WO2021049443A1 - Composition de résine durcissable par des ultraviolets, produit durci et lentille optique - Google Patents

Composition de résine durcissable par des ultraviolets, produit durci et lentille optique Download PDF

Info

Publication number
WO2021049443A1
WO2021049443A1 PCT/JP2020/033711 JP2020033711W WO2021049443A1 WO 2021049443 A1 WO2021049443 A1 WO 2021049443A1 JP 2020033711 W JP2020033711 W JP 2020033711W WO 2021049443 A1 WO2021049443 A1 WO 2021049443A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin composition
curable resin
ultraviolet curable
ultraviolet
cured product
Prior art date
Application number
PCT/JP2020/033711
Other languages
English (en)
Japanese (ja)
Inventor
吉田　淳
Original Assignee
Ａｇｃ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 Ａｇｃ株式会社 filed Critical Ａｇｃ株式会社
Priority to JP2021545512A priority Critical patent/JPWO2021049443A1/ja
Publication of WO2021049443A1 publication Critical patent/WO2021049443A1/fr

Links

Images

Classifications

    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/18—Oxetanes
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • G02B3/00—Simple or compound lenses

Definitions

  • the present invention relates to an ultraviolet curable resin composition, a cured product, and an optical lens.
  • An ultraviolet curable resin composition containing an epoxy resin having a small curing shrinkage is widely used for an optical lens used in a mobile phone, a digital camera, or the like.
  • a wafer level lens is manufactured by molding a plurality of lenses on a substrate using an ultraviolet curable resin composition, and the substrate is cut to separate the plurality of lenses to manufacture a lens module.
  • a mold having a plurality of recesses having a shape corresponding to the lens shape is used, and the UV curable resin composition is sandwiched between each recess of the mold and the substrate.
  • a method of forming a lens by curing a lens is known (Patent Document 1).
  • a mold provided with a shielding portion that blocks ultraviolet rays is used, and only the portion to be a lens in the ultraviolet curable resin composition at the time of curing is partially irradiated with ultraviolet rays to be cured.
  • the excess portion of the lens of the ultraviolet curable resin composition is not irradiated with ultraviolet rays, and is removed by cleaning after the curing step.
  • the ultraviolet curable resin composition using the conventional epoxy resin when the ultraviolet curable resin composition is cured in the exposed portion of ultraviolet rays, the curing of the ultraviolet curable resin composition is likely to proceed even in the unexposed portion. Therefore, the outer diameter dimensional stability of the formed lens tends to be inferior.
  • An object of the present invention is to provide an ultraviolet curable resin composition having excellent outer diameter dimensional stability of a cured product such as a lens, a cured product using the same, and an optical lens.
  • An ultraviolet curable resin composition containing a polyfunctional epoxy resin, an oxetane compound, and a delayed curing agent, which is irradiated with ultraviolet rays at a wavelength of 365 nm and an illuminance of 7 mW / cm 2 for 5 seconds.
  • UV curable resin composition in which 2 is less than 2 minutes.
  • [5] A cured product obtained by curing the ultraviolet curable resin composition according to any one of [1] to [4].
  • the cured product according to [5] which has an Abbe number of 50 or more.
  • an ultraviolet curable resin composition having excellent outer diameter dimensional stability of a cured product such as a lens, a cured product using the same, and an optical lens.
  • FIG. 1 is a cross-sectional view illustrating one step of a method for manufacturing a wafer level lens.
  • FIG. 2 is a cross-sectional view illustrating one step of a method for manufacturing a wafer level lens.
  • FIG. 3 is a cross-sectional view illustrating one step of a method for manufacturing a wafer level lens.
  • FIG. 4 is a cross-sectional view illustrating one step of a method for manufacturing a wafer level lens.
  • FIG. 5 is a cross-sectional view illustrating one step of a method for manufacturing a wafer level lens.
  • the meanings and definitions of the terms in the present specification are as follows.
  • the numerical range represented by "-" means a numerical range including the numerical values before and after ... as the lower limit value and the upper limit value.
  • the “delayed curing agent” means a compound that traps a cation component in a cation polymerization process initiated by irradiating an ultraviolet curable resin composition with ultraviolet rays.
