WO2021215155A1 - Composition photodurcissable - Google Patents

Composition photodurcissable Download PDF

Info

Publication number
WO2021215155A1
WO2021215155A1 PCT/JP2021/011251 JP2021011251W WO2021215155A1 WO 2021215155 A1 WO2021215155 A1 WO 2021215155A1 JP 2021011251 W JP2021011251 W JP 2021011251W WO 2021215155 A1 WO2021215155 A1 WO 2021215155A1
Authority
WO
WIPO (PCT)
Prior art keywords
meth
component
photocurable composition
acrylate
molded product
Prior art date
Application number
PCT/JP2021/011251
Other languages
English (en)
Japanese (ja)
Inventor
翔太 今井
朋哉 鈴木
Original Assignee
日産化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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 JP2022516891A priority Critical patent/JP7469746B2/ja
Publication of WO2021215155A1 publication Critical patent/WO2021215155A1/fr

Links

Images

Classifications

    • 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
    • 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
    • C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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

Definitions

  • the present invention includes a polyfunctional (meth) acrylate having two or more (meth) acryloyloxy groups in one molecule, a photoradical initiator, silica particles surface-modified with a specific silane coupling agent, and a polyfunctional thiol.
  • a photoradical initiator silica particles surface-modified with a specific silane coupling agent
  • a polyfunctional thiol a polyfunctional thiol.
  • the cured product and molded product obtained from the photocurable composition of the present invention have high transparency, the amount of warpage of the support is small, and cracks do not occur even after undergoing a developing process using an organic solvent.
  • Resin lenses are used in electronic devices such as mobile phones, smartphones, digital cameras, and in-vehicle cameras, and have high transparency, heat resistance, and high productivity that can be molded with good yield according to the intended use of the resin lens. It has been demanded.
  • a resin lens satisfying such a requirement for example, a thermoplastic transparent resin such as a polycarbonate resin, a cycloolefin polymer, or a methacrylic resin has been used.
  • Multiple lenses are used in the high resolution camera module.
  • manufacturing the lens in order to improve yield and production efficiency, and to suppress optical axis deviation during lens lamination, from injection molding of thermoplastic resin to wafer level molding using photocurable resin liquid at room temperature. The transition to is being actively considered.
  • the photocurable resin a radical curable resin composition is widely used from the viewpoint of high transparency and mold releasability.
  • a hybrid lens method in which a lens is formed on a support such as a glass substrate is generally used from the viewpoint of productivity.
  • the market demand for thinning camera modules is increasing year by year, and the thickness of the support used in the hybrid lens system is also required to be thinned. Therefore, when a general radically polymerizable resin composition is used, the support on which the molded body such as a lens is formed tends to warp, which may make it difficult to precisely assemble the camera module.
  • the cured product has high transparency that can be used as a resin lens, the amount of warpage of the support when the molded body is formed on a support such as a glass substrate is small, and the molded product is molded even after undergoing a developing process using an organic solvent. There is still no resin composition containing inorganic fine particles that does not cause cracks in the hem of the body, and its development has been desired.
  • the present invention has been made in view of such circumstances, and an object of the present invention is to provide a photocurable composition that solves the above-mentioned problems.
  • the present inventors photocured specific polyfunctional (meth) acrylates, silica particles surface-modified with specific silane coupling agents, and polyfunctional thiols, respectively.
  • the transmittance of the cured product and the molded product obtained from the photocurable composition is high, and the warp of the support when the cured product and the molded product are formed on the support.
  • the amount is small (0 ⁇ m or more and less than 3.0 ⁇ m), and that cracks do not occur in the hem of the cured product and the molded product even after undergoing a development process using an organic solvent, and the present invention has been completed.
  • the first aspect of the present invention is a photocurable composition containing the following component (a), the following component (b), the following component (c) and the following component (d).
  • X 1 represents a hydrogen atom or a (meth) acryloyloxy group
  • R 1 and R 2 independently represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms
  • m is 8 to 14. It represents an integer
  • n represents an integer of 0 to 2.
  • R 3 represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms
  • X 2 represents a single bond, an ester bond or an ether bond
  • Q 1 represents a hetero atom. It represents an organic group having 2 to 12 carbon atoms or a hetero atom containing at least one or not containing a hetero atom
  • p represents an integer of 2 to 6).
  • the photocurable composition of the present invention may further contain the following component (e).
  • the photocurable composition of the present invention may further contain the following component (f) and / or the following component (g).
  • the photocurable composition of the present invention may further contain the following component (h).
  • the component (a) is, for example, a bifunctional (meth) acrylate having two (meth) acryloyloxy groups in one molecule, or one of the bifunctional (meth) acrylate and the (meth) acryloyloxy group. It is a trifunctional (meth) acrylate having three in the molecule.
  • the component (a) includes, for example, the following component (a1) and the following component (a2).
  • R 4 represents a hydrogen atom or a methyl group
  • Q 2 represents a linear or branched alkylene group having 4 to 10 carbon atoms.
  • the component (c) is, for example, silica particles in which X 1 in the formula (1) is surface-modified with a silane coupling agent of a (meth) acryloyloxy group.
  • a second aspect of the present invention is a cured product of the photocurable composition.
  • a third aspect of the present invention is a method for producing a molded product, which comprises a step of imprint molding the photocurable composition.
  • a fourth aspect of the present invention is a method for producing a molded product of a photocurable composition, wherein the photocurable composition is applied onto a support, the photocurable composition, and a target molding.
  • the photocurable composition is exposed through the mold to form a photocurable portion.
  • a method for producing a molded product which comprises a drying step of spin-drying the support on which the photocurable portion is formed after the developing step.
  • a step of heating the photo-curing portion may be further included.
  • a rinsing step of rinsing the photocured portion with a rinsing liquid may be further included.
  • a post-exposure step of exposing the entire surface of the photocurable portion may be further included.
  • a post-exposure step After the post-exposure step, a post-baking step of heating the photocurable portion may be further included.
  • a step of forming an antireflection film on the surface of the photocurable portion may be further included.
  • a step of forming an antireflection film on the surface of the photocurable portion may be further included.
  • the molded body is, for example, a lens for a camera module.
