WO2019082625A1 - インプリント用光硬化性組成物 - Google Patents

インプリント用光硬化性組成物

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Publication number
WO2019082625A1
WO2019082625A1 PCT/JP2018/037452 JP2018037452W WO2019082625A1 WO 2019082625 A1 WO2019082625 A1 WO 2019082625A1 JP 2018037452 W JP2018037452 W JP 2018037452W WO 2019082625 A1 WO2019082625 A1 WO 2019082625A1
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WIPO (PCT)
Prior art keywords
component
photocurable composition
mass
parts
imprints
Prior art date
Application number
PCT/JP2018/037452
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
偉大 長澤
圭介 首藤
Original Assignee
日産化学株式会社
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Filing date
Publication date
Application filed by 日産化学株式会社 filed Critical 日産化学株式会社
Priority to JP2019550941A priority Critical patent/JP6974803B2/ja
Priority to KR1020207007402A priority patent/KR102649151B1/ko
Priority to CN201880068792.2A priority patent/CN111263779B/zh
Publication of WO2019082625A1 publication Critical patent/WO2019082625A1/ja

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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
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • 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
    • 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
    • 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
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • 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
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/014—Stabilisers against oxidation, heat, light or ozone
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/13—Phenols; Phenolates
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • G02B3/0006—Arrays
    • G02B3/0012—Arrays characterised by the manufacturing method
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F9/00—Registration or positioning of originals, masks, frames, photographic sheets or textured or patterned surfaces, e.g. automatically
    • G03F9/70—Registration or positioning of originals, masks, frames, photographic sheets or textured or patterned surfaces, e.g. automatically for microlithography
    • G03F9/7003—Alignment type or strategy, e.g. leveling, global alignment
    • G03F9/7042—Alignment for lithographic apparatus using patterning methods other than those involving the exposure to radiation, e.g. by stamping or imprinting

Definitions

  • the present invention relates to at least one of an alicyclic (meth) acrylate compound, a urethane (meth) acrylate compound or an epoxy (meth) acrylate compound, a silane compound having a (meth) acryloyloxy group as a polymerizable group, or the silane compound. And a photocurable composition for imprints containing a photoradical initiator.
  • the invention also relates to a photocurable composition in which a crack does not occur in the antireflective layer even after heat treatment after forming the antireflective layer (AR layer) on the upper layer of the molded product.
  • 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 devices. Moreover, according to the use aspect, high durability, for example, heat resistance and weather resistance, and high productivity which can be molded with high yield are required.
  • thermoplastic transparent resins such as polycarbonate resins, cycloolefin polymers, and methacrylic resins have been used.
  • a lens having low wavelength dispersion that is, a lens having a high Abbe number is mainly used, and an optical material for forming the lens is required.
  • resin lenses in order to improve yield and production efficiency, and to suppress misalignment of the optical axis during lens lamination, from injection molding of a thermoplastic resin, pressing using a curable resin which is liquid at room temperature The transition to wafer-level forming 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 radical curable resin composition is conventionally used from the viewpoint of high transparency, heat resistant yellowing and releasability from a mold (Patent Document 1) ).
  • cured material of a high Abbe number is obtained by containing surface-modified oxide particles, such as a silica particle surface-modified by the silane compound and a zirconium oxide particle surface-modified by the dispersing agent.
  • surface-modified oxide particles such as a silica particle surface-modified by the silane compound and a zirconium oxide particle surface-modified by the dispersing agent.
  • Patent No. 5281710 International Publication No. 2011/105473
  • JP 2014-234458 A International Publication No. 2016/104039
  • the cured product obtained from the curable composition containing the surface-modified oxide particles described in Patent Document 2 or Patent Document 3 has low segregation of the oxide particles, low transparency, brittleness and crack resistance. There is a concern that the problem is inferior. And this problem becomes remarkable as the content of the surface-modified oxide particles increases.
  • a cured product and a molded product that can be used as a lens for a high resolution camera module having a high Abbe number (for example, 53 or more) and high transparency, and the amount of warping of a support such as a glass substrate is small by a hybrid lens system. Furthermore, there is no curable resin material which does not generate a crack in the antireflective layer formed on the cured product and the upper layer of the molded product by the subsequent heat treatment, and its development has been desired.