  • the “Abbe number” refers to the inverse dispersibility of a so-called optical lens, and is based on JIS Z 8120: 2001, and is based on the refractive index measured at 25 ⁇ 10 ° C. by an Abbe refractive index meter. It is a value calculated by.
  • ⁇ d (n d -1) / (n F ⁇ n C ) ⁇ ⁇ ⁇ Equation 1
  • ⁇ d is an Abbe number.
  • n d is the refractive index for the d-line (wavelength 587.56 nm).
  • n F is the refractive index for light having a wavelength of 486 nm.
  • n C is the refractive index for light having a wavelength of 656 nm.
  • the ultraviolet curable resin composition of the present invention contains a polyfunctional epoxy resin, an oxetane compound, and a delayed curing agent. Further, the ultraviolet curable resin composition of the present invention satisfies the following conditions.
  • the ultraviolet curable resin composition of the present invention is irradiated with ultraviolet rays having a wavelength of 365 nm and an illuminance of 7 mW / cm 2 for 5 seconds
  • the storage elastic modulus of the ultraviolet curable resin composition is stored before the ultraviolet irradiation from the start of the ultraviolet irradiation. Let t 1 be the time until the time point when the elastic modulus becomes 100 times.
  • the ultraviolet curable resin composition of the present invention when the ultraviolet curable resin composition of the present invention is irradiated with ultraviolet rays having a wavelength of 365 nm and an illuminance of 7 mW / cm 2 for 20 seconds, the storage elastic modulus of the ultraviolet curable resin composition is before the ultraviolet irradiation from the start of the ultraviolet irradiation.
  • Let t 2 be the time until the time when it becomes 100 times the storage elastic modulus of. At this time, in the ultraviolet curable resin composition of the present invention, t 1 is more than 2 minutes and t 2 is less than 2 minutes.
  • the storage elastic modulus (unit: Pa) of the ultraviolet curable resin composition is a value measured at 25 ° C. and can be measured by a rheometer. Specifically, at 25 ° C., monitoring of the storage elastic modulus of the ultraviolet curable resin composition by a rheometer was started under dark conditions, and ultraviolet rays having a wavelength of 365 nm and an illuminance of 7 mW / cm 2 were applied to the ultraviolet curable resin composition for 5 seconds. After irradiation, the conditions are dark again. Then, from the start of irradiation of the ultraviolet rays and the time until the time when the storage modulus of the ultraviolet curable resin composition is 100 times the storage elastic modulus before the ultraviolet irradiation and t 1. t 2 can be measured by the same method as t 1 except that the irradiation time of ultraviolet rays is 20 seconds.
  • the ultraviolet curable resin composition of the present invention satisfies the above conditions, the contrast between the curing speeds of the exposed portion and the unexposed portion of ultraviolet rays can be increased in the production of the cured product by the imprint method. As a result, while the exposed portion is sufficiently cured, the curing of the unexposed portion can be sufficiently suppressed and removed by cleaning, so that the obtained cured product has excellent outer diameter dimensional stability.
  • t 1 is more than 2 minutes, and it is easy to sufficiently suppress the curing of the unexposed portion of ultraviolet rays. Considering that the unexposed portion is washed in a later step, t 1 is preferably 3 minutes or longer, more preferably 5 minutes or longer. The upper limit of t 1 is not particularly limited, but is substantially about 30 minutes.
  • t 2 is less than 2 minutes, preferably less than 1 minute, more preferably less than 45 seconds, from the viewpoint of curability of the exposed portion of ultraviolet rays.
  • the lower limit of t 2 is not particularly limited, but is substantially about 15 seconds.
  • the difference between t 1 and t 2 (t 1- t 2 ) is 60 seconds or more because the contrast between the curing speeds of the exposed and unexposed areas of ultraviolet rays is large and the obtained cured product has excellent outer diameter dimensional stability. Is preferable, 120 seconds or more is more preferable, and 300 seconds or more is further preferable.
  • the upper limit of the difference (t 1 to t 2 ) is not particularly limited, but is substantially about 600 seconds.
  • the adjustment of t 1 and t 2 of the ultraviolet curable resin composition of the present invention can be performed by adjusting the content of the delayed curing agent.
  • t 1 and t 2 are described above. It can be adjusted to meet the conditions. Delay t 1 and t 2 As the content increases the curing agent is reduced, t 1 and t 2 As the content of the delay curing agent is less tends to increase.
  • the slope k 1 is preferably less than 500, more preferably less than 100.
