WO2022044743A1 - Photocurable composition for imprinting - Google Patents

Abstract

[Problem] To provide a novel photocurable composition for imprinting. [Solution] This photocurable composition for imprinting contains a resin and a photoinitiator. The storage elastic modulus of a cured product of the photocurable composition for imprinting, as measured using dynamic viscoelasticity measurements, is less than 4.0×10⁹ Pa at -40°C and is 1.0×10⁷ Pa or more at 100°C. This resin contains at least one type of crosslinkable resin as an essential component and a non-crosslinkable resin as an optional component, and has a parameter X represented by formula (1) of not less than 0.10 but less than 0.60. (In the formula, m denotes the number of crosslinkable resins contained in the resin, x_i denotes the ratio (units: parts by mass) of each crosslinkable resin relative to a total of 100 parts by mass of all components of the resin, y_i denotes the polymerizable functional group equivalent amount (units: g/eq) of each crosslinkable resin, and i denotes a positive integer between 1 and m.)

Description

Photocurable composition for imprint

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. In recent years, electronic devices have become smaller and more sophisticated, and along with this, there has been a demand for thinner and higher resolution camera modules. Against this background, as a method for manufacturing a resin lens, a shift from injection molding of a thermoplastic resin to wafer-level molding by UV imprinting of a photocurable resin is being actively studied.

As a method of wafer level molding by UV imprint, 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. There are two methods, one is to mold a resin lens on the body, and 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. Can be mentioned. In particular, 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.

Here, 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.

On the other hand, since camera modules are installed in electronic devices that are indispensable in daily life, reliability that can maintain stable quality is also required. As a typical test for evaluating reliability, there is a thermal shock test (for example, a test in which the lens is repeatedly exposed to a low temperature of -20 ° C or lower and a high temperature of 80 ° C or higher alternately), and the lens cracks even after the test. Impact resistance is required so that As a means for increasing the impact resistance of a resin, it is known to reduce the storage elastic modulus of the resin.

That is, although shape retention and impact resistance are very important for a resin lens for a camera module, it is difficult to achieve both of them because the two characteristics are in a trade-off relationship from the viewpoint of storage elastic modulus. ..

For example, 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. In addition, since a hybrid lens is not assumed in Patent Document 2, the range of the storage elastic modulus proposed in Patent Document 2 is such that one surface of the resin lens is in contact with a support such as a glass substrate. It is unclear whether this applies to special cases unique to hybrid lenses.

Japanese Patent Application Laid-Open No. 2015-209520 Japanese Unexamined Patent Publication No. 2016-27403

The range of elastic modulus proposed in Patent Document 1 is insufficient for the resin lens for a camera module to secure shape retention. As mentioned above, 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. rice field. 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.

As a result of diligent studies to solve the above problems, 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.

That is, 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.

(In the formula (1), m represents the number of the crosslinkable resins contained in the resin, and _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 resin comprises, for example, a radically polymerizable resin, and the photoinitiator comprises, for example, a photoradical generator. Alternatively, 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. An imprint step of bringing the curable composition into contact with a mold having an inverted pattern of the outer shape of a target molded body and a light-shielding film, and after the imprint step, the photocurable composition for imprint via the mold. After the photo-curing step of exposing an object to form a photo-curing portion, 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. ..

After the photo-curing step, before, during, or after the mold release step, a step of heating the photo-curing portion may be further included.

After the developing step and before the drying step, a rinsing step of rinsing the photocured portion with a rinsing liquid may be further included.

After the drying step, a post-exposure step of exposing the entire surface of the photo-cured portion may be further included.

After the post-exposure step, a post-baking step of heating the photo-cured portion may be further included.

After the post-exposure step, a step of forming an antireflection film on the surface of the photocurable portion may be further included.

After the post-baking step, a step of forming an antireflection film on the surface of the photo-curing portion may be further included.

In the photocurable composition for imprint of the present invention, 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.

The photocurable composition for imprint of the present invention will be described in more detail.
[DMA]
DMA is a 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.
<Test piece preparation conditions>
The photocurable composition for imprint of the present invention is sandwiched between two glass substrates so as to have a thickness of 200 μm, 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 μm).
<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

[Storage modulus]
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. For example, 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. As 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. When 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. Here, 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. When 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. Here, 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.