  • the present invention has been made in view of such circumstances, and can form a cured product and a molded product exhibiting high Abbe's number, high refractive index, high transparency, and heat resistant yellowing, and the amount of warpage of the support is
  • a photocurable composition which is suitable for producing the cured product and the molded product by a hybrid lens system because it is smaller than the conventional one, and in which the antireflective layer on the upper layer of the cured product and the molded product is not cracked by heat treatment
  • the task is to provide goods.
  • a silane compound having a (meth) acryloyloxy group or a hydrolysis polycondensate of at least one silane compound containing the silane compound is By compounding the photocurable composition at a predetermined ratio, the cured product and the molded product obtained from the photocurable composition have a high Abbe number D D (53 or more), and 90% or more at a wavelength of 410 nm. And the amount of warping of the support is very small (0 ⁇ m to less than 1.5 ⁇ m), and the heat treatment at 175 ° C. does not cause cracks in the antireflective layer on the cured product and the upper layer of the molded product.
  • the present invention has been completed.
  • the first aspect of the present invention comprises the following components (a), (b), (c), and (d), and the sum (a) of the components (a) and (b):
  • the amount of the component (b) is 30 to 90 parts by mass and the amount of the component (c) is 1 to 100 parts by mass with respect to the mass parts; the component (a), the component (b) and the (c) And 0.1 parts by mass to 5 parts by mass of the component (d) with respect to 100 parts by mass of the sum of the components).
  • the alicyclic (meth) acrylate compound has, for example, one or two (meth) acryloyloxy groups in one molecule.
  • the hydrolytic polycondensate is, for example, an organopolysiloxane having a structural unit represented by the following formula (1a) or a structural unit represented by the following formula (1b). (Wherein, R 1 , R 2 and R 4 are as defined in the formula (1) above)
  • the component (c) may be a hydrolysis polycondensate of at least two silane compounds including the silane compound represented by the formula (1) and the silane compound represented by the following formula (2) .
  • R f represents a fluoroalkyl group having 1 to 12 carbon atoms
  • R 5 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 6 represents 1 to 4 carbon atoms Represents an alkyl group
  • b represents 2 or 3
  • Rf is, for example, a group represented by the following formula (3). (Wherein Y represents a hydrogen atom or a fluorine atom, c represents an integer of 0 to 2, d represents an integer of 1 to 6, and * represents a bond to a silicon atom)
  • the hydrolytic polycondensate is, for example, an organopolysiloxane having a structural unit represented by the following formula (1a) and a structural unit represented by the following formula (2a), or a structure represented by the following formula (1b) It is an organopolysiloxane having a unit and a structural unit represented by the following formula (2b).
  • R 1 , R 2 and R 4 are as defined in the formula (1), and R 6 and Rf are as defined in the formula (2)
  • the photocurable composition for imprints of the present invention may further comprise 0.05 to 3 parts by weight of the following (based on 100 parts by weight of the sum of the components (a), (b) and (c)): and 0.1 to 3 parts by mass of the following component (f) with respect to 100 parts by mass of the component (a) and / or the component (a), the component (b) and the component (c): Good.
  • f sulfide antioxidant
  • the photocurable composition for imprints of the present invention may further comprise 1 part by mass to 20 parts by mass of the following (g) with respect to 100 parts by mass of the sum of the components (a), (b) and (c): ) Component may be contained.
  • the refractive index n D at a wavelength of 589 nm of the cured product is 1.48 to 1.55, and the Abbe number D D of the cured product is 53 to 60. It is.
  • a second aspect of the present invention is a cured product of the photocurable composition for imprints.
  • a third aspect of the present invention is a method for producing a resin lens, which comprises the step of imprinting the photocurable composition for imprints.
  • a fourth aspect of the present invention is a method for producing a molded article of a photocurable composition for imprints, wherein the photocurable composition for imprints is a space between a support and a mold in contact with each other, or A method for producing a molded body, comprising the steps of: filling in a space inside a dividable mold; and exposing and photocuring the photocurable composition for imprints filled in the space.
  • the mold is also referred to as a mold.
  • the step of taking out and releasing the obtained photocured product after the step of photocuring, the step of taking out and releasing the obtained photocured product, and before or during the step of releasing the photocured product. It may further include the step of heating later.
  • the molded body is, for example, a lens for a camera module.