  • the cured contrast between the cured portion and the uncured portion is high, and the viscosity of the resin in the uncured portion is kept low, which is the object of the present invention. Outer diameter control becomes easier.
  • the inclination k 2 is preferably 1000 or more, and more preferably 10000 or more.
  • the slope k 2 is equal to or greater than the lower limit of the above range, the curing rate is unlikely to be extremely slow as compared with a general UV curing system. That is, the UV curing tact in the fabrication of the wafer level lens is shortened, which is advantageous in terms of productivity.
  • the polyfunctional epoxy resin is an epoxy resin having two or more epoxy groups in one molecule.
  • the polyfunctional epoxy resin include a polyfunctional aliphatic epoxy resin and a polyfunctional aromatic epoxy resin. Of these, a polyfunctional aliphatic epoxy resin is preferable, and a polyfunctional alicyclic epoxy resin is more preferable, from the viewpoint of transparency, heat resistance, and resistance to environmental reliability of the cured product in the visible light region.
  • polyfunctional alicyclic epoxy resin examples include 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and hydrogenated bisphenol A.
  • examples thereof include a type epoxy resin and a hydrogenated bisphenol F type epoxy resin.
  • a polyfunctional chain epoxy resin such as a polyglycidyl etherified product of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof, or a polyglycidyl ester of an aliphatic long-chain polybasic acid may be used.
  • polyfunctional aromatic epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolac type epoxy resin, xylylene type epoxy resin, and biphenyl type epoxy resin.
  • the polyfunctional epoxy resin contained in the ultraviolet curable resin composition may be one kind or two or more kinds.
  • oxetane compound a monofunctional oxetane compound may be used, or a polyfunctional oxetane compound may be used.
  • the monofunctional oxetane compound is an oxetane compound having one oxetanyl group in one molecule and not containing a carbon-carbon double bond.
  • the polyfunctional oxetane compound is a carbon-carbon double bond-free oxetane compound having two or more oxetanyl groups in one molecule.
  • Examples of the monofunctional oxetane compound include 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (commercially available product name: Aron Oxetane OXT-212 (manufactured by Toa Synthetic Co., Ltd.)), 3-ethyl-3. -Hydroxymethyloxetane (commercially available product name Aron Oxetane OXT-101, (manufactured by Toa Synthetic Co., Ltd.), etc.) can be exemplified.
  • polyfunctional oxetane compound examples include bis (3-ethyl-3-oxetanylmethyl) ether and 1,6-bis [(3-ethyloxetane-3-yl) methoxy] -2,2,3,3,4.
  • bis (3-ethyl-3-oxetanylmethyl) ether is preferable from the viewpoint of imparting a practical curing rate and reliability of the cured product as a lens.
  • the oxetane compound contained in the ultraviolet curable resin composition may be one kind or two or more kinds.
  • the ultraviolet curable resin composition of the present invention may contain a resin other than the polyfunctional epoxy resin and the oxetane compound.
  • resins include monofunctional epoxy resins and epoxy-modified silicone resins.
  • the total content of the polyfunctional epoxy resin and the oxetane compound in the ultraviolet curable resin composition is preferably 40% by mass to 100% by mass, preferably 60% by mass, based on the total mass of the resin components in the ultraviolet curable resin composition. By mass% or more is more preferable, and 80% by mass or more is further preferable. When the ratio is not more than the lower limit of the above range, the mechanical strength of the cured product is high while ensuring rapid ultraviolet curability, which is preferable as the physical characteristics of the lens material.
  • the ratio of the polyfunctional epoxy resin to the total mass of the polyfunctional epoxy resin and the oxetane compound in the ultraviolet curable resin composition is preferably 20% by mass to 95% by mass, more preferably 30% by mass to 90% by mass, and 40% by mass. % -80% by mass is more preferable.
  • the proportion of the polyfunctional epoxy resin is at least the lower limit of the above range, the transparency of the cured product and the crack resistance in environmental tests such as a cold heat test are excellent.
  • the proportion of the polyfunctional epoxy resin is not more than the upper limit of the above range, the ultraviolet curability is excellent.
  • the delayed curing agent examples include amine compounds, polyalkylene glycols, and crown ethers.
  • the amine compound is preferable because the contrast of the curing speed between the exposed portion and the unexposed portion of the ultraviolet rays is large and the cured product is excellent in the outer diameter dimensional stability.