  • the photocurable composition of the present invention contains the component (a) to the component (d) as an essential component, optionally contains the component (e), and optionally the component (f) and / or the (). g) Contains the component, and optionally contains the component (h). Due to the presence of the component (a) and the component (b), a three-dimensional crosslinked body is formed when the photocurable composition is exposed, and a cured product is obtained. Further, the surface of the component (c) was modified with a silane coupling agent represented by the formula (1), that is, a silane coupling agent having a long-chain hydrocarbon group having 8 to 14 carbon atoms.
  • a silane coupling agent represented by the formula (1) that is, a silane coupling agent having a long-chain hydrocarbon group having 8 to 14 carbon atoms.
  • the silica particle / organic resin interface generated when the cured product and the molded product are developed with an organic solvent. It is possible to reduce the strain of the silica particles to prevent cracks, and to increase the dispersibility of the silica particles to increase the transparency of the cured product and the molded product.
  • the cured product and the molded product obtained from the photocurable composition containing the component (a) to the component (d) show a desirable high transmission rate as a resin lens, for example, a lens for a camera module.
  • the amount of warpage of the support is small (0 ⁇ m or more and less than 3.0 ⁇ m), and further, the cured product and the molded product are molded even after undergoing a development step using an organic solvent. We found that there were no cracks in the hem of the body.
  • FIG. 1 is a schematic view showing a method for evaluating the amount of warpage of a substrate.
  • FIG. 2 is an optical micrograph showing a hem portion of a cured product prepared from the photocurable composition 15 of Example 15 treated under the development and rinsing conditions of condition D.
  • FIG. 3 is an optical micrograph showing a hem portion of a cured product prepared from the photocurable composition 18 of Comparative Example 1 when treated under the development and rinsing conditions of Condition D.
  • O) Indicates an acryloyloxy group represented by "O-"
  • the polyfunctional (meth) acrylate having two or more (meth) acryloyloxy groups in one molecule which can be used as the component (a) of the photocurable composition of the present invention, has one molecule of (meth) acryloyloxy group. It can be roughly divided into a trifunctional or higher (meth) acrylate having three or more in it and a bifunctional (meth) acrylate having two (meth) acryloyloxy groups in one molecule.
  • the photocurable composition of the present invention contains the component (a1), the cured product and the molded product obtained from the photocurable composition are excellent in adhesion to the support.
  • the photocurable composition of the present invention contains the component (a2), the cured product and the molded product obtained from the photocurable composition are excellent in flexibility and have a (meth) acryloyloxy group described later. Excellent compatibility with.
  • Examples of the trifunctional or higher (meth) acrylate include U-6LPA, U-10HA, U-10PA, UA-1100H, U-15HA, UA-53H, UA-33H, and UA-7100 (above, Shin-Nakamura).
  • UV-2750B UV-7000B, UV-7510B, UV-1700B, UV-6300B, UV-7550B, UV-7600B
  • examples thereof include urethane (meth) acrylates such as UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7640B and UV-7650B (all manufactured by Mitsubishi Chemical Co., Ltd.).
  • TEICA MF-001, MF-101 (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), M-305, M-306, M-309, M-310, M-313, M-315, M-321 , M-350, M-360, M-400, M-402, M-403, M-404, M-405, M-406, M-408, M-450, M-460 and M-471 (or more) , Made by Toa Synthetic Co., Ltd.).
  • the trifunctional or higher (meth) acrylate can be used alone or in combination of two or more.
  • examples of the bifunctional (meth) acrylate that does not correspond to either the component (a1) or the component (a2) include cyclohexanediol di (meth) acrylate and cyclohexanedimethanol di (meth).
  • the bifunctional (meth) acrylate that does not correspond to either the component (a1) or the component (a2) can be used alone or in combination of two or more.
  • (A1) component bifunctional urethane (meth) acrylate
  • the component (a1) include U-2PPA, U-200PA, U-160TM, U-290TM, UA-4200, UA-4400, UA-122P, and UA-W2A (above, Shin-Nakamura Chemical Industry Co., Ltd.). ), AH-600, UF-8001G (all manufactured by Kyoeisha Chemical Co., Ltd.), EBECRYL (registered trademark) 210, 230, 270, 280/15IB, 284, 4491, 4683, 4683.
  • the component (a1) can be used alone or in combination of two or more.
  • Component (a2) Bifunctional (meth) acrylate represented by the above formula (3)
  • Examples of the component (a2) include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, and neopentyl glycol di.
  • biscoat # 195, biscoat # 230, biscoat # 260 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), BD, NPG, A-NPG. , HD-N, A-HD-N, NOD-N, A-NOD-N, A-IND, DOD-N, A-DOD-N (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), FA-121M , FA-124M, FA-125M, FA-129AS (all manufactured by Hitachi Chemical Co., Ltd.), Light Ester 1.4BG, Light Ester NP, Light Ester 1.6HX, Light Ester 1.9ND, Light Acrylate 1.6HX -A, Light Acrylate 1.9ND-A, Light Acrylate NP-A, Light Acrylate MPD-A (above, manufactured by Kyoeisha Chemical Co., Ltd.), HDDA (above, manufactured by Daicel Ornex Co., Ltd.),
  • the component (a2) can be used alone or in combination of two or more.
  • the content of the component (a) of the photocurable composition of the present invention is 100% by mass of the sum of the components (a), (c), (d) and (e) contained in the photocurable composition. It is 30 parts by mass to 90 parts by mass, preferably 35 parts by mass to 85 parts by mass, and more preferably 40 parts by mass to 80 parts by mass. If the content of the component (a) is less than 30 parts by mass, the cured product and the molded product obtained from the photocurable composition cannot form an organic resin matrix having a sufficient crosslink density, and the cured product In addition, the molded product may become brittle due to its low crosslink density. If the content of the component (a) is more than 90 parts by mass, the heat resistance of the cured product and the molded product obtained from the photocurable composition may deteriorate.
  • the content thereof is the component (a), the component (c), the component (d) contained in the photocurable composition of the present invention.
  • All the relationships represented by the following formulas (4) to (6) are satisfied with respect to 100 parts by mass of the sum of the components (e) and (h), and preferably the following formulas (4') to (6'). ) Is satisfied, and more preferably all the relationships of the following equations (4 ′′) to (6 ′′) are satisfied.
  • the content of the component (a1) is defined as a Y part by mass
  • the content of the component (a2) is defined as a Z mass part.
  • Equation (4) 30 parts by mass ⁇ (Y + Z) ⁇ 90 parts by mass Equation (5): 0 parts by mass ⁇ Y ⁇ 80 parts by mass Equation (6): 0 parts by mass ⁇ Z ⁇ 70 parts by mass Equation (4'): 35 parts by mass ⁇ (Y + Z) ⁇ 85 parts by mass (5'): 0 parts by mass ⁇ Y ⁇ 75 parts by mass (6'): 0 parts by mass ⁇ Z ⁇ 65 parts by mass (4'): 40 parts by mass Part ⁇ (Y + Z) ⁇ 80 parts by mass Formula (5 ′′): 0 parts by mass ⁇ Y ⁇ 70 parts by mass Formula (6 ′′): 0 parts by mass ⁇ Z ⁇ 60 parts by mass
  • the content of the component (a1) is more than 80 parts by mass, the heat resistance of the cured product and the molded product obtained from the photocurable composition may deteriorate.
  • the content of the component (a2) is 70 parts by mass or less, the viscosity of the photocurable composition does not significantly decrease, and the handleability in the step of imprinting the photocurable composition is good. be.
  • Photoradical initiators examples include alkylphenones, benzophenones, dibenzoyls, anthraquinones, acylphosphine oxides, benzoylbenzoates, and oxime esters. And thioxanthones, and in particular, an intramolecular cleavage type photoradical polymerization initiator is preferable.
  • OMNIRAD registered trademark