  • the photocurable composition for imprints of the present invention comprises the above components (a) to (d), and optionally, the above components (e) and / or (f), and (g) Because the composition contains the component, the cured product and molded product obtained from the photocurable composition have desirable optical properties as an optical device, for example, a lens for a high resolution camera module, that is, high Abbe number, high refractive index, high transparency. And thermotropic yellowing. In addition, the amount of warping of the support on which the cured product and the molded product are formed is extremely small (0 ⁇ m or more and less than 1.5 ⁇ m), and heat treatment at 175 ° C. Does not occur.
  • Component (a): alicyclic (meth) acrylate compound The alicyclic (meth) acrylate compound which can be used as the component (a) of the photocurable composition for imprints of the present invention comprises at least one (meth) acryloyloxy group and one alicyclic hydrocarbon in one molecule. It has one group and excludes compounds of component (b) described later.
  • alicyclic (meth) acrylate compound for example, 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, 1,3-adamantanediol di (meth) acrylate, tricyclo [5.2.1.0 (2,6)] decanyl (meth) acrylate, tricyclo [5.2.1.
  • a commercial item may be used as said alicyclic (meth) acrylate compound,
  • biscoat # 155, IBXA, ADMA above, Osaka Organic Chemical Industry Co., Ltd. product
  • NK ester A-IB the same IB
  • the same A-DCP above, Shin-Nakamura Chemical Co., Ltd. product
  • Funkril registered trademark
  • FA-511AS the same FA-512AS, the same FA-513AS, the same FA-512M, the same FA-512MT
  • the same FA-513M can be mentioned.
  • the alicyclic (meth) acrylate compound of the said (a) component can be used individually by 1 type or in combination of 2 or more types.
  • urethane (meth) acrylate compound for example, EBECRYL (registered trademark) 230, 270, 280/15 IB, 284, 4491, 4683, 4858, 8307, 8402, 8411, 8804, 8807, 9270, 8800, 294/25 HD, 4100, 4220, 4513, 4738, 4740, 4820, 8311, 8465, 9260, 8701, KRM 7735, 8667, the same 8296 (above, made 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, Nippon Synthetic Chemical Industry Co., Ltd.), UA-306H, UA-306T
  • the epoxy (meth) acrylate compound which can be used as (b) component of the photocurable composition for imprints of this invention makes the compound which has an epoxy ring at least 2 in 1 molecule, and (meth) acrylic acid react. Ester.
  • the epoxy (meth) acrylate compound for example, EBECRYL (registered trademark) 645, 648, 860, 3500, 3608, 3702, 3708 (all manufactured by Daicel Ornex Co., Ltd.), DA-911 M , DA-920, DA-931, DA-314, DA-212 (all manufactured by Nagase ChemteX Co., Ltd.), HPEA-100 (manufactured by KaesM Co., Ltd.), and Unidic (registered trademark) V-5500, Examples thereof include V-5502 and V-5508 (manufactured by DIC Corporation).
  • the content of the component (b) of the photocurable composition for imprints of the present invention is preferably 30 parts by mass to 90 parts by mass, preferably 100 parts by mass of the sum of the components (a) and (b). Is 50 to 90 parts by mass. If the content of the component (b) is less than 30 parts by mass, warpage of the cured product obtained from the photocurable composition for imprints and the support on which the molded product is formed may be increased. When the content of the component (b) is more than 90 parts by mass, the refractive index of the cured product and the molded product obtained from the photocurable composition for imprint may be lowered to less than 1.48.
  • the urethane (meth) acrylate compound or the epoxy (meth) acrylate compound of the component (b) can be used singly or in combination of two or more.
  • Component (c) a silane compound or a hydrolytic polycondensate of at least one silane compound containing the silane compound
  • the silane compound which can be used as (c) component of the photocurable composition for imprints of this invention is a silane compound represented by said Formula (1) which has a (meth) acryloyloxy group.
  • Examples of the silane compound represented by the formula (1) include (meth) acryloyloxypropyltrimethoxysilane, (meth) acryloyloxypropyltriethoxysilane, (meth) acryloyloxyoctyltrimethoxysilane, and (meth) acryloyloxy Examples include octyl triethoxysilane, (meth) acryloyloxypropylmethyldimethoxysilane, and (meth) acryloyloxypropylmethyldiethoxysilane.
