Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
  • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
• • 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
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
• • 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
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography

Definitions

• the present invention relates to a photocurable composition for imprint that specifies a range of storage elastic modulus of the cured product.
• Resin lenses are used in camera modules mounted on electronic devices such as mobile phones, smartphones, digital cameras, and in-vehicle cameras.
• electronic devices have become smaller and more sophisticated, and along with this, there has been a demand for thinner and higher resolution camera modules.
• a shift from injection molding of a thermoplastic resin to wafer-level molding by UV imprinting of a photocurable resin is being actively studied.
• a photocurable resin is applied on a support such as a glass substrate, and then the mold is pressed against the photocurable resin to irradiate the light with light.
• a resin lens on the body
• the other is to mold a monolithic resin lens by sandwiching a photocurable resin between a pair of molds and irradiating it with light without using a support.
• the one obtained by the former method is called a hybrid lens because it has a structure in which an inorganic support and an organic resin lens are combined, and is preferably used from the viewpoint of productivity.
• a camera module is manufactured by laminating a lens molded by such a method in combination with an optical member such as an IR cut filter and an image sensor.
• a camera module particularly a high-resolution camera module, requires a plurality of lenses whose shapes are precisely designed in order to suppress image blurring and distortion called aberration. Since the deviation of the lens shape causes aberration, the lens is required to maintain the shape at the time of molding. As a means for improving the shape retention of the resin, it is known to increase the storage elastic modulus of the resin.
• Patent Document 1 proposes an optical ultraviolet curable adhesive composition having an elastic modulus of 1.0 ⁇ 10 4 to 1.0 ⁇ 105 Pa, and has an elastic modulus of 1. It is stated that when it is 0 ⁇ 10 5 Pa or less, the cushioning property against thermal impact and external impact is improved, and when it is 1.0 ⁇ 10 4 or more, the mechanical strength is improved.
• Patent Document 2 states that a wafer level lens having excellent shape retention even in a high temperature environment can be formed by setting the storage elastic modulus of the cured product at 160 ° C. to 0.1 ⁇ 109 Pa or more. Is mentioned, but impact resistance is not mentioned.
• the range of elastic modulus proposed in Patent Document 1 is insufficient for the resin lens for a camera module to secure shape retention.
• shape retention and impact resistance are in a trade-off relationship from the viewpoint of storage elastic modulus, and there is still no resin lens for camera modules that sufficiently satisfies both characteristics, and its development is desired.
• the present invention has been made in view of such circumstances, and is capable of producing a resin lens for a camera module, particularly a hybrid lens, which has both shape retention and impact resistance, and is photocurable for imprinting. It is an object of the present invention to provide a sex composition.
• the present inventor has found that the shape retention and impact resistance of the resin lens for a camera module are closely related to the storage elastic modulus of the cured product. .. Specifically, if the storage elastic modulus of the cured product measured by dynamic viscoelasticity measurement (hereinafter, abbreviated as DMA) is less than 4.0 ⁇ 109 Pa at ⁇ 40 ° C., impact resistance It was found that the property was dramatically improved, and the shape retention was dramatically improved when the temperature was 1.0 ⁇ 107 Pa or more at 100 ° C. Furthermore, they have found a unique parameter that defines the conditions necessary to satisfy the range of the storage elastic modulus, and have completed the present invention.
• DMA dynamic viscoelasticity measurement
• the first aspect of the present invention is a photocurable composition for imprint containing a resin and a photoinitiator, and the curing of the photocurable composition for imprint measured by dynamic viscoelastic measurement.
• a photocurable composition for imprint which has a storage elastic modulus of less than 4.0 ⁇ 10 9 Pa at ⁇ 40 ° C. and 1.0 ⁇ 10 7 Pa or more at 100 ° C.
• the resin contains, for example, at least one crosslinkable resin as an essential component and a non-crosslinkable resin as an optional component, and the parameter X represented by the following formula (1) is 0.10 or more and less than 0.60.
• m represents the number of the crosslinkable resins contained in the resin
• xi is the ratio (unit::) of each of the crosslinkable resins to 100 parts by mass of the sum of all the components of the resin. (Parts by mass)
• y i represents the polymerizable functional group equivalent (unit: g / eq) of each of the crosslinkable resins
• i represents a positive integer from 1 to m).
• the resin comprises, for example, a radically polymerizable resin, and the photoinitiator comprises, for example, a photoradical generator.
• the resin comprises, for example, a cationically polymerizable resin, and the photoinitiator comprises, for example, a photoacid generator.
• the photocurable composition for imprint may further contain silica particles.
