washing the uncured portion using an organic solvent. As a result, cracks occurred on the side walls of the cured film.
- the cured film obtained from the photocurable composition for imprints of the present invention exhibits a high Abbe number, a high refractive index, high transparency, and heat-resistant yellowing, and the reflection of the upper layer of the cured film. It is shown that the prevention layer has desirable characteristics as a lens for a high-resolution camera module in which neither cracks nor wrinkles are generated by heat treatment at 175 ° C., and the cured film does not crack even when exposed to an organic solvent. It was.
- a mold made of nickel (lens mold of 2 mm diameter ⁇ 300 ⁇ m depth, arranged in a total of 15 rows ⁇ 3 rows ⁇ 5 rows) and a nanoimprinter, according to the method for producing a molded body described above, is a support Molded into a lens shape on a glass substrate.
- template was previously mold-released by NOVEC (trademark) 1720 (made by 3M Japan Co., Ltd.).
- the glass substrate used was subjected to adhesion treatment by applying a solution prepared by diluting an adhesion aid (product name: KBM-5103) manufactured by Shin-Etsu Chemical Co., Ltd. with PGMEA to 5% by mass and drying. After removing the cured product from the mold, the cured product was heated on a hot plate at 100 ° C. for 10 minutes to produce a convex lens on the glass substrate subjected to the adhesion treatment.
- an adhesion aid product name: KBM-5103
- PGMEA Shin-Etsu Chemical Co., Ltd. with PGMEA
- the lens height (thickness) before and after the heating test was measured with the non-contact surface property measuring apparatus, and the rate of change was calculated by the following formula “[(lens height before heating ⁇ heating (Lens height after) / Lens height before heating] ⁇ 100 ”, and dimensional stability by heating was evaluated. Moreover, the presence or absence of the generation