  • the hydrolytic polycondensate usable as the component (c) of the photocurable composition for imprints of the present invention has a hydrolytic polycondensate of the silane compound represented by the above formula (1) and a fluoroalkyl group.
  • the hydrolytic polycondensate of the silane compound represented by the formula (2) and the silane compound represented by the formula (1), the silane compound represented by the formula (2) and the formula (1) The hydrolytic polycondensate of the silane compound and the other silane compound, or the hydrolytic polycondensate of the silane compound represented by the formula (1) and the other silane compound.
  • silane compound represented by the formula (2) for example, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropylmethyldimethoxysilane, 3,3,3-trifluoropropyl Triethoxysilane, 3,3,3-trifluoropropylmethyldiethoxysilane, trimethoxy (1H, 1H, 2H, 2H-nonafluorohexyl) silane, methyldimethoxy (1H, 1H, 2H, 2H-nonafluorohexyl) silane , Triethoxy (1H, 1H, 2H, 2H-nonafluorohexyl) silane, methyldiethoxy (1H, 1H, 2H, 2H, 2H-nonafluorohexyl) silane, trimethoxy (1H, 1H, 2H, 2H-tridecafluoro-n) -Octyl) silane, and
  • the said other silane compounds are silane compounds which do not correspond to any of the silane compound represented by said Formula (1), and the silane compound represented by said Formula (2).
  • the other silane compounds include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-hexyltrimethoxysilane, There may be mentioned n-hexyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, tetramethoxysilane and tetraethoxysilane.
  • the content of the component (c) of the photocurable composition for imprints of the present invention is 1 part by mass to 100 parts by mass, preferably 5 parts by mass with respect to 100 parts by mass of the sum of the components (a) and (b).
  • the amount is from 80 parts by mass to 80 parts by mass.
  • the content of the component (c) is less than 1 part by mass, the cured product obtained from the photocurable composition for imprints and the antireflection layer on the upper layer of the molded product are cracked by heat treatment.
  • the content of the component (c) is more than 100 parts by mass, the cured product and the molded product obtained from the photocurable composition for imprints have a reduced refractive index, and thus a lens for a high resolution camera module Is not suitable.
  • the silane compound or hydrolysis polycondensate of the component (c) can be used singly or in combination of two or more.
  • photoradical initiators examples include alkylphenones, benzophenones, ketones of Michler, acylphosphine oxides, benzoylbenzoate And oxime esters, tetramethylthiuram monosulfides and thioxanthones, and in particular, photocleavage type photo radical polymerization initiators are preferred.
  • photo radical initiator commercially available products such as IRGACURE (registered trademark) 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG 24.
  • KIP 150 KIP 65 LT, KIP 100 F, KT 37, KT 55, KTO 46, KIP 75 (above, Lamberti) Can be adopted.
  • the content of the component (d) of the photocurable composition for imprints of the present invention is 0.1 parts by mass with respect to 100 parts by mass of the components (a), (b) and (c). To 5 parts by mass, preferably 0.5 to 3 parts by mass. If the content of the component (d) is less than 0.1 parts by mass, the strength of the cured product and the molded product obtained from the photocurable composition for imprints may be reduced. When the content of the component (d) is more than 5 parts by mass, the heat resistance yellowing of the cured product and the molded product obtained from the photocurable composition for imprint may be deteriorated.
  • the photo radical initiator of the said (d) component can be used individually by 1 type or in combination of 2 or more types.
  • phenolic antioxidant which can be used as (e) component of the photocurable composition for imprints of this invention, for example, IRGANOx (registered trademark) 245, 1010, 1035, 1076, 1135 (above, BASF Japan Ltd., SUMILIZER (R) GA-80, GP, MDP-S, BBM-S, WX-R (above, Sumitomo Chemical Co., Ltd.), and Adekastab (registered trademark) AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330 (all manufactured by ADEKA Co., Ltd.).
  • the content of the component (e) of the photocurable composition for imprints of the present invention is 0.05 mass based on 100 parts by mass of the sum of the component (a), the component (b) and the component (c). Part to 3 parts by mass, preferably 0.1 part by mass to 1 part by mass.
  • the phenolic antioxidant of the said (e) component can be used individually by 1 type or in combination of 2 or more types.