• the second aspect of the present invention is a cured product of the photocurable composition for imprinting.
• a third aspect of the present invention is a molded body of the photocurable composition for imprinting.
• the molded body is, for example, a lens for a camera module.
• the lens for the camera module is, for example, a hybrid lens.
• a fourth aspect of the present invention is a method for producing a molded body of a photocurable composition for imprint, which is a coating step of applying the photocurable composition for imprint on a support, the photo for imprint.
• the mold-removing step of separating the photo-curing portion from the mold, and the demolding step, the uncured portion of the photo-curable composition for imprinting.
• Is a method for producing a molded product which comprises a developing step of removing the photo-cured portion with a developing solution to expose the photo-cured portion, and a drying step of spin-drying the support on which the photo-cured 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 photo-cured portion may be further included.
• a post-baking step of heating the photo-cured 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 photo-curing portion may be further included.
• the storage elastic modulus of the cured product of the photocurable composition for imprint satisfies the above range, and the parameter X satisfies the above range. Both excellent retention and impact resistance. Therefore, the photocurable composition for imprint of the present invention can be suitably used as a resin lens for a camera module, particularly a hybrid lens.
• DMA Dynamic Mechanical Analysis (dynamic viscoelasticity measurement), and refers to a measurement carried out under the following conditions with reference to the contents described in JIS K 7244-4.
• the photocurable composition for imprint of the present invention is sandwiched between two glass substrates so as to have a thickness of 200 ⁇ m, and an illuminance of 50 mW / cm under an air atmosphere using a UV-LED irradiation device having a maximum wavelength of 365 nm.
• UV exposure is performed at 2 for 120 seconds (exposure amount 6 J / cm 2 ), and the obtained cured product is cut to prepare a strip-shaped test piece (length 30 mm, width 4 mm, thickness 200 ⁇ m).
• Measurement mode Tension vibration
• Tension strain 0.1%
• Frequency 1Hz
• Measurement temperature range -50 ° C to 200 ° C
• Temperature rise rate 2 ° C / min
• Measurement atmosphere Air
• the storage elastic modulus in the present invention refers to the tensile storage elastic modulus measured by the DMA.
• the storage modulus is a physical property that represents the elastic properties of a material.
• a material having an extremely large storage elastic modulus such as metal and glass is hard and difficult to deform, but has poor dissipative property of stress generated by the deformation, and on the other hand, a storage elastic modulus represented by rubber or the like is extremely small.
• the material is soft and easily deformed, but is excellent in dissipating the stress generated by the deformation.
• the temperature of a general resin decreases, the storage elastic modulus increases and the elastic property becomes stronger, while as the temperature increases, the storage elastic modulus decreases and the elastic property becomes weaker.
• the impact resistance of the cured product and the molded product obtained from the photocurable composition for imprint of the present invention is closely related to the storage elastic modulus of the cured product at ⁇ 40 ° C., and the cured product is ⁇ 40.
• the storage elastic modulus at ° C. is 4.0 ⁇ 109 Pa or more
• the dissipative property of the stress generated during the thermal impact test becomes poor, so that the cured product and the molded product crack, peel off from the support, and the like.
• Impact resistance is significantly reduced.
• the reason for paying attention to the temperature of ⁇ 40 ° C. is that the minimum temperature in a general thermal shock test is around ⁇ 40 ° C.
• the shape retention of the cured product and the molded product obtained from the photocurable composition for imprint of the present invention is closely related to the storage elastic modulus of the cured product at 100 ° C., and the cured product at 100 ° C.
• the storage elastic modulus is less than 1.0 ⁇ 107 Pa
• the shape retention of the cured product and the molded product is significantly reduced.
• the reason for paying attention to the temperature of 100 ° C. is that the preferable maximum process temperature in wafer level molding by UV imprinting is around 100 ° C.
• the resin in the present invention is roughly classified into a crosslinkable resin and a non-crosslinkable resin.
• the crosslinkable resin in the present invention is a resin capable of forming a three-dimensional crosslinked product by polymerization, and at least one polymerizable functional group selected from a methacryloyloxy group, an acryloyloxy group, an epoxy group and an oxetanyl group is contained in one molecule. It is a resin having two.
• the type of polymerizable functional group contained in one molecule may be the same or different.
• the non-crosslinkable resin in the present invention is a resin having only one (meth) acryloyloxy group, an epoxy group or an oxetanyl group in one molecule, or no resin.
• the (meth) acrylate in the present invention refers to a methacrylate having at least one methacryloyloxy group in one molecule or an acrylate having at least one acryloyloxy group in one molecule.
