TW201843183A - Photocurable composition for imprint - Google Patents

Abstract

To provide a photocurable composition which has excellent optical characteristics and is capable of forming a cured product wherein the amount of warping of a supporting body after imprinting is greatly smaller than conventional ones. A photocurable composition for imprinting, which contains the component (a) described below, from 0 part by mass to 70 parts by mass (inclusive) of the component (b) described below relative to 100 parts by mass of the component (a), from 5 parts by mass to 30 parts by mass (inclusive) of the component (c) described below relative to 100 parts by mass of the total of the component (a) and the component (b), and from 0.2 part by mass to 5 parts by mass (inclusive) of the component (d) described below relative to 100 parts by mass of the total of the component (a), the component (b) and the component (c). Component (a): a di(meth)acrylate compound represented by formula (1) (In the formula, each of R1 and R2 independently represents a hydrogen atom or a methyl group; each of R3 and R4 independently represents an alkylene group having 1 to 4 carbon atoms; each of R5 and R6 independently represents a hydrogen atom or a methyl group; and each of r1 and r2 independently represents an integer of 1 to 5.) Component (b): a monofunctional or polyfunctional (meth)acrylate compound containing no aromatic ring (excluding the di(meth)acrylate compound represented by formula (1)) Component (c): a polyfunctional thiol compound having 2 to 6 mercapto groups in each molecule Component (d): an optical radical initiator.

Description

Photocurable composition for imprinting

The present invention relates to a photocurable composition for imprint, which includes a specific bifunctional (meth) acrylate compound, a polyfunctional thiol compound, and a photoradical initiator. In detail, the photocurable composition which can form the optical property (transparency, high refractive index, and high Abbe's coefficient) which is excellent, and the amount of curvature of the support after imprint is much smaller than the conventional hardened | cured material is formed.

Resin lenses are used in electronic devices such as mobile phones, digital cameras, and in-vehicle cameras, and are required to have excellent optical characteristics according to the purpose of the electronic device. In addition, high durability (for example, heat resistance and weather resistance) and high productivity that can be molded with good yield are required in combination with the use state. As a resin lens material that can satisfy such requirements, thermoplastic transparent resins such as polycarbonate resins, cycloolefin polymers, and methacrylic resins have been used.

In addition, in the high-resolution camera module, a plurality of lenses are used, but lenses having low wavelength dispersion (that is, having a high Abbe coefficient) are mainly used, and thus optical materials capable of forming such lenses are required. Furthermore, in the manufacture of resin lenses, in order to improve productivity or production efficiency, and further suppress the optical axis shift when the lenses are laminated, research into moving from injection molding of thermoplastic resins to wafer-level molding is being actively conducted. Wafer-level molding is performed by extrusion molding using a liquid curable resin at room temperature. From the viewpoint of productivity, wafer-level molding is generally a hybrid lens method in which lenses are formed on a support such as a glass substrate.

As a photocurable resin capable of wafer-level molding, a radically curable resin composition can be used from the viewpoints of good mold release properties, high transparency, and heat yellowing resistance during reflow soldering in the past. (Patent Document 1). However, with the market demand for thinning of camera modules in recent years, the thickness of the support used in the hybrid lens method is being reduced. Therefore, when the radical-curable resin composition described in Patent Document 1 is used, the problem that the support formed with a molded body such as a lens is warped after reflow is significant. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 5281710 (WO2011 / 105473)

[Problems to be Solved by the Invention]

As such, there has not yet been a hardenable resin material that can be used as a lens for a high-resolution camera module, has a high Abbe coefficient (for example, 53 or more) and high transparency, and is available in a hybrid lens system Since the amount of warpage of a support such as a glass substrate is a small hardened product, development is expected. The present invention is an invention in view of such circumstances, and it is an object of the present invention to provide a light suitable for producing a hardened body that exhibits a high Abbe coefficient, high refractive index, high transparency, and heat yellowing resistance, and that a molded body is produced by a hybrid lens method. Hardening composition. [Means for solving problems]

As a result of intensive research in order to solve the aforementioned problems, the inventors have found that a specific bifunctional (meth) acrylate compound and a polyfunctional thiol compound are blended in a photocurable composition at a specified ratio, thereby The cured product (molded article) obtained from the photocurable composition has a high Abbe coefficient ν _D (53 or more), and exhibits a high transmittance of 90% or more at a wavelength of 410 nm. The change in transmittance before and after the melting of the solder) is small (less than ± 3%), and the amount of warpage of the support is very small (0 μm or more and less than 2 μm), and the present invention has been completed.