  • sulfide antioxidant examples include Adekastab (registered trademark) AO-412S, AO-503 (all manufactured by ADEKA And IRGANOX (registered trademark) PS 802, PS 800 (manufactured by BASF Japan Ltd.), and SUMILIZER (registered trademark) TP-D (manufactured by Sumitomo Chemical Co., Ltd.).
  • the content of the component (f) of the photocurable composition for imprints of the present invention is 0.1 mass to the total 100 parts by mass of the component (a), the component (b) and the component (c). Part to 3 parts by mass, preferably 0.1 part by mass to 1 part by mass.
  • the sulfide-based antioxidants of the component (f) can be used singly or in combination of two or more.
  • the photocurable composition for imprints of the present invention may contain any one of the above component (e) and the above component (f), but may contain both.
  • the content of the component (e) and / or the component (f) is less than the lower limit value of the above range, a cured product and a molded product obtained from the photocurable composition before and after the mounting process involving heat treatment There is a possibility that the transmittance may change.
  • the content of the component (e) and / or the component (f) is more than the upper limit value of the above range, the cured product and the molded product obtained from the photocurable composition become embrittled and the sun is used in the use environment. When exposed to strong light such as light, it may turn green.
  • the polyfunctional thiol compound which can be used as (g) component of the photocurable composition for imprints of this invention is a polyfunctional thiol compound represented by said Formula (4).
  • the polyfunctional thiol compound represented by the formula (4) for example, 1,2-ethanedithiol, 1,3-propanedithiol, bis (2-mercaptoethyl) ether, trimethylolpropane tris (3-mercaptopropio) Salts), 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
  • polyfunctional thiol compound represented by said Formula (4) commercially available products, for example, Karen MT (trademark) PE1, NR1, BD1, TPMB, TEMB (above, Showa Denko KK-made), and TMMP , TEMPIC, PEMP, EGMP-4, DPMP, TMMP II-20P, PEMP II-20P, PEPT (manufactured by SC Organic Chemical Co., Ltd.) can be employed.
  • Karen MT trademark
  • PE1 NR1, BD1, TPMB
  • TEMB above, Showa Denko KK-made
  • TMMP TEMPIC
  • PEMP EGMP-4
  • DPMP TMMP II-20P
  • PEMP II-20P PEPT
  • the content of the component (g) of the photocurable composition for imprints of the present invention is 1 part by mass to 100 parts by mass of the sum of the component (a), the component (b) and the component (c). It is 25 parts by mass, preferably 5 parts by mass to 15 parts by mass.
  • the content of the component (g) is less than 1 part by mass, the warp of the cured product obtained from the photocurable composition for imprints and the support on which the molded product is formed may be increased.
  • the content of the component (g) is more than 25 parts by mass, the cured product and the molded product obtained from the photocurable composition for imprints are deteriorated in mechanical properties, so that in the mounting process involving heat treatment The cured product and the molded product may be deformed.
  • the polyfunctional thiol compounds of the component (g) can be used singly or in combination of two or more.
  • the method for preparing the photocurable composition for imprints of the present invention is not particularly limited.
  • the preparation method for example, the components (a), (b), (c) and (d), and optionally (e) and / or (f), and (g) may be used.
  • the photocurable composition for imprints of the present invention can be exposed (photocured) to obtain a cured product, and the present invention is also directed to the cured product.
  • the light beam for exposure include ultraviolet light, electron beam and X-ray.
  • a light source used for ultraviolet irradiation for example, a solar light, 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.
  • post-baking may be performed to stabilize the physical properties of the cured product.
  • the method of post-baking is not particularly limited, but it is usually performed in the range of 50 ° C. to 260 ° C. for 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 D of 53 or more, and a refractive index n D at a wavelength of 589 nm (D line) is 1. It is 48 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 articles in parallel with the formation of a cured product, for example, by using an imprint molding method.
  • a method of producing a molded body for example, a step of filling the photocurable composition for imprinting of the present invention in the space between a support and a mold which are in contact with each other, or the space inside a dividable mold; And a step of exposing and photocuring the photocurable composition for imprints filled in the step, a step of taking out and releasing the photocured product obtained by the step of photocuring, and the photocured product.
  • the method includes a heating step before, during or after the releasing step.
  • the step of light exposure and photocuring can be carried out by applying the conditions for obtaining the above-mentioned cured product.
  • the conditions for the step of heating the photocured product are not particularly limited, but are usually selected appropriately from the range of 50 ° C. to 260 ° C. and 1 minute to 24 hours.