  • the delayed curing agent contained in the ultraviolet curable resin composition may be one kind or two or more kinds.
  • the amine compound examples include aliphatic amine compounds such as isopropylamine, dimethylamine, triethylamine, tetramethylethylenediamine and N-ethyldiisopropylamine, and aromatic amines such as aniline.
  • the tertiary aliphatic amine compound is preferable because the contrast of the curing speed between the exposed portion and the unexposed portion of the ultraviolet ray is large, and the compatibility with the ultraviolet curable resin composition and the ability to trap the cation component are excellent.
  • Triethylamine and tetramethylethylenediamine are more preferable in consideration of availability.
  • polyalkylene glycol examples include ethylene glycol, polytrimethylene ether glycol, and polytetramethylene ether glycol.
  • crown ether examples include 15-crown-5-ether, 18-crown-6-ether, and cis-dicyclohexano18-crown-6-ether.
  • the content of the delayed curing agent in the ultraviolet curable resin composition is t 1 and t depending on the content of the polyfunctional epoxy resin and the oxetane compound, the type of the delayed curing agent, and the type and content of the photopolymerization initiator. 2 may be appropriately adjusted so as to satisfy the above-mentioned conditions.
  • the content of the amine compound in the ultraviolet curable resin composition is 0.01 part by mass to 1.0 part by mass with respect to 100 parts by mass of the total mass of the polyfunctional epoxy resin and the oxetane compound. It is preferably parts by mass, more preferably 0.02 parts by mass to 0.50 parts by mass, and even more preferably 0.05 parts by mass to 0.2 parts by mass.
  • the ultraviolet curable resin composition of the present invention may further contain a photopolymerization initiator.
  • the photopolymerization initiator include various photocationic polymerization initiators that generate an acid that can be cationically polymerized by irradiation with ultraviolet rays.
  • the anionic component of the cationic photopolymerization initiator for example, SbF 6 -, PF 6 - , BF 4 -, AsF 6 -, B (C 6 F 5) 4 - can be exemplified.
  • PF 6 as an anion component - or SbF 6 - onium salts such as aromatic sulfonium salts are preferred including.
  • the content of the photopolymerization initiator in the ultraviolet curable resin composition is 0.05 parts by mass to 10 parts by mass with respect to 100 parts by mass of the resin component in the ultraviolet curable resin composition. .0 parts by mass is preferable, and 0.1 parts by mass to 3.0 parts by mass is more preferable.
  • the content of the photopolymerization initiator is at least the lower limit of the above range, the curability is excellent.
  • the content of the photopolymerization initiator is not more than the upper limit of the above range, it is easy to suppress the coloring of the cured product.
  • the ultraviolet curable resin composition of the present invention can be used as a coupling agent (silane-based coupling agent, titanium-based coupling agent, etc.), flexibility-imparting agent (synthetic rubber, polyorganosiloxane, etc.), and oxidation, if necessary.
  • Additives such as inhibitors, defoamers, hydrocarbon waxes, and inorganic fillers may be included.
  • the cured product of the present invention is a cured product obtained by curing the ultraviolet curable resin composition of the present invention.
  • the application of the cured product is not particularly limited, and examples thereof include an optical lens.
  • the shape and outer diameter of the cured product can be appropriately set according to the application.
  • the thickness of the cured product is not particularly limited, and can be, for example, 0.01 mm to 5.0 mm.
  • the Abbe number of the cured product of the present invention is preferably 50 or more, more preferably 53 or more, and even more preferably 55 or more.
  • the Abbe number is not less than the lower limit of the above range, chromatic aberration is less likely to occur when used as an optical lens, and the resolution becomes high.
  • the higher the Abbe number, the better, and the upper limit is not particularly limited, but is practically about 60.
  • an imprint method using a mold can be exemplified.
  • the ultraviolet curable resin composition is cured in a state where the mold having a recess having a shape corresponding to the shape of the desired cured product on the surface and the ultraviolet curable resin composition of the present invention are in contact with each other.
  • An example of a method for producing a cured product having a desired shape can be exemplified.