- the heating test is a test in which a convex lens obtained on a glass substrate is heated on a hot plate at 175 ° C. for 2 minutes and 30 seconds and then allowed to cool to room temperature (approximately 23 ° C.). The results are shown in Table 3 below.
- the convex lens obtained from the photocurable composition for imprints of the present invention has a small change in lens height even after a thermal history of 175 ° C. for 2 minutes and 30 seconds (change rate: 0.1%). 20% or less) and high dimensional stability was obtained.
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Abstract
Description
(a):一次粒子径が1nm乃至100nmの表面修飾されたシリカ粒子
(b):1分子中に(メタ)アクリロイルオキシ基を少なくとも1つ有する脂環式(メタ)アクリレートモノマー(ただし、(c)成分の化合物を除く。)
(c):ウレタン(メタ)アクリレート化合物又はエポキシ(メタ)アクリレート化合物(ただし、(d)成分のポリマーを除く。)
(d):下記式(1)で表される繰り返し構造単位及び下記式(2)で表される繰り返し構造単位を有するポリマー
(e):光ラジカル開始剤
(f):下記式(3)で表される多官能チオール化合物
ここで、ヘテロ原子とは、炭素原子及び水素原子以外の原子を表し、例えば窒素原子、酸素原子及び硫黄原子が挙げられる。
(g):フェノール系酸化防止剤
(h):スルフィド系酸化防止剤
前記Z3がエチレンオキシ基(-CH2CH2O-基)を表す場合、該エチレンオキシ基のO原子は前記脂環式炭化水素基を表すA4と結合する。
本発明のインプリント用光硬化性組成物の(a)成分として使用可能な表面修飾されたシリカ粒子は、一次粒子径が1nm乃至100nmである。ここで、一次粒子とは、紛体を構成する粒子であり、この一次粒子が凝集した粒子を二次粒子という。前記一次粒子径は、ガス吸着法(BET法)により測定される前記表面修飾されたシリカ粒子の比表面積(単位質量あたりの表面積)S、該表面修飾されたシリカ粒子の密度ρ、及び一次粒子径Dとの間に成り立つ関係式:D=6/(ρS)から算出することができる。該関係式から算出される一次粒子径は、平均粒子径であり、一次粒子の直径である。また、前記表面修飾されたシリカ粒子は、例えば、二価の連結基を介してケイ素原子と結合した(メタ)アクリロイルオキシ基で表面修飾されている。上記表面修飾されたシリカ粒子を用いる際には、該表面修飾されたシリカ粒子をそのまま用いてもよく、該表面修飾されたシリカ粒子を分散媒である有機溶剤に予め分散させたコロイド状態のもの(コロイド粒子が分散媒に分散したゾル)を用いてもよい。該表面修飾されたシリカ粒子を含むゾルを用いる場合、固形分の濃度が10質量%乃至60質量%の範囲のゾルを用いることができる。
本発明のインプリント用光硬化性組成物の(b)成分として使用可能な脂環式(メタ)アクリレートモノマーは、該モノマー1分子中に(メタ)アクリロイルオキシ基を少なくとも1つ、例えば1つ又は2つ、及び脂環式炭化水素を1つ有し、且つ後述する(c)成分の化合物を除くモノマー化合物である。該脂環式(メタ)アクリレートモノマーとして、例えば、シクロペンチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、3,3,5-トリメチルシクロヘキシル(メタ)アクリレート、4-tert-ブチルシクロヘキシル(メタ)アクリレート、メンチル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ノルボルニル(メタ)アクリレート、1-アダマンチル(メタ)アクリレート、2-アダマンチル(メタ)アクリレート、2-メチルアダマンタン-2-イル(メタ)アクリレート、2-エチルアダマンタン-2-イル(メタ)アクリレート、トリシクロ[5.2.1.0(2,6)]デカニル(メタ)アクリレート、トリシクロ[5.2.1.0(2,6)]デカニルオキシエチル(メタ)アクリレート、1,4-シクロヘキサンジメタノールジ(メタ)アクリレート、トリシクロ[5.2.1.0(2,6)]デカンジメタノールジ(メタ)アクリレート、及び1,3-アダマンタンジオールジ(メタ)アクリレートが挙げられる。