  • 127, 184, 369, 369E, 379EG 500, 651, 819, 784, 907.
  • IGM Resins 1173, 2959, TPO H (manufactured by IGM Resins), IRGACURE (registered trademark) OXE01, OXE02, OXE03, OXE04, CGI1700, CGI1750, CGI1850, CG24-61 (above, BASF) Examples thereof include ESACURE KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46 and KIP75 (all manufactured by Lamberti).
  • the content of the component (b) of the photocurable composition of the present invention is the component (a), the component (c), the component (d), the component (e) and the component (h) contained in the photocurable composition. It is 0.1 parts by mass to 5 parts by mass, preferably 0.5 parts by mass to 3 parts by mass with respect to 100 parts by mass of the sum of the components. If the content of the component (b) is less than 0.1 parts by mass, the strength of the cured product and the molded product obtained from the photocurable composition may decrease. If the content of the component (b) is more than 5 parts by mass, the heat resistance of the cured product and the molded product may deteriorate.
  • the component (b) can be used alone or in combination of two or more.
  • Component (c) Silica particles having a primary particle size of 1 nm to 100 nm, which are surface-modified with at least one silane coupling agent represented by the above formula (1)]
  • the silane coupling agent represented by the formula (1) that modifies the surface of the silica particles of the component (c) of the photocurable composition of the present invention has m in the formula (1) of 8 to 14. It is characterized by being an integer, that is, having a linear hydrocarbon group having 8 to 14 carbon atoms in the molecule.
  • an alkoxysilane compound in which a linear alkyl group having 8 to 14 carbon atoms is bonded to a silicon atom, or a (meth) acryloyloxy group via a linear alkylene group having 8 to 14 carbon atoms. It is an alkoxysilane compound bonded to a silicon atom.
  • a silane coupling agent having m of 8 to 14 in the formula (1) the affinity / adhesion between the surface of the silica particles surface-modified with the silane coupling agent and the organic resin is improved. be able to.
  • the affinity and adhesion with the organic resin become insufficient, and the transmittance of the cured product and the molded product of the photocurable composition of the present invention becomes insufficient. There is a risk that cracks may occur in the cured product and the hem of the molded product after the development process using an organic solvent.
  • a silane coupling agent having m of 15 or more in the formula (1) the crystallinity of the linear hydrocarbon group becomes remarkable, and the silica particles surface-modified with the silane coupling agent may aggregate. ..
  • Examples of the silane coupling agent represented by the formula (1) include n-octylrimethoxysilane, n-octylriethoxysilane, n-octylmethyldimethoxysilane, n-octylethyldimethoxysilane, and n-octylmethyl.
  • silane coupling agent represented by the formula (1) specifically, KBM-5803, KBM-3103C and KBE-3083 (all manufactured by Shin-Etsu Chemical Co., Ltd.). Can be mentioned.
  • the silane coupling agent represented by the formula (1) can be used alone or in combination of two or more.
  • silane coupling agent represented by the formula (1) and another silane coupling agent not represented by the formula (1) may be used in combination, and examples of the other silane coupling agent include, for example.
  • the other silane coupling agents may be used alone or in combination of two or more.
  • silica particles are surface-modified by using the silane coupling agent represented by the formula (1) and optionally using another silane coupling agent not represented by the formula (1), these silane coupling agents are used.
  • the amount of silica particles used satisfies all the relationships represented by the following formulas (7) and (8) per 1 g of the silica particles, and is preferably represented by the following formulas (7)'and'(8)'. All the relationships are satisfied, and more preferably all the relationships represented by the following equations (7) ′′ and the following equation (8) ′′ are satisfied.
  • the amount of the silane coupling agent represented by the formula (1) is y mmol
  • the amount of the other silane coupling agent not represented by the formula (1) is z mmol.
  • the amount of the silane coupling agent represented by the formula (1) used is less than 0.1 mmol, the affinity / adhesion between the surface of the silica particles and the organic resin becomes insufficient, and the photocurability of the present invention becomes insufficient. There is a risk that the transmittance of the cured product and the molded product obtained from the composition will decrease, and that cracks will occur in the hem of the cured product and the molded product after the development step using an organic solvent.
  • the silane coupling agent is applied to the silica particles. If the silane coupling agent becomes excessive and is not consumed for surface modification of the silica particles, the storage stability and mechanical properties of the cured product and the molded product may be deteriorated.
  • the silica particles of the component (c) of the photocurable composition of the present invention have a primary particle size 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 size calculated from the above relational expression is the average particle size, which is the diameter of the primary particles. If the primary particle size is smaller than 1 nm, the silica particles tend to aggregate, and the storage stability may deteriorate. If the primary particle size is larger than 100 nm, the transparency of the cured product and the molded product may be impaired.
  • silica particles of the component (c) those obtained by reacting the unsurface-modified silica particles with the silane coupling agent by various known methods can be used.
  • the unsurface-modified silica particles for example, those in which the silica particles are dispersed in an organic solvent (organo silica sol) are preferably used.
  • organosilica sol for example, CHO-ST-M, DMAC-ST, DMAC-ST-ZL, EAC-ST, EG-ST, EG-ST-ZL, EG-ST-XL30, IPA-ST, IPA-ST-L, IPA-ST-ZL, IPA-ST-UP, methanol silica sol, MA-ST-M, MA-ST-L, MA-ST-ZL, MA-ST-UP, MEK -ST, MEK-ST-40, MEK-ST-L, MEK-ST-ZL, MEK-ST-UP, MIBK-ST, MIBK-ST-L, NMP-ST, NPC-ST-30, PMA-ST , PGM-ST, PGM-ST, PGM-ST-UP, and TOR-ST (all manufactured by Nissan Chemical Co., Ltd.).
  • organosilica sol a commercially available water-dispersed silica sol in which water is replaced with an organic solvent by a known method such as vacuum distillation or ultrafiltration, or a commercially available powdered silica particles dispersed in an organic solvent may be used. ..
  • the silica solid content concentration in the organosilica sol is not particularly limited, but is generally preferably 60% by mass or less.
  • the content of the component (c) of the photocurable composition of the present invention is the component (a), the component (c), the component (d), the component (e) and the component (h) contained in the photocurable composition. It is 5 parts by mass to 60 parts by mass, preferably 8 parts by mass to 45 parts by mass, and more preferably 10 parts by mass to 30 parts by mass with respect to 100 parts by mass of the sum of the components. If the content of the component (c) is less than 5 parts by mass, the heat resistance of the cured product and the molded product obtained from the photocurable composition may deteriorate. If the content of the component (c) is more than 60 parts by mass, haze may occur in the cured product and the molded product, and the transmittance may decrease.
  • the component (c) can be used alone or in combination of two or more.
  • a plurality of silica particles having different primary particle diameters may be combined, or a plurality of silica particles having different types and amounts of silane coupling agents used for surface modification may be combined.