That is, the first aspect of the present invention is a photocurable composition for imprinting, which comprises the following (a) component, and the content of 0 to 70 parts by mass based on 100 parts by mass of the component (a) The component (b), the following (c) component, which is 5 to 30 parts by mass based on 100 parts by mass of the total of the (a) component and the (b) component, and the (a) component, the (b) The total of 100 parts by mass of the component and the component (c) is 0.2 to 5 parts by mass of the following (d) component, (a): a di (meth) acrylate represented by the following formula (1) Compounds, (In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, R ³ and R ⁴ each independently represent an alkylene group having 1 to 4 carbon atoms, and R ⁵ and R ⁶ each independently represent a hydrogen atom. Or methyl, r ¹ and r ² each independently represent an integer of 1 to 5); (b): a monofunctional or polyfunctional (meth) acrylate compound not containing an aromatic ring (but not including the aforementioned formula ( 1) a di (meth) acrylate compound); (c): a polyfunctional thiol compound having 2 to 6 mercapto groups in the molecule; (d): a photoradical initiator.

The photocurable composition for imprint of the present invention may further contain the following from 0.05 to 1 part by mass based on 100 parts by mass of the total of the component (a), the component (b), and the component (c). (e) the component and / or the above-mentioned (f) component in an amount of 0.1 to 3 parts by mass based on 100 parts by mass of the total of the aforementioned (a) component, the aforementioned (b) component, and the aforementioned (c) component, (e): Phenol-based antioxidant; (f): Phosphite-based antioxidant.

(c) The component is, for example, a polyfunctional thiol compound represented by the following formula (2). (In the formula, R ⁷ represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms, X represents a single bond or an ester bond, and A represents a group containing at least one heteroatom or not. An organic group or heteroatom having 2 to 12 carbon atoms including a hetero atom, and r ³ represents an integer of 2 to 6).

The photocurable composition for imprinting of the present invention may further contain a monofunctional amount of 0.1 to 3 parts by mass based on 100 parts by mass of the total of the component (a), the component (b), and the component (c). Thiol compounds.

In the photocurable composition for imprinting of the present invention, the refractive index n _D of the cured product at a wavelength of 589 nm is 1.50 or more and 1.55 or less, and the Abbe coefficient ν _D of the cured product is 53 or more and 60 or less.

A second aspect of the present invention is a cured product of the photocurable composition for imprint described above.

A third aspect of the present invention is a method for manufacturing a resin lens, which includes a step of embossing the photocurable composition for imprinting.

A fourth aspect of the present invention is a method for manufacturing a molded body, which includes filling the photocurable composition for imprinting into a space between a supporting body and a model that are in contact with each other, or an interior of a divisible model. A step of space, and a step of exposing and photocuring a photocurable composition filled in the space. The aforementioned model is also called a casting mold.

The method for producing a molded body of the present invention may further include a step of taking out the obtained light-hardened article and demolding it after the photo-hardening step, and performing the photo-curing before, during, or after the demolding step. The hardened body is subjected to a heating step.

In the manufacturing method of the molded object of this invention, this molding system is a lens for camera modules, for example. [Effect of the invention]

Since the photocurable composition for imprinting of the present invention includes a di (meth) acrylate compound represented by the aforementioned formula (1) and a polyfunctional thiol compound having 2 to 6 mercapto groups in the molecule, the photocurable composition The cured product (molded article) obtained from the curable composition is an optical element (for example, a lens for a high-resolution camera module), which has suitable optical characteristics, that is, has a high Abbe coefficient, a high refractive index, and high transparency. Sex. In addition, the hardened body (molded body) has a small change in transmittance before and after heating by the solder melting temperature, and the amount of warpage of the support on which the hardened body (molded body) is formed is extremely small (0 μm or more and less than 2 μm) . Furthermore, the manufacturing method of the molded object using the photocurable composition for imprints of this invention can manufacture a lens for camera modules especially efficiently. [Illustrated simple illustration]

[Fig. 1] Fig. 1 is a schematic diagram showing a method for evaluating a warpage amount of a glass substrate.

[Best Mode for Implementing Invention]

[(a) component: di (meth) acrylate compound] The di (meth) acrylate compound (a) as the component (a) of the photocurable composition for imprint of the present invention can be used, and is a formula (1). Represents a di (meth) acrylate compound. Examples of the di (meth) acrylate compound include ethoxy-modified hydrogenated bisphenol A diacrylate, ethoxy-modified hydrogenated bisphenol A dimethacrylate, and propoxy-modified hydrogenated bisphenol. A diacrylate, propoxy modified hydrogenated bisphenol A dimethacrylate, butoxy modified hydrogenated bisphenol A diacrylate, butoxy modified hydrogenated bisphenol A dimethacrylate, ethoxylate Propyloxy modified hydrogenated bisphenol A diacrylate, ethoxypropoxy modified hydrogenated bisphenol A dimethacrylate, ethoxy modified hydrogenated bisphenol F diacrylate, and ethoxy modified The hydrogenated bisphenol F dimethacrylate is not limited to these examples.