• examples of the radically polymerizable resin include the following products and compounds. Viscoat # 195, # 230, # 260, # 310HP, # 335HP (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, DCP, A-DCP, A-DOG, 1G, 2G, 3G, 4G, 9G, 14G, 23G, A- 200, A-400, A-600, A-1000, APG-100, APG-200, APG-400, APG-700, 3PG, 9PG, A-1206PE, A-0612PE, A-0412PE, A-1000PER, A-3000PER, A-PTMG-65, ABE-300, A-BPE-4, A-BPE
• BP-4EAL, BP-4PA, HPP-A epoxy ester 40EM, 70PA, 200PA, 80MFA, 3002M (N), 3002A (N), 3000MK, 3000A (Kyoeisha Chemical Industry Co., Ltd. (Manufactured by Co., Ltd.), HDDA, DPGDA, TPGDA, IRR 214-K, EBECRYL (registered trademark) 11, 130, 145, 150, 210, 230, 270, 280/15 IB, 284, 284.
• DPE-6A (all manufactured by Kyoeisha Chemical Co., Ltd.), PETA, DPHA, PETIA, PETRA, TMPTA, OTA480, EBECRYL (registered trademark) 160S, 40, 140, 1142, 220, 8800, 294 / 25HD, 4220, 4513, 4738, 4740, 4820, 8311, 9260, 8701, 4265, 4587, 4666, 4680, 8210, 8405, 1290, 5129, 8301R, 4501, 2221, 8465, 1258, 4101, 4201, 8209, 1291, 8602, 225, KRM (registered trademark) 8667, 8296, 8528, same 8200, 8200AE, 8530, 8904, 8531BA, 8452 (all manufactured by Daicel Ornex Co., Ltd.), TMPTM, TMPT, TMP-2P, TMP-3P, TMP-3, PET-3, PETA- 4, TEICA,
• examples of the cationically polymerizable resin include the following products and compounds.
• EPICLON registered trademark
• DENACOL registered trademark
• Oxetane resins such as ETENCOLL (registered trademark) OXBP, OXIPA (above, manufactured by Ube Industries, Ltd.), Aron Oxetane (registered trademark) OXT-121 and OXT-221 (above, manufactured by Toagosei Co., Ltd.).
• examples of the radically polymerizable resin include the following products and compounds.
• FA-512MT, FA-512AS, FA-513M, FA-513AS (all manufactured by Hitachi Chemical Co., Ltd.), LMA, LA, S, AS, S-1800M, S-1800A, IB, A -IB, PHE-1G, AMP-10G, PHE-2G, AMP-20GY, M-20G, M-30G, AM-30G, M-40G, M-90G, AM-90G, M-130G, AM-130G , M-230G, AM-230G, M-30PG, AM-30PG, 702A (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.), Light Ester M, E, NB, IB, TB, EH, Same L, Same S, Same CH, Same IB-X, Same BZ, Same PO, Same THF (1000), Same 130MA, Same 041MA, Same HO-250 (N), Same HOA (N), Same DM, Same DE, Light Acrylate® LA, SA, IB-XA, PO-A, THF
• examples of the cationically polymerizable resin include the following products and compounds.
• DENACOL registered trademark
• EX-121, EX-141, EX-145, EX-146, EX-147, EX-171, EX-192, EX-731 aboveve, Nagase Chemtex (above, Nagase Chemtex) Monofunctional epoxy resin such as ED-502, ED-502S, ED-509E, ED-509S and ED-529 (all manufactured by ADEKA Corporation).
• Monofunctional oxetane resins such as ETERNCOLL (registered trademark) EHO, HBOX (above, manufactured by Ube Industries, Ltd.), Aron Oxetane (registered trademark) OXT-101 and OXT-212 (above, manufactured by Toagosei Co., Ltd.) ..
• the photocurable composition for imprint of the present invention contains a resin in which the parameter X represented by the following formula (1) is 0.10 or more and less than 0.60.
• m represents the number of the crosslinkable resins contained in the resin
• xi is the ratio (unit::) of each of the crosslinkable resins to 100 parts by mass of the sum of all the components of the resin. (Parts by mass)
• y i represents the polymerizable functional group equivalent (unit: g / eq) of each of the crosslinkable resins, and i represents a positive integer from 1 to m).
• the polymerizable functional group equivalent means the mass of the resin containing 1 gram equivalent of the polymerizable functional group, and simply, the molecular weight or the average molecular weight of the resin containing the polymerizable functional group is the number of the polymerizable functional groups. It is calculated by dividing by, or by quantitatively analyzing by various methods such as nuclear magnetic resonance spectroscopy and infrared spectroscopy.