  • Examples of the polyfunctional thiol represented by the above formula (2) that can be used as the component (d) of the photocurable composition of the present invention include 1,2-ethanedithiol, 1,3-propanedithiol, and bis.
  • a commercially available product may be used as the polyfunctional thiol compound represented by the formula (2).
  • Calends MT registered trademark
  • PE1, NR1, BD1, TPMB, TEMB all manufactured by Showa Denko KK.
  • TMMP TEMPIC
  • PEMP EGMP-4
  • DPMP TMMP II-20P
  • PEMP II-20P PEMP II-20P
  • PEPT all manufactured by SC Organic Chemistry Co., Ltd.
  • the content of the component (d) of the photocurable composition of the present invention is the component (a), the component (c), the component (d), the component (e) and the component (h) contained in the photocurable composition. It is 1 part by mass to 15 parts by mass, preferably 3 parts by mass to 10 parts by mass with respect to 100 parts by mass of the sum of the components. If the content of the component (d) is less than 1 part by mass, the amount of warpage of the cured product obtained from the photocurable composition and the support on which the molded product is formed may increase. If the content of the component (d) is more than 15 parts by mass, reliability may be deteriorated such as haze when the cured product and the molded product are exposed to a high humidity / high temperature environment.
  • the component (d) can be used alone or in combination of two or more.
  • the polyrotaxane having a (meth) acryloyloxy group that can be used as the component (e) of the photocurable composition of the present invention is a pseudopolyrotaxane in which the openings of cyclic molecules are skewered by linear molecules.
  • a blocking group is arranged so that the cyclic molecule does not escape, and the cyclic molecule has a (meth) acryloyloxy group.
  • the cyclic molecule of the polyrotaxane is not particularly limited as long as it is cyclic, has an opening, and is skewered by a linear molecule.
  • the (meth) acryloyloxy group may be directly attached to the cyclic molecule or may be attached via a spacer.
  • the cyclic molecule for example, it is preferable to select from the group consisting of ⁇ -cyclodextrin, ⁇ -cyclodextrin and ⁇ -cyclodextrin.
  • linear molecule The linear molecule of the polyrotaxane is not particularly limited as long as it can be skewered into the opening of the cyclic molecule to be used.
  • linear molecule include polymers selected from the group consisting of polyethylene glycol, polyisobutylene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol and polyvinyl methyl ether.
  • polyethylene glycol is particularly preferable.
  • the linear molecule has a weight average molecular weight of 1,000 or more, preferably 3,000 to 100,000, and more preferably 6,000 to 50,000.
  • the combination of (cyclic molecule, linear molecule) is particularly preferably (derived from ⁇ -cyclodextrin, derived from polyethylene glycol).
  • the blocking group of the polyrotaxane is not particularly limited as long as it is a group that is arranged at both ends of the pseudopolyrotaxane and acts so that the cyclic molecule used does not desorb.
  • a blocking group selected from the group consisting of dinitrophenyl groups, cyclodextrins, adamantyl groups, trityl groups, fluoresceins, silsesquioxanes, and pyrenes is preferable, and more preferable. It is an adamantyl group or a cyclodextrin.
  • CELM registered trademark superpolymer
  • SA1303P SA1305P
  • SA1305P-10 SA1305P-20
  • SA2403P SA2405P-10
  • SA2405P-20 SA2405P-20
  • SA3403P SM1303P, SM1305P-20, SM2403P, SM2405P-20 and SM3403P [all manufactured by ASM Co., Ltd. (formerly Advanced Soft Materials Co., Ltd.)].
  • the content thereof is the component (a), the component (c), the component (d), and the component (e) contained in the photocurable composition.
  • 1 part by mass to 15 parts by mass preferably 3 parts by mass to 10 parts by mass with respect to 100 parts by mass of the sum of the components (h).
  • the component (e) can be used alone or in combination of two or more.
  • Component (f) Phenolic antioxidant
  • IRGANOX registered trademark
  • 1010, 1035, 1076, and 1135 above, BASF Japan
  • the content thereof is the component (a), the component (c), the component (d), (e) contained in the photocurable composition. It is 0.05 parts by mass to 3 parts by mass, preferably 0.1 parts by mass to 1 part by mass with respect to 100 parts by mass of the sum of the component and the component (h).
  • the component (f) can be used alone or in combination of two or more.
  • sulfide-based antioxidant examples include ADEKA STAB (registered trademark) AO-412S and AO-503 (all manufactured by ADEKA Corporation). Examples thereof include IRGANOX (registered trademark) PS802, PS800 (above, manufactured by BASF Japan Ltd.), and SUMILIZER (registered trademark) TP-D (manufactured by Sumitomo Chemical Co., Ltd.).
  • the photocurable composition of the present invention contains the component (g), the content thereof is the component (a), the component (c), the component (d), and the component (e) contained in the photocurable composition. And, with respect to 100 parts by mass of the sum of the components (h), it is 0.05 parts by mass to 3 parts by mass, preferably 0.1 parts by mass to 1 part by mass.
  • the component (g) can be used alone or in combination of two or more.
  • Examples of the monomer having one (meth) acryloyloxy group or allyloxy group in one molecule that can be used as the component (h) of the photocurable composition of the present invention include methyl (meth) acrylate and ethyl (meth).
  • n-butyl (meth) acrylate isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (Meta) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, benzyl (meth) acrylate, Phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (
  • the content thereof is the component (a), the component (c), the component (d), (e) contained in the photocurable composition. It is 0.5 parts by mass to 40 parts by mass, preferably 1 part by mass to 30 parts by mass, and more preferably 5 parts by mass to 15 parts by mass with respect to 100 parts by mass of the sum of the component and the component (h).
  • the photocurable composition of the present invention reduces the viscosity of the photocurable composition according to the type of the component (h), and the photocurable composition.
  • the component (h) can be used alone or in combination of two or more.
  • the photocurable composition of the present invention can be used as a monofunctional acrylate, a chain transfer agent, an ultraviolet absorber, a light stabilizer, a leveling agent, a rheology adjuster, if necessary, as long as the effects of the present invention are not impaired.
  • Adhesive aids such as silane coupling agents and additives such as pigments, dyes and defoamers can be contained.
  • the method for preparing the photocurable composition of the present invention is not particularly limited.
  • the preparation method includes, for example, (a) component, (b) component, (c) component and (d) component, and if necessary, (e) component, (f) component and / or (g) component, and (h). )
  • a method of mixing the components at a predetermined ratio to obtain a uniform solution can be mentioned.
  • the photocurable composition 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 10 ⁇ m or the like.
  • the photocurable composition of the present invention can be exposed (photocured) to obtain a cured product, and the present invention also covers the cured product.
  • the light beam to be exposed is not particularly limited as long as the cured product can be obtained, and examples thereof include ultraviolet rays, electron beams, and X-rays.
  • the light source used for ultraviolet irradiation for example, a sunbeam, 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 applied to stabilize the physical properties of the cured product.
  • the method of post-baking is not particularly limited, but is usually carried out 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 of the present invention has a high transmittance of 90% or more at a wavelength of 410 nm. Therefore, the photocurable composition of the present invention can be suitably used for forming a resin lens.