[resin]
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. Further, 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.

Among the crosslinkable resins that can be used in the photocurable composition for imprint of the present invention, 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-10, A-BPE-20, A-BPE-30, A-BPP-3, U-2PPA, U- 200PA, U-160TM, U-290TM, UA-4200, UA-4400, UA-122P, UA-W2A (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.), Funkrill (registered trademark) FA-121M, FA -124M, FA-125M, FA-129AS, FA-222A, FA-220M, FA-240M, FA-240A, FA-P240A, FA-P270A, FA-023M, FA -PTG9M, FA-PTG9A, FA-320M, FA-321M, FA-3218M, FA-321A, FA-324A (all manufactured by Hitachi Chemical Co., Ltd.), AH-600, UF-8001G , Light Ester 1.4BG, NP, 1.6HX, 1.9ND, 2EG, 3EG, 4EG, 9EG, 14EG, BP-2EMK, Light Acrylate (registered trademark) 1.6HX- A, 1.9ND-A, NP-A, MPD-A, DCP-A, 3EG-A, 4EG-A, 9EG-A, 14EG-A, PTMGA-250, PTMGA-250. 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. 4491, 4683, 4858, 8307, 8402, 8411, 8413, 8804, 8807, 9270, 246/20 HEMA, 1271, 286, 4859, 8409, 8809, 8810, 8811, KRM 7735, 8961, 8191. (The above is manufactured by Daicel Ornex Co., Ltd.), HDDA, L-C9A, ND-DA, PE-200, PE-300, PE-400, PE-600, PEM-1000, BPEM-4, BPE-4, BPEM-10, BPE-10, BPE-20, HBPE-4, HBPEM-10, HPN (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), M-1100, M-1200 (all manufactured by Toa Synthetic Co., Ltd.), UM-90 (3/1) DM, UM-90 (1/1) DM, UM-90 (1/3) DM, UM-90 (3/1) DA, UM-90 (1/1) DA, UM-90 (1/3) DA (above, manufactured by Ube Industries, Ltd.), UV-2000B, UV-3000B, UV-3200B, UV-3300B, UV-3310B, UV-3500BA, UV-3520EA, UV- Bifunctional (meth) acrylates such as 3700B, UV-6640B and UV-6630B (all manufactured by Mitsubishi Chemical Corporation);
Viscoat # 295, # 300, # 802 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), A-9300, A-9300-1CL, A-GLY-9E, A-GLY-20E, A-TMM- 3, A-TMM-3L, A-TMM-3LM-N, TMPT, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, A-DPH, U-6LPA, U-10HA, U-10PA, UA-1100H, U-15HA, UA-53H, UA-33H, UA-7100 (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.), Funkrill (registered trademark) FA-731A, FA-137M (The above is manufactured by Hitachi Chemical Co., Ltd.), UA-306H, UA-306T, UA-306I, UA-510H, Light Ester TMP, Light Acrylate (registered trademark) TMP-A, PE-3A, PE-4A. , 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, 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, M-471 ( As mentioned above, manufactured by Toa Synthetic Co., Ltd.), UV-2750B, UV-77000B, UV-7510B, UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620E A, UV-7630B, UV-7640B, UV-7650B (all manufactured by Mitsubishi Chemical Corporation) and other polyfunctional (meth) acrylates;
In addition, a polymer and a dendrimer having at least two polymerizable functional groups in one molecule.