本発明のインプリント用光硬化性組成物の(c)成分として使用可能なウレタン(メタ)アクリレート化合物は、1分子中に(メタ)アクリロイルオキシ基を少なくとも2つ及び“-NH-C(=O)O-”で表されるウレタン構造を少なくとも2つ有し、且つ後述する(d)成分のポリマーを除く化合物である。該ウレタン(メタ)アクリレート化合物として、例えば、EBECRYL(登録商標)230、同270、同280/15IB、同284、同4491、同4683、同4858、同8307、同8402、同8411、同8804、同8807、同9270、同8800、同294/25HD、同4100、同4220、同4513、同4738、同4740、同4820、同8311、同8465、同9260、同8701、KRM7735、同8667、同8296(以上、ダイセル・オルネクス(株)製)、UV-2000B、UV-2750B、UV-3000B、UV-3200B、UV-3210EA、UV-3300B、UV-3310B、UV-3500B、UV-3520EA、UV-3700B、UV-6640B、UV-6630B、UV-7000B、UV-7510B、UV-7461TE(以上、日本合成化学(株)製)、UA-306H、UA-306T、UA-306I、UA-510H、UF-8001G(以上、共栄社化学(株)製)、M-1100、M-1200(以上、東亞合成(株)製)、及びNKオリゴU-2PPA、同U-6LPA、同U-200PA、U-200PA、同U-160TM、同U-290TM、同UA-4200、同UA-4400、同UA-122P、同UA-7100、同UA-W2A(以上、新中村化学工業(株)製)が挙げられる。
本発明のインプリント用光硬化性組成物の(d)成分として使用可能なポリマーは、重合性基を含む共重合体であり、前記式(1)で表される繰り返し構造単位及び前記式(2)で表される繰り返し構造単位を少なくとも有し、前記式(4)で表される繰り返し構造単位をさらに有してもよい。
本発明のインプリント用光硬化性組成物の(e)成分として使用可能な光ラジカル開始剤として、例えば、アルキルフェノン類、ベンゾフェノン類、ミヒラー(Michler)のケトン類、アシルホスフィンオキシド類、ベンゾイルベンゾエート類、オキシムエステル類、テトラメチルチウラムモノスルフィド類及びチオキサントン類が挙げられ、特に、光開裂型の光ラジカル重合開始剤が好ましい。前記光ラジカル開始剤として市販品、例えば、IRGACURE(登録商標)184、同369、同651、同500、同819、同907、同784、同2959、同CGI1700、同CGI1750、同CGI1850、同CG24-61、同TPO、同1116、同1173(以上、BASFジャパン(株)製)、及びESACURE KIP150、同KIP65LT、同KIP100F、同KT37、同KT55、同KTO46、同KIP75(以上、Lamberti社製)を採用することができる。
本発明のインプリント用光硬化性組成物の(f)成分として使用可能な多官能チオール化合物は、前記式(3)で表される多官能チオール化合物である。該式(3)で表される多官能チオール化合物として、例えば、1,2-エタンジチオール、1,3-プロパンジチオール、ビス(2-メルカプトエチル)エーテル、トリメチロールプロパントリス(3-メルカプトプロピオネート)、トリス-[(3-メルカプトプロピオニルオキシ)-エチル]-イソシアヌレート、テトラエチレングリコールビス(3-メルカプトプロピオネート)、ジペンタエリスリトールヘキサキス(3-メルカプトプロピオネート)、ペンタエリスリトールテトラキス(3-メルカプトブチレート)、1,4-ビス(3-メルカプトブチリルオキシ)ブタン、1,3,5-トリス(3-メルカプトブチリルオキシエチル)-1,3,5-トリアジン-2,4,6-(1H,3H,5H)-トリオン、トリメチロールプロパントリス(3-メルカプトブチレート)、及びトリメチロールエタントリス(3-メルカプトブチレート)、ペンタエリスリトールトリス(3-メルカプトプロピル)エーテルが挙げられる。前記式(3)で表される多官能チオール化合物として、市販品、例えば、カレンズMT(登録商標)PE1、同NR1、同BD1、TPMB、TEMB(以上、昭和電工(株)製)、及びTMMP、TEMPIC、PEMP、EGMP-4、DPMP、TMMP II-20P、PEMP II-20P、PEPT(以上、SC有機化学(株)製)を採用することができる。