  • the method for producing a molded product of the present invention includes a step of applying the photocurable composition of the present invention on a support.
  • the support may have a pattern having an opening, and the pattern is formed by patterning a negative photosensitive resin composition or a positive photosensitive resin composition, and the shape thereof is, for example, a grid pattern.
  • the support may be, for example, a semiconductor substrate such as silicon coated with a silicon oxide film, a semiconductor substrate such as silicon nitride film or silicon coated with a silicon oxide film, a silicon nitride substrate, a quartz substrate, or a glass substrate (non-alkali). (Including glass, low alkali glass, and crystallized glass), and a glass substrate on which an ITO film is formed can be mentioned.
  • the photocurable composition is applied onto the photocurable composition by an appropriate application method such as a dispenser or a spinner.
  • the method for producing a molded product of the present invention includes an imprinting step of bringing the photocurable composition into contact with a mold having an inverted pattern of a target lens shape and a light-shielding film.
  • the target lens shape is a concave lens
  • the inversion pattern is a convex lens pattern.
  • the material of the mold is not limited as long as it is a material that transmits light such as ultraviolet rays used in the photocuring step described later, and for example, a (meth) acrylic resin such as polymethylmethacrylate, a cycloolefin polymer (COP) resin, and the like.
  • examples include quartz, borosilicate glass and calcium fluoride.
  • the material of the mold is a resin
  • it may be either a non-photosensitive resin or a photosensitive resin.
  • the photosensitive resin include replica molding materials for imprints disclosed in International Publication No. 2019/031359.
  • the material of the light-shielding film is not limited as long as it is a material that does not transmit light such as ultraviolet rays used in the photocuring step described later, and examples thereof include aluminum, chromium, nickel, cobalt, titanium, tantalum, tungsten, and molybdenum. Can be mentioned. It is desirable that the mold is used after the mold release treatment is performed by applying a mold release agent and drying for the mold release step described later.
  • the release agent is available as a commercially available product, and is, for example, Novec (registered trademark) 1700, 1710, 1720 (all manufactured by 3M Japan Co., Ltd.), Fluorosurf (registered trademark) FG-5084, and the same.
  • the method for producing a molded product of the present invention includes, after the imprinting step, a photocuring step of exposing the photocurable composition through the mold to form a photocurable portion.
  • the light beam to be exposed is not particularly limited as long as the photocurable portion can be formed, and examples thereof include ultraviolet rays, electron beams, and X-rays.
  • the light source used for ultraviolet irradiation for example, a sunbeam, 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 film thickness of the photocurable portion is preferably 100 ⁇ m to 1000 ⁇ m, and more preferably 300 ⁇ m to 700 ⁇ m. Since the mold is made of a material that transmits light such as ultraviolet rays and has a light-shielding film that does not transmit light such as ultraviolet rays, it is used as a mask in this step.
  • the method for producing a molded product of the present invention includes a mold release step for separating the photocurable portion and the mold.
  • the mold release method is not particularly limited as long as the photocurable portion can be completely separated from the mold without being damaged or deformed.
  • the mold can be easily separated from the photocurable portion by a mold release process in which the mold release agent is applied and dried.
  • the heating means is not particularly limited, and examples thereof include a hot plate and an oven.
  • the method for producing a molded product of the present invention includes a developing step of removing the uncured portion of the photocurable composition with a developing solution to expose the photocurable portion after the mold release step.
  • the developing method is not particularly limited, and examples thereof include a dip method, a paddle method, a spray method, a dynamic dispensing method, and a static dispensing method.
  • the development conditions are appropriately selected from, for example, a development temperature of 5 ° C. to 50 ° C. and a development time of 10 seconds to 300 seconds.
  • the developer is not particularly limited as long as it can remove the uncured portion of the photocurable composition, but is organic such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofurfuryl alcohol, and ⁇ -butyrolactone. Solvents are preferred.
  • the developer can be used alone or in combination of two or more.
  • the method for producing a molded product of the present invention may include a rinsing step of rinsing the photocured portion with a rinsing solution after the developing step and before the drying step described later.
  • the rinsing method is not particularly limited, and examples thereof include a dip method, a paddle method, a spray method, a dynamic discharge method, and a static discharge method.
  • the rinsing conditions are appropriately selected from the range of a rinsing temperature of 5 ° C. to 50 ° C. and a rinsing time of 10 seconds to 300 seconds.
  • the rinse solution is not particularly limited as long as the developer can be washed away without damaging the photocurable portion.
  • the rinsing solution include ethanol, tetrahydrofurfuryl alcohol, 1,1,1,2,3,4,5,5,5-decafluoropentane, ethyl lactate, cyclohexanol and methylcyclohexane. ..
  • the rinse liquid can be used alone or in combination of two or more.
  • the developer and rinse solution used in the method for producing a molded product of the present invention further contains a surfactant as an additive for the purpose of improving the wettability to the photocured portion and efficiently proceeding with development and rinsing. You can also do it.
  • the surfactant may be used alone or in combination of two or more. When the surfactant is used, its content in the developer or rinse solution is preferably 0.001 part by mass to 5 parts by mass with respect to 100 parts by mass of the developer or rinse solution. Is 0.01 part by mass to 3 parts by mass, more preferably 0.05 part by mass to 1 part by mass.
  • the developer and rinse solution used in the method for producing a molded product of the present invention may contain an antioxidant as another additive, if necessary. Examples of the antioxidant include a phenol-based antioxidant of the component (f), a sulfide-based antioxidant of the component (g), and a phosphite-based antioxidant.
  • the method for producing a molded product of the present invention includes, after the developing step, a drying step of spin-drying the support on which the photocurable portion is formed. This step can be carried out by rotating the support with a spin-drying device such as a spinner or a coater.
  • the drying conditions are not particularly limited, but are appropriately selected from, for example, a rotation speed of 200 rpm to 3000 rpm, 10 seconds to 10 minutes.
  • the method for producing a molded product of the present invention may include a post-exposure step of exposing the entire surface of the photocurable portion after the drying step. As the light beam exposed in this step, a light ray that can be used in the photocuring step can be used.
  • the method for producing a molded product of the present invention may include a post-baking step of heating the photocurable portion after the post-exposure step.
  • the post-baking conditions are appropriately selected from, for example, 50 ° C. to 260 ° C., 1 minute to 24 hours.
  • the heating means is not particularly limited, and examples thereof include a hot plate and an oven.