  • the wafer level lens includes a substrate and a plurality of optical lenses provided on the substrate. It should be noted that the outer diameter dimensions and the like of the figures illustrated in the following description are examples, and the present invention is not necessarily limited thereto, and the present invention can be appropriately modified without changing the gist thereof. Is.
  • the wafer level lens manufacturing method of the present embodiment includes, for example, the following steps (a) to (d).
  • Step (a) As shown in FIG. 1, the ultraviolet curable resin composition 20 is placed in each recess 12 of the mold 10 provided with recesses 12 having a shape corresponding to the shape of the optical lens.
  • a plurality of molding portions 16 are provided on the plate-shaped portion 14, and a recess 12 is formed on the upper surface of the molding portion 16.
  • a shielding portion 18 that blocks the transmission of ultraviolet rays is provided between the recesses 12 of the adjacent molding portions 16 in the surface layer portion on the molding portion 16 side of the plate-shaped portion 14.
  • the shape and outer diameter of the recess 12 correspond to the shape of the optical lens 34.
  • Examples of the material for forming the plate-shaped portion 14 other than the shielding portion 18 and the molding portion 16 in the mold 10 include a translucent material.
  • a material for forming the shielding portion 18 a non-transmissive material can be exemplified.
  • Examples of the translucent material include a cured product of an acrylic UV curable resin, glass such as quartz glass, polydimethylsiloxane, cyclic polyolefin, polycarbonate, polyethylene terephthalate, and transparent fluororesin.
  • Examples of the non-transmissive material include chromium, nickel, copper, titanium, oxides thereof, silicon carbide, and mica.
  • Examples of the method for arranging the ultraviolet curable resin composition 20 in the recess 12 of the mold 10 in the step (a) include an inkjet method, a potting method (dispensing method), a spin coating method, a roll coating method, a casting method, and a dip coating method. Examples include the method, the die coat method, and the Langmüller project method.
  • the press pressure (gauge pressure) when the ultraviolet curable resin composition 20 is sandwiched between the mold 10 and the substrate 32 is preferably more than 0 MPa and 10 MPa or less, more preferably 0.1 MPa to 5 MPa. preferable.
  • the temperature at which the ultraviolet curable resin composition 20 is sandwiched between the mold 10 and the substrate 32 is preferably 0 ° C to 110 ° C, more preferably 10 ° C to 80 ° C.
  • the thickness of the substrate 32 is not particularly limited, and can be, for example, 0.1 mm to 2.0 mm.
  • step (c) ultraviolet rays are irradiated from the side opposite to the shielding portion 18 of the plate-shaped portion 14 in the mold 10.
  • Ultraviolet rays are transmitted from between the shielding portions 18 and partially irradiate each ultraviolet curable resin composition 20.
  • the ultraviolet curable resin composition 20 is cured to form the optical lens 34 in the exposed portion between the shielding portions 18, that is, the recess 12. Since ultraviolet rays are blocked by the shielding portion 18 between the adjacent recesses 12, it becomes an unexposed portion. Since the UV-curable resin composition 20 has a large contrast between the curing speeds of the exposed portion and the unexposed portion, the curing of the UV-curable resin composition 20 is sufficiently suppressed in the unexposed portion between the adjacent recesses 12. ..
  • Examples of the light source of ultraviolet rays include UV-LED, low-pressure mercury lamp, high-pressure mercury lamp, and ultra-high-pressure mercury lamp.
  • the irradiation dose of ultraviolet rays is preferably 100mJ / cm 2 ⁇ 30,000mJ / cm 2, 1,000mJ / cm 2 ⁇ 20,000mJ / cm 2 is more preferable.
  • the mold 10 is separated, and the ultraviolet curable resin composition 20 in the unexposed portion shown in FIG. 4 is washed and removed.
  • a wafer level lens 30 in which a plurality of optical lenses 34 are provided on the substrate 32 can be obtained.
  • the temperature at which the optical lens 34 and the mold 10 are separated is preferably 0 ° C. to 110 ° C., more preferably 10 ° C. to 80 ° C.
  • the cleaning method include spin cleaning, dip cleaning, and ultrasonic cleaning.
  • the ultraviolet curable resin composition contains a delayed curing agent and t 1 and t 2 are controlled under specific conditions, the curing speed in the exposed portion and the unexposed portion is different.