本発明のインプリント用光硬化性組成物の(g)成分として使用可能なフェノール系酸化防止剤として、例えば、IRGANOX(登録商標)245、同1010、同1035、同1076、同1135(以上、BASFジャパン(株)製)、SUMILIZER(登録商標)GA-80、同GP、同MDP-S、同BBM-S、同WX-R(以上、住友化学(株)製)、及びアデカスタブ(登録商標)AO-20、同AO-30、同AO-40、同AO-50、同AO-60、同AO-80、同AO-330(以上、(株)ADEKA製)が挙げられる。
本発明のインプリント用光硬化性組成物の(h)成分として使用可能なスルフィド系酸化防止剤として、例えば、アデカスタブ(登録商標)AO-412S、同AO-503(以上、(株)ADEKA製)、IRGANOX(登録商標)PS802、同PS800(以上、BASF社製)、及びSUMILIZER(登録商標)TP-D(住友化学(株)製)が挙げられる。
本発明のインプリント用光硬化性組成物の調製方法は、特に限定されない。調製法としては、例えば、(a)成分、(b)成分、(c)成分、(d)成分及び(e)成分、並びに所望により(f)成分、(g)成分及び/又は(h)成分を所定の割合で混合し、均一な溶液とする方法が挙げられる。
本発明のインプリント用光硬化性組成物を、露光(光硬化)して、硬化物を得ることができ、本発明は該硬化物も対象とする。露光する光線としては、例えば、紫外線、電子線及びX線が挙げられる。紫外線照射に用いる光源としては、例えば、太陽光線、ケミカルランプ、低圧水銀灯、高圧水銀灯、メタルハライドランプ、キセノンランプ、及びUV-LEDが使用できる。また、露光後、硬化物の物性を安定化させるためにポストベークを施してもよい。ポストベークの方法としては、特に限定されないが、通常、ホットプレート、オーブン等を使用して、50℃乃至260℃、1分乃至24時間の範囲で行われる。
本発明のインプリント用光硬化性組成物は、例えばインプリント成形法を使用することによって、硬化物の形成と並行して各種成形体を容易に製造することができる。成形体を製造する方法としては、例えば接し合う支持体と鋳型との間の空間、又は分割可能な鋳型の内部の空間に本発明のインプリント用光硬化性組成物を充填する充填工程、該空間に充填されたインプリント用光硬化性組成物を露光して光硬化する光硬化工程、該光硬化工程により得られた光硬化物を取り出す離型工程、並びに、該光硬化物を、該離型工程の前、中途又は後において加熱する加熱工程を含む方法が挙げられる。その際、前記光硬化工程により得られた光硬化物を取り出す離型工程の後、前記加熱工程の前に有機溶媒にて未硬化部を洗浄・除去する現像工程をさらに含んでもよい。前記未硬化部を作製する手法としては、特に制限はないが、マスク露光、投影露光等により所定の位置のみを露光することで露光されない部分、すなわち未硬化部を作製することができる。さらに、必要に応じて、前記現像工程後の光硬化物を、再度露光して光硬化してもよい。
装置:(株)島津製作所製 GPCシステム
カラム:昭和電工(株)製 Shodex(登録商標)GPC KF-804L、GPC KF-803L
カラム温度:40℃
溶媒:テトラヒドロフラン
標準試料:ポリスチレン
(2)撹拌脱泡機
装置:(株)シンキー製 自転・公転ミキサー あわとり練太郎(登録商標)ARE-310
(3)UV露光
装置:アイグラフィックス(株)製 バッチ式UV照射装置(高圧水銀灯2kW×1灯)
(4)透過率
装置:日本分光(株)製 紫外可視近赤外分光光度計V-670
リファレンス:空気
(5)屈折率nD、アッベ数νD
装置:アントンパール社製 多波長屈折計Abbemat MW
測定温度:23℃
(6)光学顕微鏡(有機溶媒を用いた現像工程における耐クラック性の評価)
装置:オリンパス(株)製 MX61A、DP72、BX-UCB