• the resin containing the polymerizable functional group is (meth) acrylate
• the (meth) acrylic equivalent is measured by the method described in JIS K 2605
• the epoxy equivalent is measured by the method described in JIS K 7236. be able to.
• Parameter X is a unique parameter found by the present inventor that estimates the crosslink density of a three-dimensional crosslinked product obtained by curing the photocurable composition for imprint of the present invention at the stage of the composition before curing. , Consists of sections relating to crosslinkable resins.
• the content ratio is multiplied by the inverse of the polymerizable functional group equivalent, that is, the number of polymerizable functional groups per unit mass (x i / y i ), and each crosslinkable resin x It is the sum of i / y i and means the contribution of the crosslinkable resin to the crosslink density of the three-dimensional crosslinker.
• the contribution of the non-crosslinkable resin to the crosslink density of the three-dimensional crosslinked product was regarded as zero. The reason is that the non-crosslinkable resin does not polymerize by itself, or even if it polymerizes, it does not form a three-dimensional crosslinked product and only extends between the crosslink points.
• the more the crosslinkable resin or the non-crosslinkable resin having a large polymerizable functional group equivalent is contained in the resin the smaller the parameter X becomes, and the cured product of the photocurable composition for imprint of the present invention.
• the parameter X of the photocurable composition for imprint of the present invention is closely related to the storage elastic modulus of the cured product of the photocurable composition for imprint, and the parameter X is 0.10 or more and 0.60.
• the storage elastic modulus of the cured product of the photocurable composition for imprint is less than 4.0 ⁇ 109 Pa at ⁇ 40 ° C. and 1 at 100 ° C. The condition that it is 0.0 ⁇ 10 7 Pa or more is satisfied.
• the storage elastic modulus of the cured product of the photocurable composition for imprint is 4.0 ⁇ 109 Pa or more at ⁇ 40 ° C.
• the impact resistance of the cured product and the molded product obtained from the photocurable composition for imprinting is significantly reduced.
• the storage elastic modulus of the cured product of the photocurable composition for imprint is less than 1.0 ⁇ 107 Pa at 100 ° C.
• the shape retention of the cured product and the molded product obtained from the photocurable composition for imprint is significantly reduced.
• the type of resin contained in the photocurable composition for imprinting in the present invention is not particularly limited as long as the parameter X is 0.10 or more and less than 0.60. Even if the photocurable composition for imprint in the present invention contains silica particles and other additives in addition to the resin and the photoinitiator, the resin is prepared so that the parameter X is 0.10 or more and less than 0.60. It is desirable to contain it.
• the photoinitiator in the present invention is roughly classified into a photoradical generator and a photoacid generator. It is desirable to use the photoradical generator in combination with a radically polymerizable resin and the photoacid generator in combination with a cationically polymerizable resin.
• intramolecular cleavage type photoradical generators are preferable.
• Commercially available products may be used as the photoradical generator, for example, OMNIRAD (registered trademark) 127, 184, 369, 369E, 379EG, 500, 651, 819, 784, 907.
• IGM Resins 1173, 2959, TPO H (above, 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).
• Examples of the photoacid generator that can be used in the photocurable composition for imprint of the present invention include aryl sulfonium salts and aryl iodonium salts.
• Commercially available products may be used as the photoacid generator, for example, CPI (registered trademark) -100P, -101A, -110P, -200K, -210S, -300, -310B, -.
• TPS-PFBS examples thereof include TPS-PFBS and DTBPI-PFBS (all manufactured by Toyo Synthetic Industry Co., Ltd.).
• the content of the photoinitiator of the photocurable composition for imprint of the present invention is 0.05 part by mass with respect to 100 parts by mass of the sum of all the resin components contained in the photocurable composition for imprint. It is 5 parts by mass, preferably 0.1 part by mass to 3 parts by mass, and more preferably 0.5 part by mass to 2 parts by mass.
• the photoinitiator may be used alone or in combination of two or more.
• the photocurable composition for imprint of the present invention may contain silica particles, and the silica particles that can be used have a primary particle diameter of 1 nm to 100 nm.
• the primary particles are particles constituting the powder, and the particles in which the primary particles are aggregated are referred to as secondary particles.
• the primary particle diameter calculated from the above relational expression is an average particle diameter, which is the diameter of the primary particle.
• silica particles either the surface-modified silica particles or the surface-modified silica particles may be used.
• the unsurface-modified silica particles include CHO-ST-M, DMAC-ST, DMAC-ST-ZL, EAC-ST, EG-ST, EG-ST-ZL, EG-ST-XL30, IPA-.