  • the method for producing a molded product of the present invention further includes a step of forming an antireflection film on the surface of the photocurable portion after the post-exposure step or, if the post-baking step is performed, the post-baking step. You may.
  • the antireflection film is formed on the surface of the photocured product in order to suppress the reflection of light incident on the photocured product and improve the transmittance.
  • Examples of the method for forming the antireflection film include a vacuum deposition method, a sputtering method, a CVD method, a mist method, a spin coating method, a dip coating method and a spray coating method.
  • examples of the antireflection film include an inorganic film such as magnesium fluoride and silicon dioxide, and an organic film such as organopolysiloxane.
  • the molded product produced by such a method can be suitably used as a lens for a camera module.
  • Hem crack observation device Optical microscope MX61A manufactured by Olympus Corporation Conditions: Bright field, objective 10 times (5)
  • Transmittance measuring device JASCO Corporation Ultraviolet visible near infrared spectrophotometer V-670 Reference: Air (6)
  • Substrate warpage measuring device Non-contact surface property measuring device PF-60 manufactured by Mitaka Kohki Co., Ltd.
  • the sources of the compounds used in each production example, example and comparative example are as follows.
  • A-DOG Made by Shin-Nakamura Chemical Industry Co., Ltd.
  • Product name: NK ester APG-400 A-TMPT Made by Shin-Nakamura Chemical Industry Co., Ltd.
  • Product name: NK ester A-TMPT UA-4200 Made by Shin-Nakamura Chemical Industry Co., Ltd.
  • A-DOG, APG-100, APG-400, A-TMPT, UA-4200, V # 195 and V # 260 have a (meth) acryloyloxy group in one molecule that can be used as the component (a). It is a polyfunctional (meth) acrylate having two or more. Of these, A-DOG, APG-100, APG-400, UA-4200, V # 195 and V # 260 are bifunctional (meth) acrylates having two (meth) acryloyloxy groups in one molecule. Of these, UA-4200 is the bifunctional urethane (meth) acrylate of the component (a1), and V # 195 and V # 260 are represented by the formula (3) of the component (a2). It is a bifunctional (meth) acrylate.
  • I184 is a photoradical initiator that can be used as the component (b).
  • OTES and MOTMS are silane coupling agents represented by the formula (1) that modify the surface of silica particles of the component (c), and MPTMS is another silane not represented by the formula (1). It is a coupling agent.
  • silica sol i methanol-dispersed silica sol, primary particle diameter 20 nm to 25 nm, silica particle concentration 40% by mass
  • silica sol ii methanol-dispersed silica sol, primary particle diameter 10 nm to 15 nm, silica particle concentration 30% by mass
  • NR1 and PEPT are polyfunctional thiols represented by the formula (2) that can be used as the component (d).
  • SA1303P Cyclic molecule is cyclodextrin, linear molecule is polyethylene glycol chain, blocking group is adamantyl group, and the side chain of the cyclic molecule is a methylethylketone dispersion of polyrotaxane having an acrylicloyloxy group via a spacer, solid content. (Concentration: 50% by mass) is a polyrotaxane having a (meth) acryloyloxy group that can be used as the component (e).
  • I245 is a phenolic antioxidant that can be used as the component (f).
  • the AO503 is a sulfide-based antioxidant that can be used as the component (g).
  • IBXA and AOMA are monomers having one (meth) acryloyloxy group or allyloxy group in one molecule, which can be used as the component (h).
  • Methanol was distilled off under the conditions of 60 ° C. and a reduced pressure of 133.3 Pa or less to obtain a UA-4200 dispersion of MOTMS and MPTMS-modified silica particles (concentration of the MOTMS and MPTMS-modified silica particles was 55% by mass). ..
  • the surface-modified silica particles of the component (c) when the surface-modified silica particles of the component (c) are blended, the UA-4200 obtained in Production Examples 1 to 7 is used. It was blended as a dispersion liquid or an APG-100 dispersion liquid, and when the polyrotaxane of the component (e) was blended, it was blended as the V # 260 dispersion liquid obtained in Production Example 8.
  • Example 1 1.0 g of UA-4200 and 4.3 g of V # 260 as the component (a), 0.1 g of I184 as the component (b), and the UA-4200 dispersion obtained in Production Example 1 as the component (c).
  • 4.2 g of the liquid (2.3 g in terms of MOTMS-modified silica particles) and 0.07 g of I245 as the component (f) were mixed, and the mixture was shaken at 50 ° C. for 15 hours to mix, and then the component (d).
  • 0.5 g of PEPT was added, and the mixture was stirred and defoamed for 10 minutes using the stirring defoaming machine to prepare a photocurable composition 1.
  • Example 2 The photocurable composition 2 was prepared in the same procedure as in Example 1 except that 2.0 g of UA-4200 and 3.3 g of V # 195 were used as the component (a).
  • Example 3 The photocurable composition 3 was prepared in the same procedure as in Example 1 except that 2.0 g of UA-4200 and 3.3 g of A-DOG were used as the component (a).
  • Example 4 The photocurable composition 4 was prepared in the same procedure as in Example 1 except that 2.6 g of UA-4200 and 2.7 g of A-TMPT were used as the component (a).
  • Example 5 4.2 g of APG-400 and 1.1 g of APG-100 were used as the component (a), and 4.2 g (MOTMS-modified silica particles) of the APG-100 dispersion obtained in Production Example 2 was used as the component (c).
  • the photocurable composition 5 was prepared in the same procedure as in Example 1 except that 2.3 g) was used in terms of conversion and 0.5 g of NR1 was used as the component (d).
  • Example 6 The photocurable composition was prepared in the same procedure as in Example 1 except that 4.2 g (2.3 g in terms of MOTMS-modified silica particles) of the UA-4200 dispersion obtained in Production Example 3 was used as the component (c). Object 6 was prepared.
  • Example 7 Photo-curing in the same procedure as in Example 1 except that 4.2 g (2.3 g in terms of MOTMS and MPTMS-modified silica particles) of the UA-4200 dispersion obtained in Production Example 4 was used as the component (c).
  • the sex composition 7 was prepared.
  • Example 8 Photo-curing in the same procedure as in Example 1 except that 4.2 g (2.3 g in terms of MOTMS and OTES-modified silica particles) of the UA-4200 dispersion obtained in Production Example 5 was used as the component (c).
  • the sex composition 8 was prepared.
  • Example 9 1.7 g of UA-4200 and 5.1 g of V # 260 were used as the component (a), and 2.7 g (MOTMS-modified silica particles) of the UA-4200 dispersion obtained in Production Example 6 was used as the component (c).
  • the photocurable composition 9 was prepared in the same procedure as in Example 1 except that it was used (1.2 g in conversion).
  • Example 10 1.2 g of UA-4200 and 5.0 g of V # 260 as the component (a), 0.1 g of I184 as the component (b), and the UA-4200 dispersion obtained in Production Example 1 as the component (c). 3.3 g of the liquid (1.8 g in terms of MOTMS-modified silica particles), 0.07 g of I245 as the component (f), and 0.05 g of AO-503 as the component (g) were blended at 50 ° C. After shaking and mixing for 15 hours, 0.5 g of PEPT was added as the component (d), and the mixture was stirred and defoamed for 10 minutes using the stirring defoaming machine to prepare a photocurable composition 10.
  • Example 11 The photocurable composition 11 was prepared in the same procedure as in Example 1 except that NR1 was used as the component (d).
  • Example 12 0.8 g of UA-4200 and 4.3 g of V # 260 as the component (a), 0.1 g of I184 as the component (b), and the UA-4200 dispersion obtained in Production Example 1 as the component (c).
  • 0.07 g of I245 is mixed, and the mixture is shaken at 50 ° C. for 15 hours to mix, then 0.5 g of PEPT is added as the component (d), and the mixture is stirred and defoamed for 10 minutes using the stirring defoaming machine.
  • the photocurable composition 12 was prepared.