条件:反射(明視野)、対物5倍
(7)反射防止層の成膜
装置:サンユー電子(株)製 RFスパッタ装置SRS-700T/LL
方式:RFスパッタ・マグネトロン方式
条件:ターゲット材=シリコン、RFパワー=250W、
ターゲット・基板間の垂直距離=100mm、オフセット距離=100mm、
Ar流量=45sccm、O2流量=2sccm、
温度=室温、スパッタ時間=15分
(8)光学顕微鏡(反射防止膜の観察)
装置:(株)キーエンス製 VHX-1000、VH-Z1000R
条件:反射(明視野)、対物500倍
(9)レンズ成型
装置:明昌機工(株)製 6インチ対応ナノインプリンター
光源:高圧水銀灯、i線バンドパスフィルターHB0365(朝日分光(株)製)を介 して露光
成型条件:押し付け圧100N、20mW/cm2×300秒
(10)レンズ高さ測定
装置:三鷹光器(株)製 非接触表面性状測定装置PF-60
A-DCP:新中村化学工業(株)製 商品名:NKエステル A-DCP
MEK-AC-2140Z:日産化学(株)製 商品名:オルガノシリカゾル MEK-AC-2140Z
AOI:昭和電工(株)製 商品名:カレンズAOI(商標登録)
BEI:昭和電工(株)製 商品名:カレンズBEI(商標登録)
FA-513AS:日立化成(株)製 商品名:ファンクリル(登録商標)FA-513AS
UA-4200:新中村化学工業(株)製 商品名:NKオリゴ UA-4200
DA-212:ナガセケムテックス(株)製 商品名:デナコールアクレートDA-212
NR1:昭和電工(株)製 商品名:カレンズ(登録商標)MT NR1
I184:BASFジャパン(株)製 商品名:Irgacure(登録商標)184
I245:BASFジャパン(株)製 商品名:Irganox(登録商標)245
AO-503:(株)ADEKA製 商品名:アデカスタブ(登録商標)AO-503
500mLナスフラスコに、(b)前記脂環式(メタ)アクリレートモノマーとしてA-DCP 120gを秤量し、メチルエチルケトン(以下、本明細書ではMEKと略称する。)120gにて溶解させた。その後、(a)前記表面修飾されたシリカ粒子として、MEK-AC-2140Z((メタ)アクリロイルオキシ基で表面修飾された一次粒子径10nm~15nmのシリカ粒子、固形分46質量%のMEK分散液)260.3gを加え、撹拌して均一化した。その後、エバポレーターを用いて、50℃、減圧度133.3Pa以下の条件でMEKを留去し、前記表面修飾されたシリカ粒子のA-DCP分散液(該表面修飾されたシリカ粒子含有量50質量%)を得た。
500mLナスフラスコに、(b)前記脂環式(メタ)アクリレートモノマーとしてA-DCP 112.5gを秤量し、メチルエチルケトン(以下、本明細書ではMEKと略称する。)112.5gにて溶解させた。その後、(a)前記表面修飾されたシリカ粒子として、MEK-AC-2140Z((メタ)アクリロイルオキシ基で表面修飾された一次粒子径10nm~15nmのシリカ粒子、固形分46質量%のMEK分散液)305gを加え、撹拌して均一化した。その後、エバポレーターを用いて、50℃、減圧度133.3Pa以下の条件でMEKを留去し、前記表面修飾されたシリカ粒子のA-DCP分散液(該表面修飾されたシリカ粒子含有量55質量%)を得た。
滴下ロート付き4つ口フラスコ中にプロピレングリコールモノメチルエーテルアセテート(以下、本明細書ではPGMEAと略称する。)を45.2g仕込み、さらに該滴下ロート中にメチルメタクリレート50.0g、イソボルニルアクリレート29.7g、2-ヒドロキシエチルメタクリレート9.28g、及び2,2’-アゾビスイソブチロニトリル5.86gをPGMEA176.2gに溶解させた溶液を加えた。前記4つ口フラスコ内の雰囲気を窒素置換後、該4つ口フラスコ内を80℃に昇温し、前記滴下ロート中の溶液を3時間かけて該4つ口フラスコ中に滴下した。滴下終了後、12時間反応させ、さらに110℃で1時間撹拌した後、前記4つ口フラスコ内の温度を60℃まで低下させた。得られた反応溶液にp-メトキシフェノール0.266g、ジラウリン酸ジブチル錫0.451g、及びAOI 15.1gを加え、60℃で3時間撹拌させた。反応溶液を室温に戻し、10℃に冷却したメタノールを用いて再沈殿・乾燥させることで、下記式(A)で表される繰り返し構造単位を有するポリマー1を53.0g得た。得られたポリマー1の、GPCによるポリスチレン換算で測定される重量平均分子量Mwは、12,900であった。