  • the contrast is high. Therefore, when producing a cured product such as an optical lens, the cured product can be formed while sufficiently suppressing the curing of the ultraviolet curable resin composition in the unexposed portion, which is an extra portion of the product. As a result, the ultraviolet curable resin composition in the unexposed portion can be stably removed, so that the obtained cured product is excellent in outer diameter dimensional stability.
  • Examples 2, 3, 5, 6, 8, 9, 11, and 12 are examples, and examples 1, 4, 7, and 10 are comparative examples. [Abbreviation] The abbreviations of the raw materials used in this example are shown below.
  • A-1 jER YX8000 (hydrogenated bisphenol A type epoxy resin monomer, manufactured by Mitsubishi Chemical Corporation)
  • A-2 Celoxide 2021P (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, manufactured by Daicel Corporation)
  • A-3 CELVENUS LU1701HA (mixture of polyfunctional epoxy resin and oxetane compound, manufactured by Daicel Corporation)
  • A-4 jER YX8040 (hydrogenated bisphenol A type epoxy resin oligomer, manufactured by Mitsubishi Chemical Corporation)
  • A-5 TEPIC-FL (1,3,5-tris (6- (oxylan-2-yl) hexyl) -1,3,5-triazine-2,4,6-trione, manufactured by Nissan Chemical Industries, Ltd.)
  • A-6 OXT-221 (bis (3-ethyl-3-oxetanylmethyl) ether, manufactured by Toagosei Co., Ltd.)
  • B-1 Triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • B-2 Tetramethylethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • the time until the time when the storage modulus of the ultraviolet curable resin composition is 100 times the storage elastic modulus before the ultraviolet irradiation was t 1.
  • Plotting the storage modulus versus time, in the graph when the irradiation for 5 seconds UV, the rise of the slope of the storage modulus of the cured start was k 1.
  • the time t 2 and the slope k 2 were measured in the same manner as the time t 1 and the slope k 1 except that the irradiation time of ultraviolet rays was 20 seconds.
  • a wafer level lens was manufactured by the following procedure.
  • the ultraviolet curable resin composition shown in Table 2 was used as the ultraviolet curable resin composition 20.
  • a mold 10 having a circular shape in a plan view, a plurality of recesses 12 having a depth of 0.5 mm at the deepest portion and a diameter of 2.0 mm in a plan view, and an opening diameter of a shielding portion of 1.8 mm was prepared. ..
  • the ultraviolet curable resin composition 20 was arranged in each recess 12 of the mold 10 having recesses 12 having a shape corresponding to the shape of the optical lens. As shown in FIG.
  • the substrate 32 was arranged on the concave portion 12 side of the mold 10, and the ultraviolet curable resin composition 20 was sandwiched between the mold 10 and the substrate 32.
  • each ultraviolet curable resin composition 20 was partially irradiated with ultraviolet rays at 2,500 mJ / cm 2 to cure the exposed portion to form an optical lens 34.
  • the mold 10 was separated.
  • the ultraviolet curable resin composition 20 in the unexposed portion was removed by spin cleaning using an organic solvent to obtain a wafer level lens 30.
  • the outer diameter dimensional stability of the optical lens in the wafer level lens obtained in each example was evaluated by the following method. 1000 lenses per wafer surface were imprinted, and the outer diameter defect rate was calculated using the automatic image measurement system NEXIV VMZ-R4540 (manufactured by Nikon Corporation). As a criterion for shape defect, the outer diameter of the lens was set to exceed the diameter of the mold shielding portion by 10% or more. A: Defect rate less than 10% B: Defect rate 10% or more Table 2 shows the evaluation results of each example.
  • Table 2 shows the measurement results of the Abbe number ⁇ d of the cured product constituting the wafer level lenses of Examples 1 to 12.
  • the method of preparing the evaluation sample and the method of measurement are shown below.
  • An ultraviolet curable composition was sandwiched between two glass substrates that had undergone a mold release treatment. At this time, the curable composition was sandwiched so that the thickness of the cured product (distance between the glass substrates) was 500 ⁇ m.
  • the ultraviolet curable composition is irradiated with ultraviolet rays (using a 365 nm LED lamp) through a glass substrate that has undergone a mold release treatment at an exposure amount of 4000 mJ / cm 2 , and then heated on a hot plate at 80 ° C. for 30 minutes. And cured.
  • a film-like cured product was obtained by releasing the cured product from the glass substrate.
  • the obtained cured product was heat-treated in a nitrogen atmosphere at 180 ° C. for 3 hours to obtain a cured product as an evaluation sample. Evaluation samples were prepared for each of the ultraviolet curable compositions X-1 to X-8 and Y-1 to Y-4 by the above method.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Epoxy Resins (AREA)