  • a heating means although it does not specifically limit, a hot plate and oven are mentioned, for example.
  • the molded product produced by such a method can be suitably used as a lens for a camera module.
  • Optical microscope Device manufactured by Keyence Corporation VHX-1000, VH-Z1000R Conditions: reflection (bright field), objective 500 times (8) lens molding Device: Meisho Kiko Co., Ltd.
  • the weight average molecular weight Mw of the organopolysiloxane shown in the following synthesis example is a measurement result by gel permeation chromatography (hereinafter, abbreviated as GPC in the present specification).
  • GPC gel permeation chromatography
  • GPC system configuration system controller CBM-20A, column oven: CTO-20A, auto sampler: SIL-10AF, detector: SPD-20A and RID-10A, exhaust unit: DGU-20A3
  • GPC column Shodex (registered trademark) KF-804L and KF-803L Column temperature: 40 ° C
  • Solvent tetrahydrofuran Flow rate: 1 mL / min Standard sample: 5 types of polystyrene of different weight average molecular weights (197000, 55100, 12800, 3950, 1260)
  • A-DCP Shin-Nakamura Chemical Co., Ltd. product name: NK ester
  • A-DCP FA 513 AS manufactured by Hitachi Chemical Co., Ltd.
  • APTMS Acryloyloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.
  • KBM-5103 MPTMS methacryloyloxypropyl trimethoxysilane, Shin-Etsu Chemical Co., Ltd.
  • KBM-503 TFPTMS 3, 3, 3- trifluoropropyl trimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.
  • KBM-7103 TDFOTMS trimethoxy (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) silane, Tokyo Chemical Industry Co., Ltd.
  • NPTMS n-propyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.
  • KBM- 3033 NR1 Showa Denko KK product name: Kalens (registered trademark) MT NR1
  • I184 BASF Japan Ltd.
  • the reaction product obtained is cooled to room temperature (approximately 25 ° C.), and 20.7 g of ion exchange resin Amberlyst® 15 JWET and powdered cellulose KC floc® W-100 GK (Nippon Paper Co., Ltd.) 4.15 g was added, and the reaction was stopped by stirring for 1 hour. Thereafter, the resultant was filtered through a 0.5 ⁇ m membrane filter, and the filtrate was washed with 207.4 g of ethyl acetate.
  • organopolysiloxane (AF-55) to be obtained was obtained.
  • the obtained organopolysiloxane (AF-55) was measured by GPC to find that the weight average molecular weight Mw was 2,200 in terms of polystyrene, and the degree of dispersion: Mw / Mn was 1.1.
  • the reaction product obtained is cooled to room temperature (approximately 25 ° C.), and 19.2 g of ion exchange resin Amberlyst® 15 JWET and powdered cellulose KC floc® W-100 GK (Nippon Paper Co., Ltd. 3.85g was added, and the reaction was stopped by stirring for 1 hour. Thereafter, the resultant was filtered through a 0.5 ⁇ m membrane filter, and the filtrate was washed with 192.4 g of ethyl acetate.
  • organopolysiloxane (MF-55) was measured by GPC to find that the weight average molecular weight Mw was 2,000 and the degree of dispersion: Mw / Mn was 1.1 in terms of polystyrene.
  • reaction product After stirring, the reaction product is cooled to room temperature (approximately 25 ° C.), and 4.73 g of ion exchange resin Amberlyst® 15JWET and powdered cellulose KC floc® W-100GK (Nippon Paper Co., Ltd. 0.946 g was added and the reaction was stopped by stirring for 1 hour. Thereafter, the resultant was filtered through a 0.5 ⁇ m membrane filter, and the filtrate was washed with 47.3 g of ethyl acetate.
  • ion exchange resin Amberlyst® 15JWET and powdered cellulose KC floc® W-100GK Naippon Paper Co., Ltd. 0.946 g
  • organopolysiloxane (M6FP-50545).
  • the obtained organopolysiloxane (M6FP-50545) was measured by GPC to find that the weight average molecular weight Mw was 4,400, and the degree of dispersion: Mw / Mn was 1.6, in terms of polystyrene.