Among the crosslinkable resins that can be used in the photocurable composition for imprinting of the present invention, examples of the cationically polymerizable resin include the following products and compounds.
EPICLON (registered trademark) 830, 830-S, 835, 840, 840-S, 850, 850-S, 850-LC, HP-820 (all manufactured by DIC Co., Ltd.), DENACOL (registered trademark) EX-201, EX-211, EX-212, EX-252, EX-810, EX-811, EX-821, EX-830, EX-832, EX-832. EX-841, EX-850, EX-851, EX-861, EX-920, EX-931, EX-991L, EX-313, EX-314, EX-321, EX-321L, EX-411, EX-421, EX-512, EX-521, EX-612, EX-614, EX-614B, EX-622 (above, Nagase Chemtex (above, Nagase Chemtex) (Co., Ltd.), jER (registered trademark) 152, 630, 825, 827, 828, 828EL, 828US, 828XA (above, Mitsubishi Chemical Co., Ltd.), TETRAD (registered trademark) -C , X (above, manufactured by Mitsubishi Gas Chemicals Co., Ltd.), Cellokiside (registered trademark) 2021P, 2081, Eporide (registered trademark) GT401 (above, manufactured by Daicel Co., Ltd.), Epototo (registered trademark) YD-115 , YD-115CA, YD-127, YD-128, YD-128G, YD-128S, YD-128CA, YD-8125, YD-825GS, YDF-170, YDF-170N , YDF-8170C, YDF-870GS, ZX-1059, YH-404, YH-434, YH-434L, YH-513, YH-523, ST-3000 (all, Nittetsu) Chemical & Materials Co., Ltd.), Adecaledin (registered trademark) EP-4100, EP-4100G, EP-4100E, EP-4100TX, EP-4300E, EP-4100, EP-4400, EP -4520S, EP-4530, EP-4901, EP-4901E, EP-4000, EP-4005, EP-7001, EP-4080E, EPU-6, EPU-7N, EPU -11F, EPU-15F, EPU-1395, EPU-73B, EPU-17, EPU-17T-6, EPR-1415-1, EPR-2000, EPR-2007, Adecaglycyllol (Registered Trademarks) ED-503, ED-503G, ED-5 06, ED-523T, ED-505 (all manufactured by ADEKA Corporation), Sumiepoxy (registered trademark) ELM-434, ELM-434L, ELM-434VL, ELM-100, ELM-100H ( Sumitomo Chemical Co., Ltd.), Epolite M-1230, 40E, 100E, 200E, 400E, 70P, 200P, 400P, 1500NP, 1600, 80MF, 4000, 3002. (N) (These are manufactured by Kyoeisha Chemical Co., Ltd.) and THI-DE (manufactured by ENEOS Co., Ltd.) and other epoxy resins;
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.).

Among the non-crosslinkable resins that can be used in the photocurable composition for imprinting of the present invention, examples of the radically polymerizable resin include the following products and compounds.
AIB, TBA, NOAA, IOAA, LA, STA, ISTA, IBXA, 1-ADA, 1-ADMA, Viscort # 150, # 155, # 160, # 190, # 192, # MTG, Bismer # MPE400A, # MPE500A, HEA, 4-HBA (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Funkrill (registered trademark) FA-BZM, FA-BZA, FA-511AS, FA-512M, the same. 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-A, MTG-A, 130A, DPM-A, EC-A, Monofunctional (meth) acrylates such as epoxy ester M-600A (above, manufactured by Kyoeisha Chemical Co., Ltd.), VEEM and VEEA (above, manufactured by Nippon Catalyst Co., Ltd.);
Radical cyclization polymerizable compound such as FX-AO-MA (manufactured by Nippon Shokubai Co., Ltd.).

Among the non-crosslinkable resins that can be used in the photocurable composition for imprinting of the present invention, 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 (above, 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.) ..

[Parameter X]
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.

(In the formula (1), m represents the number of the crosslinkable resins contained in the resin, and _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. When the resin containing the polymerizable functional group is (meth) acrylate, the (meth) acrylic equivalent is measured by the method described in JIS K 2605, and in the case of an epoxy resin, the epoxy equivalent is measured by the method described in JIS K 7236. be able to.

Here, the meaning of the parameter X in the present invention will be described. 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. In the above formula (1), for each crosslinkable resin, 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 having a small polymerizable functional group equivalent is contained in the resin, the larger the parameter X becomes, and the higher the crosslink density of the cured product of the photocurable composition for imprint of the present invention. On the contrary, 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. Has a smaller crosslink density.

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. By selecting the resin so as to be less than, 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. In the photocurable composition for imprint having a parameter X of 0.60 or more, 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. In the photocurable composition for imprint having a parameter X of less than 0.10, 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.

[Light initiator]
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.

Examples of photoradical generators that can be used in the photocurable composition for imprint of the present invention include alkylphenones, benzophenones, dibenzoyls, anthraquinones, acylphosphine oxides, benzoylbenzoates, oxime esters and thioxanthones. In particular, 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. 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, -. 400, -410S, IK-1 (above, manufactured by San-Apro Co., Ltd.), IRGACURE (registered trademark) PAG103, PAG121, the same PAG203 (above, manufactured by BASF Japan Ltd.), TPS-TF, TPS-CS, 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. By setting the content of the photoinitiator within the above range, the photocurable composition for imprinting of the present invention can be cured by exposure.
The photoinitiator may be used alone or in combination of two or more.