滴下ロート付き4つ口フラスコ中にPGMEAを26.5g仕込み、さらに該滴下ロート中にメチルメタクリレート45.0g、2-ヒドロキシエチルメタクリレート6.50g、及び2,2’-アゾビスイソブチロニトリル4.10gをPGMEA103.3gに溶解させた溶液を加えた。前記4つ口フラスコ内の雰囲気を窒素置換後、該4つ口フラスコ内を80℃に昇温し、前記滴下ロート中の溶液を3時間かけて該4つ口フラスコ中に滴下した。滴下終了後、12時間反応させ、さらに110℃で1時間撹拌した後、前記4つ口フラスコ内の温度を60℃まで低下させた。得られた反応溶液にp-メトキシフェノール0.186g、ジラウリン酸ジブチル錫0.315g、及びAOI 10.6gを加え、60℃で3時間撹拌させた。反応溶液を室温に戻し、10℃に冷却したメタノールを用いて再沈殿・乾燥させることで、下記式(B)で表される構造単位を有するポリマー2を27.7g得た。得られたポリマー2の、GPCによるポリスチレン換算で測定される重量平均分子量Mwは、10,200であった。
滴下ロート付き4つ口フラスコ中にPGMEAを33.1g仕込み、さらに該滴下ロート中にメチルメタクリレート25.0g、イソボルニルアクリレート20.8g、2-ヒドロキシエチルメタクリレート19.5g、及び2,2’-アゾビスイソブチロニトリル4.10gをPGMEA128.9gに溶解させた溶液を加えた。前記4つ口フラスコ内の雰囲気を窒素置換後、該4つ口フラスコ内を80℃に昇温し、前記滴下ロート中の溶液を3時間かけて該4つ口フラスコ中に滴下した。滴下終了後、12時間反応させ、さらに110℃で1時間撹拌した後、前記4つ口フラスコ内の温度を60℃まで低下させた。得られた反応溶液にp-メトキシフェノール0.558g、ジラウリン酸ジブチル錫0.946g、及びBEI 53.8gを加え、60℃で3時間撹拌させた。反応溶液を室温に戻し、10℃に冷却したメタノールを用いて再沈殿・乾燥させることで、下記式(C)で表される構造単位を有するポリマー3を4.36g得た。得られたポリマー3の、GPCによるポリスチレン換算で測定される重量平均分子量Mwは、17,000であった。
(a)前記表面修飾されたシリカ粒子として製造例1で得た前記A-DCP分散液の固形分、(b)前記脂環式(メタ)アクリレートモノマーとしてA-DCP、(c)ウレタン(メタ)アクリレート化合物としてUA-4200、(d)前記ポリマーとして前記製造例3で得たポリマー1、(e)光ラジカル開始剤としてI184、(g)フェノール系酸化防止剤としてI245、及び(h)スルフィド系酸化防止剤としてAO-503を、それぞれ下記表1に記載の割合で配合した。なお、下記表1に示すA-DCPの割合は、前記A-DCP分散液に含まれるA-DCP成分を含む。その後、配合物を50℃で3時間振とうさせ、混合した後、(f)前記多官能チオール化合物としてNR1を添加し、前記撹拌脱泡機を用いて30分間、撹拌混合した。さらに同装置を用いて10分間撹拌脱泡することでインプリント用光硬化性組成物1を調製した。なお、下記表1中、「部」は「質量部」を表す。
前記実施例1と同様の手順にて、(a)成分乃至(h)成分を下記表1に示す割合で混合することで、インプリント用光硬化性組成物2乃至11を調製した。ただし、実施例4は(f)成分を使用せず、比較例1は(a)成分及び(d)成分並びに(f)成分を使用せず、比較例2は(a)成分及び(f)成分を使用せず、比較例3は(d)成分及び(f)成分を使用しない。
実施例1乃至実施例8及び比較例1乃至比較例3で調製した各インプリント用光硬化性組成物を、500μm厚のシリコーンゴム製スペーサーとともに、NOVEC(登録商標)1720(スリーエムジャパン(株)製)を塗布し乾燥することで離型処理したガラス基板2枚で挟み込んだ。この挟み込んだインプリント用光硬化性組成物を、前記UV照射装置を用いてi線バンドパスフィルター(朝日分光(株)製)を介して20mW/cm2で300秒間UV露光した。露光後得られた硬化物を、前記離型処理したガラス基板から剥離した後、100℃のホットプレートで10分間加熱することで、直径3cm、厚さ0.5mmの硬化膜を作製した。