  • Example 1 (A) A-DCP as the alicyclic (meth) acrylate compound, (b) UA-4200 as the urethane (meth) acrylate compound, (d) I184 as the photo radical initiator, and (e) phenolic antioxidant As I, I245 was mix
  • Example 8 and Example 9 In the same manner as in Example 1, components (a) to (e) were mixed in the proportions shown in Table 1 below to prepare photocurable compositions 8 and 9 for imprints.
  • Comparative Example 1 The photocurable composition for imprints by mixing the components (a), (b), (d) and (e) in the proportions shown in Table 1 in the same procedure as in Example 1 above. Preparation 10 was made.
  • Comparative Example 2 In the same manner as in Example 1, the proportions of TFPTMS as a silane compound not corresponding to the components (a), (b), (d) and (e), and (c) are shown in Table 1 below. The mixture was mixed to prepare a photocurable composition 11 for imprinting.
  • Comparative Example 3 In the same manner as in Example 1, components (b) to (e) were mixed at a ratio shown in Table 1 below to prepare a photocurable composition 12 for imprinting.
  • permeability of wavelength 410nm of the cured film produced by said method was measured using the said ultraviolet visible near-infrared spectrophotometer. The results are shown in Table 2 below. Furthermore, the cured film was placed on a silicon wafer, and the heat resistance test was performed by heating for 2 minutes and 30 seconds on a hot plate heated to 175 ° C. through the silicon wafer. The transmittance
  • the photocurable composition on the first glass substrate was sandwiched between the second glass substrate (1.0 cm square, 0.5 mm thickness) which was treated to be in close contact with each other.
  • the sandwiched photocurable composition was subjected to UV exposure at 20 mW / cm 2 for 300 seconds through an i-line band pass filter (manufactured by Asahi Spectroscopic Co., Ltd.) using the UV irradiation apparatus.
  • the cured product obtained after exposure is peeled off from the first glass substrate, and then heated for 10 minutes on a hot plate at 100 ° C. to obtain a diameter of 0.5 cm and a thickness of 0 on the second glass substrate.
  • a cured film of .5 mm and a mass of 0.01 g was produced.
  • the heat resistance test was done by heating the 2nd glass substrate in which the said cured film was produced for 2 minutes and 30 seconds with a 175 degreeC hotplate.
  • the second glass substrate on which the cured film was produced was placed on the stage of the noncontact surface texture measuring apparatus so that the second glass substrate was on the top.
  • the center of the second glass substrate was used as the measurement start point, and the displacement in the direction (Z axis) perpendicular to the stage was measured toward the four apexes of the second glass substrate.
  • the amount of displacement in the vertical direction (Z axis) between the center of the second glass substrate and each vertex of the second glass substrate was calculated from the measurement data, and the average value thereof was defined as the amount of warpage.
  • the curvature amount evaluation method of a glass substrate is typically shown in FIG. The results are shown in Table 2 below.
  • the photocurable composition for imprinting on the first glass substrate was sandwiched between the second glass substrate (6 cm square, 0.7 mm thickness) which was treated to be in close contact with each other.
  • the sandwiched photocurable composition was subjected to UV exposure at 20 mW / cm 2 for 300 seconds through an i-line band pass filter (manufactured by Asahi Spectroscopic Co., Ltd.) using the UV irradiation apparatus.
  • the cured product obtained after exposure is peeled off from the first glass substrate, and then heated for 10 minutes on a hot plate at 100 ° C. to obtain a diameter of 1 cm and a thickness of 0.5 mm on the second glass substrate. And the cured film of mass 0.040g was produced. The same operation was repeated to produce three cured films on the second glass substrate.
  • a silicon oxide layer having a thickness of 200 nm was formed as an antireflective layer under the film forming conditions using the RF sputtering apparatus.
  • Heat resistance is achieved by heating the second glass substrate with a hot plate at 175 ° C. for 2 minutes and 30 seconds after observing the antireflective layers on the three cured films using the optical microscope to confirm the presence or absence of cracks. The sex test was done. Also about the said 2nd glass substrate after a heat resistance test, the presence or absence of the crack of the reflection prevention layer on said 3 cured film was observed using the said optical microscope, and the crack resistance of this reflection prevention layer was determined.
  • the antireflection layer formed on the cured film produced from the photocurable composition for imprints of Comparative Example 1 and Comparative Example 2 which does not contain the component (c) has heat resistance After the test, a crack was generated.