[Silica particles]
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. Here, 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 is a relationship established between the specific surface area (surface area per unit mass) S of the silica particles measured by the gas adsorption method (BET method), the density ρ of the silica particles, and the primary particle diameter D. It can be calculated from the formula: D = 6 / (ρS). The primary particle diameter calculated from the above relational expression is an average particle diameter, which is the diameter of the primary particle. By setting the primary particle size within the above range, silica particles can be blended without impairing the transparency of the photocurable composition for imprint of the present invention.

As the silica particles, either the surface-modified silica particles or the surface-modified silica particles may be used. Examples of 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-. 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 Industries, Ltd.) can be mentioned. 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.

When the photocurable composition for imprint of the present invention contains the silica particles, 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. By containing the silica particles within the above range, the effect of improving the heat resistance of the cured product and the molded product obtained from the photocurable composition for imprinting of the present invention can be imparted.

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.

[Other additives]
Further, 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.

[Method for preparing photocurable composition for imprint]
The method for preparing the photocurable composition for imprint of the present invention is not particularly limited. Examples of 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 μm to 10 μm or the like.

[Cursed product]
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. As 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.

[Molded body]
In the photocurable composition for imprint of the present invention, various molded bodies can be easily produced in parallel with the formation of the cured product by the UV imprint method. Hereinafter, a detailed process regarding the production of the molded body will be described.

[Applying process]
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.

[Imprint process]
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. Here, when the shape of the target molded body is a concave surface, 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. When the material of the mold is a resin, it may be either a non-photosensitive resin or a photosensitive resin. Examples of 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. FG-5093 (above, manufactured by Fluoro Technology Co., Ltd.), Durasurf (registered trademark) DP-500, DP-200, DS-5400, DH-100, DH-405TH, DH-610, same DS-5800, DS-5935 (all manufactured by Harves Co., Ltd.), Polyflon (registered trademark) PTFE TC-7105GN, PTFE TC-7109BK, PTFE TC-7113LB, PTFE TC-7400CR, PTFE TC- 7405GN, PTFE TC-7408GY, PTFE TC-7409BK, PTFE TC-7609M1, PTFE TC-7808GY, PTFE TC-7809BK, PTFE TD-7139BD, Optool (registered trademark) E, Optoace (registered trademark) WP-140, Die-free (registered trademark) GW-4000, GW-4010, GW-4500, GW-4510, GW-8000, GW-8500, MS- 175, GF-700, GF-750, MS-600, GA-3000, GA-9700, GA-9750 (all manufactured by Daikin Industries, Ltd.), Megafuck (registered trademark) F- 553, F-555, F-558, F-561 (all manufactured by DIC Co., Ltd.), SFE-DP02H, SNF-DP20H, SFE-B002H, SNF-B200A, SCV-X008, SFEX008, SNF- X800, SR-4000A, S-680, S-685, MR F-6441-AL, MR F-6711-AL, MR F-6758-AL, MR F-681-AL, and MR EF-6521-AL ( As mentioned above, AGC Seimi Chemical Co., Ltd.) can be mentioned. Examples of the mold release agent include mold release agents disclosed in International Publication No. 2019/031312, in addition to the above-mentioned commercial products.

[Photo-curing process]
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. As 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 μm to 2000 μm, preferably 100 μm to 1000 μm, and more preferably 300 μm to 700 μm. 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.

[Release process]
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. After the photo-curing step, before, during, or after the main release step, 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.

[Development process]
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 γ-. 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.

[Rinse process]
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.

[Drying process]
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.

[Post-exposure process]
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. As the light beam exposed in this post-exposure step, a light ray that can be used in the photocuring step can be used.

[Post-baking process]
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.

[Antireflection film forming process]
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. Further, 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.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. The devices used for sample preparation and evaluation in the following Examples and Comparative Examples are as follows.