  • Example 13 0.5 g of UA-4200 and 4.0 g of V # 260 were used as the component (a), and 0.8 g of the dispersion obtained in Production Example 8 as the component (e) (0.4 g in terms of polyrotaxane).
  • the photocurable composition 13 was prepared in the same procedure as in Example 12 except that it was used.
  • Example 14 0.3 g of UA-4200 and 3.6 g of V # 260 were used as the component (a), and 1.4 g of the dispersion obtained in Production Example 8 as the component (e) (0.7 g in terms of polyrotaxane).
  • the photocurable composition 14 was prepared in the same procedure as in Example 12 except that it was used.
  • Example 15 0.2 g of UA-4200 and 3.3 g of V # 260 were used as the component (a), and 1.8 g of the V # 260 dispersion obtained in Production Example 8 as the component (e) (0 in terms of polyrotaxan). .9 g)
  • the photocurable composition 15 was prepared in the same procedure as in Example 12 except that it was used.
  • Example 16 4.7 g of V # 260 as the component (a), 0.1 g of I184 as the component (b), and 3.3 g (MOTMS-modified) of the UA-4200 dispersion obtained in Production Example 1 as the component (c). 1.8 g in terms of silica particles), 0.07 g of I245 as the component (f), and 1.5 g of IBXA as the component (h), respectively, and shaking at 50 ° C. for 15 hours to mix, and then the above.
  • the photocurable composition 16 was prepared by adding 0.5 g of PEPT as a component (d) and stirring and defoaming for 10 minutes using the stirring defoaming machine.
  • Example 17 1.7 g of UA-4200 and 5.1 g of V # 260 were used as the component (a), and 2.2 g (MOTMS-modified silica particles) of the UA-4200 dispersion obtained in Production Example 1 was used as the component (c).
  • the photocurable composition 17 was prepared in the same procedure as in Example 16 except that 1.2 g) was used in conversion and 0.5 g of AOMA was used as the component (h).
  • the components of the photocurable compositions 1 to 20 prepared in Examples 1 to 17 and Comparative Examples 1 to 3 are shown in Table 2 below.
  • “part” represents “part by mass”.
  • the mass part of the component (c) is only the surface-modified silica particle component in the UA-4200 dispersion or the APG-100 dispersion obtained in Production Examples 1 to 7.
  • the mass part of the component (e) represents only the polyrotaxane component in the V # 260 dispersion obtained in Production Example 8.
  • Each photocurable composition prepared in Examples 1 to 17 and Comparative Examples 1 to 3 is subjected to mold release treatment by applying Novec (registered trademark) 1720 (manufactured by 3M Japan Ltd.) and drying.
  • the two glass substrates were sandwiched between the two glass substrates via a silicone rubber spacer having a thickness of 500 ⁇ m.
  • the photocurable composition sandwiched between the two release-treated glass substrates was UV- exposed at 30 mW / cm 2 for 200 seconds using the UV-LED irradiation device.
  • the cured product obtained after exposure was peeled from the mold-released glass substrate and then heated on a hot plate at 100 ° C.
  • the photocurable composition was UV- exposed at 30 mW / cm 2 for 200 seconds using a UV-LED irradiator.
  • the cured product obtained after the exposure was peeled off from the mold release-treated glass substrate, and then heated on a hot plate at 100 ° C. for 10 minutes on the non-alkali glass substrate to be subjected to the close contact treatment to have a diameter of 0.5 cm.
  • a cured product having a thickness of 500 ⁇ m was prepared. Further, it was heated on a hot plate at 175 ° C. for 2 minutes and 30 seconds.
  • FIG. 1 is a schematic diagram showing a method for evaluating the amount of warpage of a glass substrate. The obtained results are shown in Table 4 below.
  • the photocurable composition was UV-exposed at 50 mW / cm 2 for 9 seconds via the photomask substrate that had been demolded using the UV-LED irradiator manufactured by Iwasaki Electric Co., Ltd. to obtain light. A hardened part was formed. After the non-alkali glass substrate to which the photocurable portion was in close contact was peeled off from the photomask substrate which had been subjected to the mold release treatment, only development or development and rinsing were performed using the developing apparatus.
  • the developing solution and developing time used, and the rinsing solution and rinsing time are any of the conditions A to E of the developing / rinsing conditions shown in Table 3 below.
  • the rotation speed of the non-alkali glass substrate during development is 300 rpm
  • the rotation speed of the non-alkali glass substrate during rinsing is 200 rpm
  • the discharge flow rate of the developer and the rinse liquid is 200 mL / min.
  • the non-alkali glass substrate was rotated at 3000 rpm for 30 seconds using the developing apparatus to dry the glass substrate.
  • UV exposure was performed at 50 mW / cm 2 for 111 seconds using the UV-LED device manufactured by CCS Inc., and further 10 minutes on a hot plate at 100 ° C.
  • a cured product having a thickness of 1 cm square and 500 ⁇ m was prepared on the non-alkali glass substrate which had been subjected to the close contact treatment.
  • the top surface of the produced 1 cm square, 500 ⁇ m thick cured product has a planar shape.
  • a cured product having a lens shape was also prepared by the following procedure. That is, the release-treated photomask substrate is changed to a resin mold with a light-shielding film (a shape of an inverting lens having a thickness of about 100 ⁇ m), and the 500 ⁇ m-thick silicone rubber spacer is made of 600 ⁇ m-thick silicone rubber.
  • a cured product having a lens shape was produced by the same method as the method for producing a cured product having a thickness of 1 cm square and 500 ⁇ m except that the spacer was used.
  • the top surface of the produced cured product having a lens shape has a curved surface shape.
  • the mold release treatment method for the resin mold with a light-shielding film is the same as the mold release treatment method for the photomask substrate.
  • PGMEA is propylene glycol monomethyl ether acetate
  • PGME is propylene glycol monomethyl ether
  • GBL is ⁇ -butyrolactone
  • EL is ethyl lactate
  • THFA is tetrahydrofurfuryl alcohol
  • CHA is cyclohexanol
  • MCH Represents methylcyclohexane.
  • the developer under condition C and the developer and rinse solution under condition E are mixed solvents, and their components and mixing ratios are shown in Table 3 by mass ratio.
  • the cured product prepared from the photocurable compositions prepared in Examples 1 to 17 showed high transmittance (90% or more) and a low substrate warpage amount (less than 3.0 ⁇ m), and further, Conditions A to Condition E No cracks were observed at the hem regardless of the development / rinsing conditions, or the top surface shape of either a flat surface or a curved surface.
  • FIG. 2 shows the hem portion when the cured product prepared from the photocurable composition 15 prepared in Example 15 is treated under the development / rinsing condition of Condition D.
  • FIG. 3 shows the hem portion when the cured product prepared from the photocurable composition 18 prepared in Comparative Example 1 was treated under the development / rinsing condition of Condition D. The plurality of arrows in FIG. 3 indicate the crack occurrence location. Further, in the cured product prepared from the photocurable compositions prepared in Comparative Example 2 and Comparative Example 3 in which the component (d) was not used, the amount of substrate warpage was 3.0 ⁇ m or more.
  • the cured product (molded product) obtained from the photocurable composition containing the component (a) to the component (d) of the present invention exhibits high transmittance, and the cured product (molded product) is placed on the support.
  • the amount of warpage of the support when the body) is formed is small, and cracks do not occur at the hem of the cured product (molded product) even after undergoing a development process using an organic solvent. It was shown to have desirable properties as a lens of.