  • the cured film produced from the photocurable composition of Comparative Example 3 which does not contain the component (a) shows good characteristics of heat-resistant yellowing and the amount of warping of the glass substrate, and reflections formed on the cured film
  • the preventive layer exhibits crack resistance, the refractive index n D is as low as less than 1.48. This result suggests that the cured film produced from the photocurable composition of Comparative Example 3 is not suitable for a lens for a high pixel camera module.
  • the cured film produced from the photocurable composition of the present invention has all the characteristics of the initial transmittance, heat yellowing resistance, the amount of warp, and the crack resistance of the antireflective layer formed on the cured film.
  • the refractive index n D and the Abbe number ⁇ D suitable for a lens having a high Abbe number and good characteristics are shown, and the superiority of the present invention is confirmed.
  • Photocurable composition 5 for imprints prepared in Example 5 was prepared using a nickel mold (a total of 15 lens molds of 2 mm diameter ⁇ 300 ⁇ m depth, 3 vertical rows ⁇ 5 horizontal rows) and a nano imprinter Using the above-described method for forming a molded body, and molded into a lens shape on a glass substrate as a support.
  • the mold used was subjected to release treatment in advance with NOVEC (registered trademark) 1720 (manufactured by 3M Japan Co., Ltd.). Further, the used glass substrate was subjected to adhesion treatment in advance with an adhesion aiding agent (product name: KBM-503) manufactured by Shin-Etsu Chemical Co., Ltd. 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.
  • the lens height (thickness) before and after the heating test is measured by the non-contact surface texture measuring apparatus, and the rate of change is measured according to the following formula "[((height of lens before heating-heating) The lens stability after heating / the lens height before heating] ⁇ 100 ′ ′ was calculated, and the dimensional stability due to heating was evaluated. In addition, the occurrence of cracks in the convex lens after the heating test was observed with a microscope attached to the non-contact surface texture measuring apparatus.
  • the heating test is a test in which a convex lens obtained on a glass substrate is heated for 2 minutes and 30 seconds on a hot plate at 175 ° C., 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 passing a heat history of 175 ° C. for 2 minutes and 30 seconds, and the dimensional stability is The result was high.
  • FIG. 1 is a schematic view showing a method of evaluating the amount of warpage of a glass substrate.

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JP2012214716A (ja) * 2011-03-30 2012-11-08 Kyoritsu Kagaku Sangyo Kk インプリント成型用光硬化性樹脂組成物、インプリント成型硬化体及びこれらの製造方法
JP2014234458A (ja) * 2013-06-03 2014-12-15 昭和電工株式会社 硬化性組成物およびその硬化物
WO2015129818A1 (ja) * 2014-02-28 2015-09-03 日産化学工業株式会社 反応性シルセスキオキサン化合物を含む重合性組成物
WO2015190544A1 (ja) * 2014-06-13 2015-12-17 東亞合成株式会社 硬化型組成物
JP2017049461A (ja) * 2015-09-02 2017-03-09 日産化学工業株式会社 反応性シロキサン化合物を含むインプリント成形用重合性組成物
JP2018009102A (ja) * 2016-07-14 2018-01-18 協立化学産業株式会社 インプリント成型用光硬化性樹脂組成物

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WO2017038943A1 (ja) * 2015-09-02 2017-03-09 日産化学工業株式会社 アクリル基を有するシルセスキオキサン化合物を含む重合性組成物

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JP2012214716A (ja) * 2011-03-30 2012-11-08 Kyoritsu Kagaku Sangyo Kk インプリント成型用光硬化性樹脂組成物、インプリント成型硬化体及びこれらの製造方法
JP2014234458A (ja) * 2013-06-03 2014-12-15 昭和電工株式会社 硬化性組成物およびその硬化物
WO2015129818A1 (ja) * 2014-02-28 2015-09-03 日産化学工業株式会社 反応性シルセスキオキサン化合物を含む重合性組成物
WO2015190544A1 (ja) * 2014-06-13 2015-12-17 東亞合成株式会社 硬化型組成物
JP2017049461A (ja) * 2015-09-02 2017-03-09 日産化学工業株式会社 反応性シロキサン化合物を含むインプリント成形用重合性組成物
JP2018009102A (ja) * 2016-07-14 2018-01-18 協立化学産業株式会社 インプリント成型用光硬化性樹脂組成物

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