(1) Stirring and defoaming Co., Ltd. Shinky Co., Ltd. Rotating / revolutioning mixer Awatori Rentaro (registered trademark) ARE-310
(2) UV exposure Batch type UV-LED irradiation device manufactured by CCS Inc. (maximum wavelength 365 nm)
(3) Storage elastic modulus measurement Dynamic viscoelasticity measuring device Q800 manufactured by TA Instruments Japan Co., Ltd.
Air Chiller System ACS-3 manufactured by TA Instruments Japan Co., Ltd.
(4) Impact resistance evaluation Small thermal impact tester TSE-11-A manufactured by ESPEC CORPORATION
(5) Shape retention evaluation Mitaka Kohki Co., Ltd. non-contact surface property measuring device PF-60

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. Product name: NK ester A-DCP
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. Product name: 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. Product name: EBECRYL (registered trademark) 5129
V # 190: Made by Osaka Organic Chemical Industry Co., Ltd. Product name: Viscote # 190
V # 260: Made by Osaka Organic Chemical Industry Co., Ltd. Product name: Viscote # 260
UM-90 (1/3) DA: Made by Ube Industries, Ltd. Product name: UM-90 (1/3) DA
THI-DE: Made by ENEOS Co., Ltd. Product name: THI-DE
GT401: Made by Daicel Co., Ltd. Product name: Epolide (registered trademark) GT401
I184: Made by IGM Resins Product name: OMNIRAD (registered trademark) 184
I110P: Made by Sun Appro Co., Ltd. Product name: CPI (registered trademark) -110P
MEK-AC-2140Z: Made by Nissan Chemical Industries, Ltd. Product name: MEK-AC-2140Z

[Manufacturing Example 1]
120 g of A-DCP and 120 g of methyl ethyl ketone were weighed in a 500 mL eggplant flask and stirred to homogenize. Then, 260 g of MEK-AC-2140Z (silica particles having a primary particle diameter of 10 nm to 15 nm surface-modified with a methacryloyloxy group, a solid content of 46% by mass, a methyl ethyl ketone dispersion) was added, and the mixture was stirred and homogenized. Then, using an evaporator, methyl ethyl ketone was distilled off under the conditions of 50 ° C. and a reduced pressure of 133.3 Pa or less to obtain an A-DCP dispersion liquid of silica particles (silica particle concentration 50% by mass).

[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.

[Comparative Example 1]
10.0 g of A-DCP 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 10 using the stirring defoaming machine. A photocurable composition 17 for imprint was prepared by stirring and defoaming for a minute.

[Comparative Example 2]
7.0 g of A-DCP and 1.0 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 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 18 was prepared.

[Comparative Example 3]
As the crosslinkable resin, 3.0 g of A-DCP and 1.0 g of APG-700, and 6.0 g of the A-DCP dispersion liquid of the silica particles prepared in Production Example 1 as the silica particles (3.0 g as 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 19 was prepared.

[Comparative Example 4]
10.0 g of A-DOG 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 10 using the stirring defoaming machine. A photocurable composition 20 for imprint was prepared by stirring and defoaming for a minute.

[Comparative Example 5]
10.0 g of E5129 as the crosslinkable resin and 0.1 g of I184 as the photoinitiator are mixed, 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 21 for imprint was prepared.

[Comparative Example 6]
8.0 g of E5129 and 2.0 g of V # 260 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 22 for imprint was prepared by stirring and defoaming for 10 minutes using a foaming machine.

[Comparative Example 7]
6.0 g of E5129 and 4.0 g of V # 260 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 23 for imprint was prepared by stirring and defoaming for 10 minutes using a foaming machine.

[Comparative Example 8]
10.0 g of UA-510H 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 10 using the stirring defoaming machine. A photocurable composition 24 for imprint was prepared by stirring and defoaming for a minute.

[Comparative Example 9]
10.0 g of 1 G as the crosslinkable resin and 0.1 g of I184 as the photoinitiator are mixed, 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 25 for imprint was prepared.

[Comparative Example 10]
10.0 g of DCP as the crosslinkable resin and 0.1 g of I184 as the photoinitiator are blended, 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 26 for imprint was prepared.

[Comparative Example 11]
6.0 g of THI-DE and 4.0 g of GT401 as the crosslinkable resin and 0.1 g of I110P 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 27 for imprint was prepared by stirring and defoaming for 10 minutes using a foaming machine.