前記の方法で作製した硬化膜の波長410nmの透過率を、前記紫外可視近赤外分光光度計を用いて測定した。結果を下記表2に示す。さらに前記硬化膜をシリコンウェハ上に置き、該シリコンウェハを介して、175℃に加熱したホットプレート上で2分30秒間加熱し、耐熱性試験を行った。耐熱性試験後の硬化膜の波長410nmの透過率を、前記紫外可視近赤外分光光度計を用いて測定し、加熱前後の透過率変化から耐熱黄変性を評価した。結果を下記表2に合わせて示す。
前記の方法で作製した硬化膜の波長589nmにおける屈折率nD、及びアッベ数νDを、前記多波長屈折計を用いて測定した。結果を下記表2に合わせて示す。
実施例1乃至実施例8及び比較例1乃至比較例3で調製した各インプリント用光硬化性組成物を、NOVEC(登録商標)1720(スリーエムジャパン(株)製)を塗布し乾燥することで離型処理したフォトマスク基板(開口部1cm角)上に滴下した。その後、500μm厚のシリコーンゴム製スペーサーを介して、信越化学工業(株)製接着補助剤(製品名:KBM-5103)をPGMEAで5質量%に希釈した溶液を塗布し乾燥することで密着処理した4インチガラスウェハ(0.7mm厚)で挟み込んだ。この挟み込んだ光硬化性組成物を、前記UV照射装置を用いてi線バンドパスフィルター(朝日分光(株)製)を介して62mW/cm2で5秒間UV露光した。露光後得られた硬化物を、前記離型処理したガラス基板から剥離した後、撹拌されたPGMEA中に浸漬(現像)し、さらにPGMEAでリンスして未露光部を除去することで、前記密着処理した4インチガラスウェハ上に、1cm角、厚さ0.5mmの硬化膜を作製した。得られた硬化膜を、前記オリンパス(株)製光学顕微鏡にて硬化膜の側面を観察し、クラックが確認されるものを×、クラックが観測されないものを○と判定した。結果を下記表2に合わせて示す。
実施例1乃至実施例8及び比較例1乃至比較例3で調製した各インプリント用光硬化性組成物0.020gを、NOVEC(登録商標)1720(スリーエムジャパン(株)製)を塗布し乾燥することで離型処理したガラス基板上に秤量した。その後、300μm厚のシリコーンゴム製スペーサーを介して、信越化学工業(株)製接着補助剤(製品名:KBM-5103)をPGMEAで5質量%に希釈した溶液を塗布し乾燥することで密着処理した石英基板(6cm角、1mm厚)で、前記ガラス基板上のインプリント用光硬化性組成物を挟み込んだ。この挟み込んだ光硬化性組成物を、前記UV照射装置を用いてi線バンドパスフィルター(朝日分光(株)製)を介して20mW/cm2で300秒間UV露光した。露光後得られた硬化物を、前記ガラス基板から剥離した後、100℃のホットプレートで10分間加熱することで、前記石英基板上に、直径1cm、厚さ0.3mm及び質量0.020gの硬化膜を作製した。
実施例1で調製したインプリント用光硬化性組成物1、実施例4で調製したインプリント用光硬化性組成物4及び実施例8で調製したインプリント用光硬化性組成物8を、それぞれ、ニッケル製の鋳型(2mm径×300μm深さのレンズ型を、縦3列×横5列の計15個配置)及びナノインプリンターを用い、前述の成形体の製造方法に従って、支持体であるガラス基板上でレンズ形状に成形した。なお、使用した鋳型は、予めNOVEC(登録商標)1720(スリーエムジャパン(株)製)で離型処理した。また、使用したガラス基板は、予め信越化学工業(株)製接着補助剤(製品名:KBM-5103)をPGMEAで5質量%に希釈した溶液を塗布し乾燥することで密着処理した。前記鋳型から硬化物を外した後、該硬化物を100℃のホットプレートで10分間加熱することで、前記密着処理したガラス基板上に凸レンズを作製した。
Claims (15)
- 下記(a)成分、下記(b)成分、下記(c)成分、下記(d)成分及び下記(e)成分を含み、該(a)成分、該(b)成分、該(c)成分及び該(d)成分の和100質量部に対し、該(a)成分が10質量部乃至40質量部、該(b)成分が10質量部乃至50質量部、該(c)成分が10質量部乃至50質量部、該(d)成分が1質量部乃至10質量部、及び該(e)成分が0.1質量部乃至5質量部である、インプリント用光硬化性組成物。
(a):一次粒子径が1nm乃至100nmの表面修飾されたシリカ粒子
(b):1分子中に(メタ)アクリロイルオキシ基を少なくとも1つ有する脂環式(メタ)アクリレートモノマー(ただし、(c)成分の化合物を除く。)
(c):ウレタン(メタ)アクリレート化合物又はエポキシ(メタ)アクリレート化合物(ただし、(d)成分のポリマーを除く。)