• Examples of the surface-modified silica particles include MEK-AC-2140Z, MEK-AC-4130Y, MEK-AC-5140Z, PGM-AC-2140Y, PGM-AC-4130Y, MIBK-AC-2140Z, and MIBK-SD-L. (The above is manufactured by Nissan Chemical Industries, Ltd.), ELCOM (registered trademark) V-8802 and V-8804 (all manufactured by JGC Catalysts and Chemicals Co., Ltd.). In addition to commercially available products, those obtained by reacting the unsurface-modified silica particles with a silane coupling agent by various known methods can be used.
• the content thereof is 100 parts by mass based on the sum of all the components of the resin contained in the photocurable composition for imprint. 5, 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.
• the silica particles can be used alone or in combination of two or more. For example, a plurality of silica particles having different primary particle diameters may be combined, or a plurality of silica particles having different types or amounts of silane coupling agents used for surface modification may be combined.
• the photocurable composition for imprint of the present invention may be used as an antioxidant, a chain transfer agent, an ultraviolet absorber, a light stabilizer, a leveling agent, if necessary, as long as the effects of the present invention are not impaired. It can contain a rheology adjuster, an adhesion aid such as a silane coupling agent, and an additive such as a pigment, a dye, and an antifoaming agent.
• the method for preparing the photocurable composition for imprint of the present invention is not particularly limited.
• the preparation method include a method of mixing a resin, a photoinitiator, and if necessary, silica particles and other additives in a predetermined ratio to obtain a uniform solution. It is desirable that the photocurable composition for imprint of the present invention prepared in a solution is used after being filtered using a filter having a pore size of 0.1 ⁇ m to 10 ⁇ m or the like.
• the photocurable composition for imprint 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.
• the method for producing a molded product of the present invention includes a coating step of applying the photocurable composition for imprint of the present invention onto a support.
• the imprint photocurable composition is applied onto the support by an appropriate application method such as a dispenser or a spinner.
• 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. Is.
• the support may be, for example, a semiconductor substrate such as silicon coated with a silicon oxide film, a semiconductor substrate such as silicon coated with a silicon nitride film or 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 glass substrates on which an ITO film is formed.
• the support is a primer between the support and the photocurable composition for imprint in order to improve the adhesion to the cured product and the molded body obtained from the photocurable composition for imprint. It may have a layer.
• the method for producing a molded body of the present invention includes an imprinting step of bringing the photocurable composition for imprint into contact with a mold having an inverted pattern of the outer shape of the desired molded body and a light-shielding film.
• the inverted pattern is a convex surface.
• 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 mold 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 a photocuring step of exposing the photocurable composition for imprint through the mold to form a photocurable portion after the imprinting step.
• 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 photo-cured portion is usually 1 ⁇ m to 2000 ⁇ m, 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 treatment in which the mold release agent is applied and dried.
• the photo-curing portion may be further heated.
• the means for heating the photo-cured portion is not particularly limited, and examples thereof include a hot plate and an oven.
• the step of heating the photocured portion is 1 minute to 1 hour, preferably 1 minute to 30 minutes in a temperature range of 50 ° C. to 200 ° C., preferably 50 ° C. to 150 ° C., more preferably 50 ° C. to 100 ° C. , More preferably for 1 to 10 minutes.
• the method for producing a molded product of the present invention includes, after the mold release step, a developing step of removing the uncured portion of the photocurable composition for imprint with a developing solution to expose the photocured portion.
• the means of this development step 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 main development step is carried out in a temperature range of 5 ° C. to 50 ° C., preferably 15 ° C. to 35 ° C., more preferably 20 ° C. to 30 ° C. for 10 seconds to 10 minutes, preferably 10 seconds to 3 minutes, more preferably 10. It is performed for 1 second to 1 minute.
• the developing solution is not particularly limited as long as it can remove the uncured portion of the photocurable composition for imprint, but propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclopentanone, cyclohexanone and ⁇ -. Butyrolactone is preferred, with propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate being more 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 means of this rinsing step 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.
• This rinsing step takes 10 seconds to 10 minutes, preferably 10 seconds to 3 minutes, more preferably 10 in a temperature range of 5 ° C to 50 ° C, preferably 15 ° C to 35 ° C, more preferably 20 ° C to 30 ° C. It is performed for 1 second to 1 minute.
• the rinse solution is not particularly limited as long as the developer can be washed away without damaging the photocured portion.
• the developer and the rinse solution used in the method for producing a molded product of the present invention further contain a surfactant for the purpose of improving the wettability to the photocured portion and efficiently advancing the development and rinsing. You may.