Abstract

La présente invention concerne une composition de résine durcissable par des ultraviolets qui contient une résine époxy multifonctionnelle, un composé oxétane et un retardateur de durcissement. Si elle est exposée à de la lumière ultraviolette ayant une longueur d'onde de 365 nm et un éclairement de 7 mW/cm2 pendant 5 secondes, le temps t1 du début de l'exposition à de la lumière ultraviolette jusqu'au point auquel le module d'élasticité de conservation de la composition de résine durcissable par des ultraviolets est de 100 fois son module d'élasticité de conservation avant l'exposition à de la lumière ultraviolette est supérieur à 2 minutes ; et si elle est exposée à de la lumière ultraviolette ayant une longueur d'onde de 365 nm et un éclairement de 7 mW/cm2 pendant 20 secondes, le temps t2 du début de l'exposition à de la lumière ultraviolette jusqu'au point auquel le module d'élasticité de conservation de la composition de résine durcissable par des ultraviolets est de 100 fois son module d'élasticité de conservation avant l'exposition à de la lumière ultraviolette est inférieur à 2 minutes.
PCT/JP2020/033711 2019-09-12 2020-09-07 Composition de résine durcissable par des ultraviolets, produit durci et lentille optique WO2021049443A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2021545512A JPWO2021049443A1 (fr) 2019-09-12 2020-09-07

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019166513 2019-09-12
JP2019-166513 2019-09-12

Publications (1)

Publication Number Publication Date
WO2021049443A1 true WO2021049443A1 (fr) 2021-03-18

Family

ID=74866613

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/033711 WO2021049443A1 (fr) 2019-09-12 2020-09-07 Composition de résine durcissable par des ultraviolets, produit durci et lentille optique

Country Status (2)

Country Link
JP (1) JPWO2021049443A1 (fr)
WO (1) WO2021049443A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005194379A (ja) * 2004-01-07 2005-07-21 Konica Minolta Medical & Graphic Inc 活性光線硬化型組成物、活性光線硬化型インク、それを用いた画像形成方法及びインクジェット記録装置
JP2008189821A (ja) * 2007-02-05 2008-08-21 Fujifilm Corp 光硬化性組成物
JP2010195932A (ja) * 2009-02-25 2010-09-09 Sekisui Chem Co Ltd 光学成型用樹脂組成物及び光学部材
JP2012136571A (ja) * 2010-12-24 2012-07-19 Nippon Shokubai Co Ltd 光学レンズ用カチオン硬化性樹脂組成物
JP2013043983A (ja) * 2011-08-26 2013-03-04 Fujifilm Corp 光硬化性樹脂組成物、ウエハレベルレンズ、および、その製造方法
JP2013091676A (ja) * 2011-10-24 2013-05-16 Panasonic Corp 新規ｕｖ硬化性樹脂組成物
WO2018174177A1 (fr) * 2017-03-22 2018-09-27 パナソニックＩｐマネジメント株式会社 Composition de résine photodurcissable, adhésif, corps stratifié, procédé de production de corps stratifié et dispositif d'affichage
JP2019143006A (ja) * 2018-02-19 2019-08-29 四国化成工業株式会社 光学部材、及びそれを用いた光学装置