[Comparative Example 12]
2.5 g of UM-90 (1/3) DA as the crosslinkable resin, 7.5 g of AM-90G as the non-crosslinkable resin, and 0.1 g of I184 as the photoinitiator were blended at 50 ° C. The photocurable composition 28 for imprint was prepared by stirring and defoaming for 10 minutes using the stirring defoaming machine after shaking and mixing for 15 hours.

[Comparative Example 13]
Add 2.5 g of UA-4200 as the crosslinkable resin, 7.5 g of AM-90G as the non-crosslinkable resin, and 0.1 g of I184 as the photoinitiator, and shake at 50 ° C. for 15 hours. After mixing and stirring, the photocurable composition 29 for imprint was prepared by stirring and defoaming for 10 minutes using the stirring defoaming machine.

[Comparative Example 14]
2.5 g of E4513 as the crosslinkable resin, 7.5 g of AM-90G as the non-crosslinkable resin, and 0.1 g of I184 as the photoinitiator were mixed and shaken at 50 ° C. for 15 hours to mix. Then, the photocurable composition 30 for imprint was prepared by stirring and defoaming for 10 minutes using the stirring defoaming machine.

The compounding ratios of the photocurable compositions for imprint 1 to 30 prepared in Examples 1 to 16 and Comparative Examples 1 to 14 are shown in Table 1 below. In Table 1 below, "part" represents "part by mass".

Table 1

[Measurement of storage elastic modulus]
The photocurable compositions for imprint prepared in Examples 1 to 16 and Comparative Examples 1 to 14 were sandwiched between two glass substrates via a silicone rubber spacer having a thickness of 200 μm. The glass substrate is mold-released by applying Novec (registered trademark) 1720 (manufactured by 3M Japan Ltd.) in advance and drying it. Then, the photocurable composition for imprint sandwiched between the two demolded glass substrates was subjected to 120 seconds at an illuminance of 50 mW / cm ² in an air atmosphere using the UV-LED irradiation device (the UV-LED irradiation device). Exposure amount 6J / cm ² ) UV exposure. 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 μm). 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

Two strip-shaped test pieces were prepared from each of the imprint photocurable compositions, the storage elastic modulus of each of the two strip-shaped test pieces was measured, and the average value thereof was used as the final storage elastic modulus. Adopted. For each of the imprint photocurable compositions, the average value of the storage elastic modulus at −40 ° C. and the average value of the storage elastic modulus at 100 ° C. are shown in Table 3 below.

[Calculation of parameter X]
For each imprint photocurable composition prepared in Examples 1 to 16 and Comparative Examples 1 to 14, the parameter X was calculated based on the above formula (1). As the polymerizable functional group equivalent (unit: g / eq) of the crosslinkable resin, the numerical values described in the product catalog etc. are adopted as they are, and those not described are the structures described in the product catalog etc. The one obtained by referring to the information of the formula, the average molecular weight and the number of functional groups was adopted. The polymerizable functional group equivalent (unit: g / eq) of each crosslinkable resin is shown in Table 2 below.
Table 2

[Impact resistance evaluation]
An appropriate amount of each imprint photocurable composition prepared in Examples 1 to 16 and Comparative Examples 1 to 14 was dropped onto a non-alkali glass substrate (5 cm square, 700 μm thick). The non-alkali glass substrate is previously coated with a solution of KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.) diluted to 10% by weight with propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA in the present specification). By drying, it is adhered. Then, 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. Subsequently, 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. After that, 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. As a result, a lens having a concave surface of 6 mm × 7 mm, a thickest portion of 400 μm, and a thinnest portion of about 30 μm was molded on the non-alkali glass substrate.

Next, 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 thermal shock test conditions are as follows.
<Thermal impact test conditions>
Low temperature tank temperature: -40 ° C
High temperature tank temperature: 85 ° C
Exposure time at each temperature: 30 minutes (1 cycle = 1 hour)
Number of cycles: 50

After the completion of the thermal impact test, the impact resistance of the lens was determined to be "x" although cracks could be confirmed by visual observation, and the impact resistance was determined to be "◯" even though no cracks could be confirmed. The results are shown in Table 3 below.