• the surfactant may be used alone or in combination of two or more. When the surfactant is used, its content is 0.001 part by mass to 5 parts by mass, preferably 0.01 part by mass with respect to 100 parts by mass of the developer or the rinse solution. It is 3 parts by mass, more preferably 0.05 part by mass to 1 part by mass.
• 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.
• the means of this drying step is not particularly limited, and examples thereof include a method of rotating the support using a spin-drying device such as a spinner or a coater.
• This drying step is carried out in a rotation speed range of 200 rpm to 3000 rpm, preferably 500 rpm to 2000 rpm, more preferably 1000 rpm to 1500 rpm for 10 seconds to 10 minutes, preferably 10 seconds to 3 minutes, more preferably 10 seconds to 1 minute. Will be.
• the method for producing a molded product of the present invention may include a post-exposure step of exposing the entire surface of the light-cured portion after the drying step.
• the atmosphere of the post-exposure process is not particularly limited, and examples thereof include an air atmosphere and a nitrogen atmosphere.
• 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 photo-cured portion after the post-exposure step.
• the means of this post-baking process is not particularly limited, and examples thereof include a hot plate and an oven.
• This post-baking step is carried out in a temperature range of 50 ° C. to 200 ° C., preferably 50 ° C. to 150 ° C., more preferably 50 ° C. to 100 ° C. for 1 minute to 1 hour, preferably 1 minute to 30 minutes, more preferably. It is carried out for 1 to 10 minutes.
• 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, in the case of performing the post-baking step, 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 vapor 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 body produced by such a method can be suitably used as a lens for a camera module.
• the sources of the resin, photoinitiator and silica particles used in the following production examples, examples and comparative examples are as follows.
• A-DCP Made by Shin Nakamura Chemical Industry Co., Ltd.
• A-DOG Made by Shin Nakamura Chemical Industry Co., Ltd.
• Product name: NK Ester A-DOG APG-700 Made by Shin Nakamura Chemical Industry Co., Ltd.
• Product name: NK Ester APG-700 A-600 Made by Shin Nakamura Chemical Industry Co., Ltd.
• Product name: NK Ester A-600 AM-90G Made by Shin Nakamura Chemical Industry Co., Ltd.
• NK Ester AM-90G 1G Made by Shin Nakamura Chemical Industry Co., Ltd.
• Product name: NK Ester 1G DCP Made by Shin Nakamura Chemical Industry Co., Ltd.
• Product name: NK Ester DCP UA-4200 Made by Shin Nakamura Chemical Industry Co., Ltd.
• Product name: NK Oligo UA-4200 UA-510H Made by Kyoeisha Chemical Co., Ltd.
• Product name: UA-510H E4513 Made by Daisel Ornex Co., Ltd.
• Product name: EBECRYL (registered trademark) 4513 E5129 Made by Daisel Ornex Co., Ltd.
• Example 1 6.0 g of A-DCP and 4.0 g of APG-700 as the crosslinkable resin and 0.1 g of I184 as the photoinitiator were blended, and the mixture was shaken at 50 ° C. for 15 hours and mixed.
• a photocurable composition 1 for imprint was prepared by stirring and defoaming for 10 minutes using a stirring defoaming machine.
• Example 2 4.0 g of A-DCP and 6.0 g of APG-700 as the crosslinkable resin and 0.1 g of I184 as the photoinitiator were blended, and the mixture was shaken at 50 ° C. for 15 hours and mixed.
• the photocurable composition 2 for imprint was prepared by stirring and defoaming for 10 minutes using a stirring defoaming machine.
• Example 3 3.0 g of A-DCP and 7.0 g of APG-700 as the crosslinkable resin and 0.1 g of I184 as the photoinitiator were blended, and the mixture was shaken at 50 ° C. for 15 hours and mixed.
• the photocurable composition 3 for imprint was prepared by stirring and defoaming for 10 minutes using a stirring defoaming machine.
• Example 4 2.0 g of A-DCP and 8.0 g of APG-700 as the crosslinkable resin and 0.1 g of I184 as the photoinitiator were blended, and the mixture was shaken at 50 ° C. for 15 hours and mixed.
• the photocurable composition 4 for imprint was prepared by stirring and defoaming for 10 minutes using a stirring defoaming machine.
• Example 5 4.0 g of A-DCP and 4.0 g of APG-700 as the crosslinkable resin, and 2.0 g of the A-DCP dispersion liquid of the silica particles prepared in Production Example 1 as the silica particles (1.0 g as the silica particles). ) And 0.1 g of I184 as the photoinitiator, each of which is shaken at 50 ° C. for 15 hours to mix, and then stirred and defoamed for 10 minutes using the stirring defoaming machine for imprinting. A photocurable composition 5 was prepared.