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005194379A (ja) * 2004-01-07 2005-07-21 Konica Minolta Medical & Graphic Inc 活性光線硬化型組成物、活性光線硬化型インク、それを用いた画像形成方法及びインクジェット記録装置
JP2008189821A (ja) * 2007-02-05 2008-08-21 Fujifilm Corp 光硬化性組成物
JP2010195932A (ja) * 2009-02-25 2010-09-09 Sekisui Chem Co Ltd 光学成型用樹脂組成物及び光学部材
JP2012136571A (ja) * 2010-12-24 2012-07-19 Nippon Shokubai Co Ltd 光学レンズ用カチオン硬化性樹脂組成物
JP2013043983A (ja) * 2011-08-26 2013-03-04 Fujifilm Corp 光硬化性樹脂組成物、ウエハレベルレンズ、および、その製造方法
JP2013091676A (ja) * 2011-10-24 2013-05-16 Panasonic Corp 新規ｕｖ硬化性樹脂組成物
WO2018174177A1 (fr) * 2017-03-22 2018-09-27 パナソニックＩｐマネジメント株式会社 Composition de résine photodurcissable, adhésif, corps stratifié, procédé de production de corps stratifié et dispositif d'affichage
JP2019143006A (ja) * 2018-02-19 2019-08-29 四国化成工業株式会社 光学部材、及びそれを用いた光学装置

Also Published As

Publication number Publication date
JPWO2021049443A1 (fr) 2021-03-18

Similar Documents

Publication Publication Date Title
US11029497B2 (en) Curable composition, cured product thereof, optical member and optical device
TWI680155B (zh) 透鏡用硬化性組成物及其用途、透鏡及其製造方法、以及光學裝置
EP2128183B1 (fr) Composition de résine pour composants optiques, composant optique l'utilisant et procédé de production de lentille optique
WO2014185180A1 (fr) Composition de résine photodurcissable pour éléments optiques, élément optique l'utilisant et procédé de production d'un élément optique
JP5329299B2 (ja) 光学レンズ
JP7169052B2 (ja) フレネルレンズ、及びその製造方法
JP5070131B2 (ja) 光学部品用樹脂組成物およびそれを用いた光学部品
JP5415371B2 (ja) 光学レンズ用光硬化型樹脂組成物およびそれを用いた光学レンズ
WO2021049443A1 (fr) Composition de résine durcissable par des ultraviolets, produit durci et lentille optique
JP6418672B2 (ja) 光学部品用樹脂組成物およびそれを用いた光学部品
JP5415370B2 (ja) 光硬化型樹脂組成物およびそれを用いた光学部品
WO2022131069A1 (fr) Composition de résine durcissable, objet durci, lentille, et lentille supportée par un substrat
WO2012169120A1 (fr) Procédé de fabrication d'un composé et composé
JP5184336B2 (ja) 紫外線硬化型樹脂組成物およびそれを用いて得られる光学レンズ
JP6938187B2 (ja) シリコーンモールド
JP2009288598A (ja) 光学レンズの製法およびそれにより得られた光学レンズ
TW201833166A (zh) 含脂環式環氧化合物之壓印成形用光聚合性組成物
TWI516517B (zh) 光硬化樹脂組合物及使用其之光學元件
WO2015151688A1 (fr) Composition de résine pour utilisation dans un composant optique et composant optique l'utilisant

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: 20862641

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021545512

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: 20862641

Country of ref document: EP

Kind code of ref document: A1