[Evaluation of shape retention]
The photocurable compositions for imprints prepared in Examples 1 to 16, Comparative Example 1, Comparative Example 4, and Comparative Examples 10 to 14 are subjected to the thermal shock described in the above-mentioned [Impact resistance evaluation]. The lens was molded on the non-alkali glass substrate in the same procedure as the procedure immediately before charging into the testing machine. The shape of the concave surface of the lens was measured using the non-contact surface property measuring device, and the difference (μm) between the thickness of the thickest part and the thickness of the thinnest part of the lens was calculated (calculated here). The value is called "difference A"). Subsequently, 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 (μm) 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 (μm). For each of the imprint photocurable compositions, the shape retention when the shape change amount was 10 μm or more was determined to be “x”, and the shape retention when the shape change amount was 2 μm or less was determined to be “◯”. .. The results are shown in Table 3 below.

Table 3

In the photocurable compositions for imprints prepared in Examples 1 to 16, 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.

On the other hand, in the photocurable compositions for imprints prepared in Comparative Examples 1 to 10, 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.

In the photocurable composition for imprint prepared in Comparative Example 11, 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.

In the photocurable compositions for imprint prepared in Comparative Examples 12 to 14, 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.

From the above results, a photocurable composition for imprint in which the storage elastic modulus of the cured product is less than 4.0 × 10 ⁹ Pa at −40 ° C. and 1.0 × 10 ⁷ Pa or more at 100 ° C. , And 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.

Claims (16)

1. A photocurable composition for imprint containing a resin and a photoinitiator, and the storage elastic modulus of the cured product of the photocurable composition for imprint measured by dynamic viscoelasticity measurement is −40 ° C. A photocurable composition for imprint, which is less than 4.0 × 10 ⁹ Pa and 1.0 × 10 ⁷ Pa or more at 100 ° C.
2. According to claim 1, the resin contains 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. The photocurable composition for imprint described.
   

   

   (In the formula (1), m represents the number of the crosslinkable resins contained in the resin, and _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).
3. The photocurable composition for imprint according to claim 1 or 2, wherein the resin contains a radically polymerizable resin, and the photoinitiator contains a photoradical generator.
4. The photocurable composition for imprint according to claim 1 or 2, wherein the resin contains a cationically polymerizable resin, and the photoinitiator contains a photoacid generator.
5. The photocurable composition for imprint according to any one of claims 1 to 4, further comprising silica particles.
6. The cured product of the photocurable composition for imprint according to any one of claims 1 to 5.
7. The molded body of the photocurable composition for imprint according to any one of claims 1 to 5.
8. The molded body according to claim 7, which is a lens for a camera module.
9. The molded body according to claim 8, wherein the lens for the camera module is a hybrid lens.
10. A coating step for producing a molded product of a photocurable composition for imprint, wherein the photocurable composition for imprint according to any one of claims 1 to 5 is applied onto a support. An imprint step of bringing the photocurable composition for imprint into contact with a mold having an inverted pattern of the outer shape of a target molded body and a light-shielding film, and after the imprint step, the inn via the mold. After the photo-curing step of exposing the photo-curable composition for printing to form a photo-curing portion, the mold-removing step of separating the photo-curing portion from the mold, and the mold-removing step, the photo-curing for imprinting. The present invention comprises a developing step of removing the uncured portion of the sex composition with a developing solution to expose the photocured portion, and a drying step of spin-drying the support on which the photocured portion is formed after the developing step. Manufacturing method of molded body.
11. The method for producing a molded product according to claim 10, further comprising a step of heating the photo-curing portion after the photo-curing step and before, during, or after the mold release step.
12. The method for producing a molded product according to claim 10 or 11, further comprising a rinsing step of rinsing the photocurable portion with a rinsing solution after the developing step and before the drying step.
13. The method for producing a molded product according to any one of claims 10 to 12, further comprising a post-exposure step of exposing the entire surface of the light-cured portion after the drying step.
14. The method for producing a molded product according to claim 13, further comprising a post-baking step of heating the photo-cured portion after the post-exposure step.
15. The method for manufacturing a molded product according to claim 13, further comprising a step of forming an antireflection film on the surface of the photocurable portion after the post-exposure step.
16. The method for producing a molded product according to claim 14, further comprising a step of forming an antireflection film on the surface of the photocurable portion after the post-baking step.