• Example 6 8.0 g of A-DCP and 2.0 g of A-600 as the crosslinkable resin and 0.1 g of I184 as the photoinitiator were blended, and the mixture was shaken at 50 ° C. for 15 hours and mixed.
• a photocurable composition 6 for imprint was prepared by stirring and defoaming for 10 minutes using a stirring defoaming machine.
• Example 7 6.0 g of A-DCP and 4.0 g of A-600 as the crosslinkable resin and 0.1 g of I184 as the photoinitiator were blended, and the mixture was shaken at 50 ° C. for 15 hours and mixed.
• a photocurable composition 7 for imprint was prepared by stirring and defoaming for 10 minutes using a stirring defoaming machine.
• Example 8 4.0 g of A-DCP and 6.0 g of A-600 as the crosslinkable resin and 0.1 g of I184 as the photoinitiator were blended, and the mixture was shaken at 50 ° C. for 15 hours and mixed.
• a photocurable composition 8 for imprint was prepared by stirring and defoaming for 10 minutes using a stirring defoaming machine.
• Example 9 6.0 g of A-DOG and 4.0 g of A-600 as the crosslinkable resin and 0.1 g of I184 as the photoinitiator were blended, and the mixture was shaken at 50 ° C. for 15 hours and mixed.
• a photocurable composition 9 for imprint was prepared by stirring and defoaming for 10 minutes using a stirring defoaming machine.
• Example 10 3.0 g of A-DOG and 7.0 g of APG-700 as the crosslinkable resin and 0.1 g of I184 as the photoinitiator were blended, and the mixture was shaken at 50 ° C. for 15 hours and mixed.
• the photocurable composition 10 for imprint was prepared by stirring and defoaming for 10 minutes using a stirring defoaming machine.
• Example 11 2.0 g of A-DOG and 8.0 g of APG-700 as the crosslinkable resin and 0.1 g of I184 as the photoinitiator were blended, and the mixture was shaken at 50 ° C. for 15 hours and mixed.
• the photocurable composition 11 for imprint was prepared by stirring and defoaming for 10 minutes using a stirring defoaming machine.
• Example 12 10.0 g of UM-90 (1/3) DA as the crosslinkable resin and 0.1 g of I184 as the photoinitiator were blended, and the mixture was shaken at 50 ° C. for 15 hours to mix, and then the stirring was removed.
• the photocurable composition 12 for imprint was prepared by stirring and defoaming for 10 minutes using a foaming machine.
• Example 13 9.0 g of UM-90 (1/3) DA as the crosslinkable resin, 1.0 g of V # 190 as the non-crosslinkable resin, and 0.1 g of I184 as the photoinitiator were blended and 50.
• the photocurable composition 13 for imprint was prepared by shaking and mixing at ° C. for 15 hours and then stirring and defoaming for 10 minutes using the stirring defoaming machine.
• Example 14 8.0 g of UM-90 (1/3) DA as the crosslinkable resin, 2.0 g of V # 190 as the non-crosslinkable resin, and 0.1 g of I184 as the photoinitiator were blended and 50.
• the photocurable composition 14 for imprint was prepared by shaking and mixing at ° C. for 15 hours and then stirring and defoaming for 10 minutes using the stirring defoaming machine.
• Example 15 9.0 g of UM-90 (1/3) DA as the crosslinkable resin, 1.0 g of AM-90G as the non-crosslinkable resin, and 0.1 g of I184 as the photoinitiator were blended and 50.
• the photocurable composition 15 for imprint was prepared by shaking and mixing at ° C. for 15 hours and then stirring and defoaming for 10 minutes using the stirring defoaming machine.
• Example 16 10.0 g of E4513 as the crosslinkable resin and 0.1 g of I184 as the photoinitiator are blended, and the mixture is shaken at 50 ° C. for 15 hours to mix, and then stirred for 10 minutes using the stirring defoaming machine. By defoaming, a photocurable composition 16 for imprint was prepared.
• the cured product obtained after exposure was peeled off from the mold-released glass substrate and cut to prepare a strip-shaped test piece (length 30 mm, width 4 mm, thickness 200 ⁇ m).
• the storage elastic modulus of the strip-shaped test piece was measured using the dynamic viscoelasticity measuring device connected to the air chiller system.
• the measurement conditions are as follows. ⁇ Measurement conditions> Measurement mode: Tension vibration Tension strain: 0.1% Frequency: 1Hz Measurement temperature range: -50 ° C to 200 ° C Temperature rise rate: 2 ° C / min Measurement atmosphere: Air
• the photocurable composition for imprinting dropped onto the non-alkali glass substrate was sandwiched between convex molds made of transparent resin with a light-shielding film (opening 6 mm ⁇ 7 mm).