(d):下記式(1)で表される繰り返し構造単位及び下記式(2)で表される繰り返し構造単位を有するポリマー
(e):光ラジカル開始剤
- さらに、前記(a)成分、前記(b)成分、前記(c)成分及び前記(d)成分の和100質量部に対し0.05質量部乃至3質量部の下記(g)成分、及び/又は前記(a)成分、前記(b)成分、前記(c)成分及び前記(d)成分の和100質量部に対し0.1質量部乃至3質量部の下記(h)成分を含む、請求項1又は請求項2に記載のインプリント用光硬化性組成物。
(g):フェノール系酸化防止剤
(h):スルフィド系酸化防止剤 - 前記(a)成分が、二価の連結基を介してケイ素原子と結合した(メタ)アクリロイルオキシ基で表面修飾されたシリカ粒子である、請求項1乃至請求項3のいずれか一項に記載のインプリント用光硬化性組成物。
- 前記(c)成分のウレタン(メタ)アクリレート化合物又はエポキシ(メタ)アクリレート化合物は、1分子中に(メタ)アクリロイルオキシ基を2つ又は3つ有する化合物である、請求項1乃至請求項4のいずれか一項に記載のインプリント用光硬化性組成物。
- 前記炭素原子数5乃至13の脂環式炭化水素基は、シクロペンチル基、シクロヘキシル基、イソボルニル基、ジシクロペンタニル基、ジシクロペンテニル基、又は炭素原子数1乃至3のアルキル基を置換基として有してもよいアダマンチル基である、請求項6に記載のインプリント用光硬化性組成物。
- 前記インプリント用光硬化性組成物は、その硬化物の波長589nmにおける屈折率nDが1.50以上であり、かつ該硬化物のアッベ数νDが53以上である、請求項1乃至請求項8のいずれか一項に記載のインプリント用光硬化性組成物。
- 請求項9に記載のインプリント用光硬化性組成物の硬化物。
- 請求項1乃至請求項9のいずれか一項に記載のインプリント用光硬化性組成物をインプリント成形する工程を含む、樹脂レンズの製造方法。
- インプリント用光硬化性組成物の成形体の製造方法であって、請求項1乃至請求項9のいずれか一項に記載のインプリント用光硬化性組成物を、接し合う支持体と鋳型との間の空間、又は分割可能な鋳型の内部の空間に充填する充填工程、及び該空間に充填されたインプリント用光硬化性組成物を露光して光硬化する光硬化工程を含む、成形体の製造方法。
- 前記光硬化工程の後、得られた光硬化物を取り出す離型工程、並びに、該光硬化物を、該離型工程の前、中途又は後において加熱する加熱工程を含む、請求項12に記載の成形体の製造方法。
- 前記離型工程後、前記加熱工程の前に有機溶媒を用いて未硬化部を洗浄する現像工程をさらに含む、請求項13に記載の成形体の製造方法。
- 前記成形体がカメラモジュール用レンズである、請求項12乃至請求項14のいずれか一項に記載の成形体の製造方法。
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- 2019-01-18 KR KR1020207026632A patent/KR20200128404A/ko unknown
- 2019-01-18 WO PCT/JP2019/001392 patent/WO2019167461A1/ja active Application Filing
- 2019-01-18 CN CN201980015183.5A patent/CN111801770A/zh active Pending
- 2019-01-30 TW TW108103417A patent/TW201940602A/zh unknown
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KR20230083284A (ko) | 2020-10-08 | 2023-06-09 | 디아이씨 가부시끼가이샤 | 활성 에너지선 경화성 조성물, 경화물, 렌즈 및 카메라 모듈 |
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CN111801770A (zh) | 2020-10-20 |
TW201940602A (zh) | 2019-10-16 |
JPWO2019167461A1 (ja) | 2021-03-11 |
KR20200128404A (ko) | 2020-11-12 |
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