Abstract

La présente invention vise à fournir une nouvelle composition photodurcissable. L'invention concerne par conséquent une composition photodurcissable qui comprend le composant (a), le composant (b), le composant (c) et le composant (d) suivants. (a) : au moins un (méth)acrylate polyfonctionnel ayant deux groupes (méth)acryloyloxy ou plus par molécule. (b) : un initiateur photoradicalaire. (c) : des particules de silice ayant une taille de particule primaire de 1 à 100 nm, les particules de silice étant modifiées en surface par au moins un agent de couplage au silane représenté par la formule (1). (d) : un thiol polyfonctionnel. L'invention concerne également un thiol polyfonctionnel spécifique. (Dans la formule, X1 représente un atome d'hydrogène ou un groupe (méth) acryloyloxy, R1 et R2 représentent chacun indépendamment un atome d'hydrogène ou un groupe alkyle en C1-2, m représente un nombre entier de 8 à 14, et n représente un nombre entier de 0 à 2.)
PCT/JP2021/011251 2020-04-20 2021-03-18 Composition photodurcissable WO2021215155A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2022516891A JP7469746B2 (ja) 2020-04-20 2021-03-18 光硬化性組成物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020074903 2020-04-20
JP2020-074903 2020-04-20

Publications (1)

Publication Number Publication Date
WO2021215155A1 true WO2021215155A1 (fr) 2021-10-28

Family

ID=78269411

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/011251 WO2021215155A1 (fr) 2020-04-20 2021-03-18 Composition photodurcissable

Country Status (3)

Country Link
JP (1) JP7469746B2 (fr)
TW (1) TW202206466A (fr)
WO (1) WO2021215155A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011202127A (ja) * 2010-03-26 2011-10-13 Asahi Kasei E-Materials Corp 感光性樹脂組成物及び硬化物
JP2013151609A (ja) * 2012-01-25 2013-08-08 Shin-Etsu Chemical Co Ltd 硬化性樹脂組成物並びにその硬化成形品及び硬化皮膜を有する物品
JP2015172176A (ja) * 2014-02-18 2015-10-01 日立化成株式会社 光硬化性樹脂組成物並びにそれを用いた光硬化性遮光塗料、光漏洩防止材、液晶表示パネル及び液晶表示装置、並びに光硬化方法
JP2017114962A (ja) * 2015-12-22 2017-06-29 日立化成株式会社 先供給型アンダーフィル材及びその硬化物、並びに電子部品装置及びその製造方法
WO2017203979A1 (fr) * 2016-05-27 2017-11-30 富士フイルム株式会社 Composition durcissable, film durci, filtre de couleur, film de blocage de lumière, élément d'imagerie à l'état solide, dispositif d'affichage d'image, et procédé de production de film durci
WO2018155013A1 (fr) * 2017-02-22 2018-08-30 日産化学工業株式会社 Composition photodurcissable pour impression

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011202127A (ja) * 2010-03-26 2011-10-13 Asahi Kasei E-Materials Corp 感光性樹脂組成物及び硬化物
JP2013151609A (ja) * 2012-01-25 2013-08-08 Shin-Etsu Chemical Co Ltd 硬化性樹脂組成物並びにその硬化成形品及び硬化皮膜を有する物品
JP2015172176A (ja) * 2014-02-18 2015-10-01 日立化成株式会社 光硬化性樹脂組成物並びにそれを用いた光硬化性遮光塗料、光漏洩防止材、液晶表示パネル及び液晶表示装置、並びに光硬化方法
JP2017114962A (ja) * 2015-12-22 2017-06-29 日立化成株式会社 先供給型アンダーフィル材及びその硬化物、並びに電子部品装置及びその製造方法
WO2017203979A1 (fr) * 2016-05-27 2017-11-30 富士フイルム株式会社 Composition durcissable, film durci, filtre de couleur, film de blocage de lumière, élément d'imagerie à l'état solide, dispositif d'affichage d'image, et procédé de production de film durci
WO2018155013A1 (fr) * 2017-02-22 2018-08-30 日産化学工業株式会社 Composition photodurcissable pour impression

Also Published As

Publication number Publication date
JP7469746B2 (ja) 2024-04-17
JPWO2021215155A1 (fr) 2021-10-28
TW202206466A (zh) 2022-02-16

Similar Documents

Publication Publication Date Title
KR101070656B1 (ko) 경화성 조성물 및 반사 방지용 적층체
KR102549487B1 (ko) 임프린트용 광경화성 조성물
KR20130087576A (ko) 경화성 수지 조성물
WO2020003863A1 (fr) Composition photodurcissable pour impression
KR102496908B1 (ko) 임프린트용 광경화성 조성물
TWI363764B (fr)
KR20200128404A (ko) 폴리머를 포함하는 임프린트용 광경화성 조성물
WO2021215155A1 (fr) Composition photodurcissable
WO2023100991A1 (fr) Dérivé de silsesquioxane, composition durcissable, agent de revêtement dur, objet durci, revêtement dur, et substrat
WO2022202005A1 (fr) Composition photodurcissable pour formation de film
JP7091683B2 (ja) オルガノポリシロキサン
TWI785132B (zh) 壓印用光硬化性組成物
WO2022044743A1 (fr) Composition photodurcissable pour empreinte
JP2022092626A (ja) インプリント用光硬化性組成物
WO2006054470A1 (fr) Procede de production d’un corps multicouche
WO2023100992A1 (fr) Dérivé de silsesquioxane, composition durcissable, objet durci, et substrat
TW202406993A (zh) 倍半矽氧烷衍生物及其製造方法、硬化性組成物、硬塗劑、硬化物、硬塗層、以及基材
JP2022182542A (ja) 光硬化性樹脂組成物およびその用途

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21792400

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022516891

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21792400

Country of ref document: EP

Kind code of ref document: A1