• the mold is mold-released by applying Novec (registered trademark) 1720 (manufactured by 3M Japan Ltd.) and drying.
• the photocurable composition for imprint sandwiched between the non-alkali glass substrate and the mold is passed through the mold with an illuminance of 50 mW / cm 2 for a predetermined time using the UV-LED irradiation device. UV exposure was performed to form a photocurable portion.
• the UV exposure time at this time was 5 seconds for Examples 1 to 7, Examples 10 to 16, and Comparative Examples 1 to 10, and Examples 8 and 9 and Comparative Example. It takes 3 seconds for 12 to 14 and 20 seconds for Comparative Example 11.
• the mold is released, the non-alkali glass substrate to which the photocurable portion is in close contact is immersed (developed) in agitated PGMEA for 1 minute, and further rinsed with PGMEA to unexposed portion (undured portion). Part) was removed.
• a lens having a concave surface of 6 mm ⁇ 7 mm, a thickest portion of 400 ⁇ m, and a thinnest portion of about 30 ⁇ m was molded on the non-alkali glass substrate.
• the lens molded on the non-alkali glass substrate was UV-exposed again at an illuminance of 50 mW / cm 2 for a predetermined time using the UV-LED irradiation device, and then put into the thermal shock tester.
• a thermal shock test was performed.
• the UV exposure time at this time was 115 seconds for Examples 1 to 7, Examples 10 to 16, Comparative Examples 1 to 10, and Examples 8, 9, and Comparative Examples 12 to 12. It is 117 seconds for Comparative Example 14 and 100 seconds for Comparative Example 11 (for each of the above-mentioned photocurable compositions for imprint, the total exposure time of the two UV exposures is 120 seconds, that is, the total exposure amount is the same (the total exposure amount is the same). Unified to 6J / cm 2 )).
• the non-alkali glass substrate on which the lens was molded was placed on a hot plate at 100 ° C. for 10 minutes to heat it, and 10 minutes after it was removed from the hot plate, the concave shape of the lens was again reshaped.
• the difference ( ⁇ m) between the thickness of the thickest part and the thickness of the thinnest part of the lens was calculated by measuring using the non-contact surface property measuring device (the value calculated here is referred to as “difference B”). ).
• the value obtained by subtracting the difference B from the difference A was defined as the amount of change in the shape of the lens ( ⁇ m).
• the shape retention when the shape change amount was 10 ⁇ m or more was determined to be “x”, and the shape retention when the shape change amount was 2 ⁇ m or less was determined to be “ ⁇ ”. ..
• the results are shown in Table 3 below.
• the storage elastic modulus of the cured product obtained from the composition was less than 4.0 ⁇ 109 Pa at ⁇ 40 ° C. Moreover, it was 1.0 ⁇ 107 Pa or more at 100 ° C., and the parameter X was 0.10 or more and less than 0.60.
• the lens produced from the photocurable composition for imprint was judged as " ⁇ " in the impact resistance evaluation and the shape retention evaluation.
• the storage elastic modulus of the cured product obtained from the composition was 1.0 ⁇ 107 Pa or more at 100 ° C. However, it was 4.0 ⁇ 109 Pa or more at ⁇ 40 ° C., and the parameter X was 0.60 or more.
• the lenses produced from the photocurable composition for imprint were all judged as "x" in the impact resistance evaluation.
• the storage elastic modulus of the cured product obtained from the composition was 4.0 ⁇ 109 Pa or more at ⁇ 40 ° C. and at 100 ° C. It was less than 1.0 ⁇ 10 7 Pa, and the parameter X was 0.60 or more.
• the lens produced from the photocurable composition for imprint was judged as "x" in the impact resistance evaluation and the shape retention evaluation.
• the storage elastic modulus of the cured product obtained from the composition was less than 4.0 ⁇ 109 Pa at ⁇ 40 ° C. However, it was less than 1.0 ⁇ 107 Pa at 100 ° C., and the parameter X was less than 0.10.
• the lenses produced from the photocurable composition for imprint were judged as " ⁇ " in the impact resistance evaluation, but were judged as "x" in the shape retention evaluation.
• the photocurable composition for imprint in which the parameter X is 0.10 or more and less than 0.60 has both shape retention and impact resistance, while the storage elastic modulus and the parameter X of the cured product are described above. It has been shown that the photocurable composition for imprint, which is out of the range, cannot achieve both shape retention and impact resistance.

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