As the di (meth) acrylate compound represented by the aforementioned formula (1), commercially available products such as New Frontier (registered trademark) HBPE-4, and HBPEM-10 (both manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) can be used. .

The di (meth) acrylate compound which is the component (a) of the photocurable composition for imprint of the present invention can be used, and it does not contain an aromatic ring and has a hydrogenated bisphenol skeleton. When a di (meth) acrylate compound having a bisphenol skeleton containing an aromatic ring is used in the photocurable composition for imprint, the Abbe coefficient of the cured product obtained from the photocurable composition It is reduced, so that a high Abbe coefficient, which is the object of the present invention, cannot be obtained.

The di (meth) acrylate compound of the component (a) may be used alone or in combination of two or more.

[(b) component: monofunctional or polyfunctional (meth) acrylate compound] A monofunctional or polyfunctional (meth) acrylate which is the (b) component of the photocurable composition for imprint of the present invention can be used The compound does not include an aromatic ring as a requirement, and does not include a di (meth) acrylate compound represented by the formula (1). Examples of the monofunctional (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, Isoamyl (meth) acrylate, norbornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, 2-methyladamantane-2 -Yl (meth) acrylate, 2-ethyladamantane-2-yl (meth) acrylate, 1,3-adamantanediol (meth) acrylate, tricyclic [5.2.1.0 ^2,6 ] Decyl (meth) acrylate and tricyclic [5.2.1.0 ^2,6 ] decyl-4-enyl (meth) acrylate, but are not limited to these examples. Examples of the polyfunctional (meth) acrylate compound include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and ethoxylated trimethylolpropane tri (methyl) Acrylate), ethoxylated glycerol tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, polyglycerol monoepoxy Ethane poly (meth) acrylate, dipentaerythritol hexa (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (methyl) ) Acrylate, tricyclodecanedimethanol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and isocyanurate (2-propenyloxyethyl) ester , But not limited to such examples.

The aforementioned monofunctional or polyfunctional (meth) acrylate compounds can be Fancryl (registered trademark) FA-511AS, the same as FA-512AS (above Hitachi Chemical Co., Ltd.), EtADA, EAMA (P), ADA, ADMA, IBXA, Viscoat # 150, same # 155, same # 200 (above Osaka Organic Chemical Co., Ltd.), NK Ester A-200, same A-400, same A-600, same A-1000, same A-9300, Same as A-9300-1CL, same as UA-53H, same as 1G, same as 2G, same as 3G, same as 4G, same as 9G, same as 14G, same as 23G, same as A-GLY-3E, same as A-GLY-9E, and same as A- GLY-20E, same A-TMPT-3EO, same A-TMPT-9EO, same ATM-4E, same ATM-35E, same A-DPH, same A-TMPT, same A-DCP, same A-HD-N, Same as AD-TMP, same A-DOG, same TMPT, same DCP, same NPG, same HD-N, same D-TMP, NK Oligo U-15HA (above Shin Nakamura Chemical Industry Co., Ltd.), KAYARAD (registered trademark ) DPEA-12, same as PEG400DA, same as THE-330, same as RP-1040 (above Nippon Kayaku Co., Ltd.), M-210, M-350, MacromonomerAA-6, and AB-6 (above East Asia Synthetic (stock )), And commercially available products such as KAYARAD (registered trademark) DPHA, NPGDA, and PET30 (above the Nippon Kayaku Co., Ltd.).

The content of the component (b) of the photocurable composition for imprint of the present invention is 0 to 70 parts by mass based on 100 parts by mass of the component (a). The content of the component (b) is in a range of 0 parts by mass, that is, the component (b) is not an essential component. If the content of the component (b) is more than 70 parts by mass, the mechanical properties of the cured product obtained from the photocurable composition will be lowered, and the lens will be deformed or the support will be deformed in the reflow soldering step described above. Warpage will increase.

The (b) component of the monofunctional or polyfunctional (meth) acrylate compound may be used alone or in combination of two or more.

[Component (c): Polyfunctional thiol compound having 2 to 6 mercapto groups in the molecule] The component (c) of the photocurable composition for imprint of the present invention can be used with 2 to 6 in the molecule Examples of thiol-functional polythiol compounds include 1,2-ethanedithiol, 1,3-propanedithiol, bis (2-mercaptoethyl) ether, and trimethylolpropane (3-mercaptopropane). Acid ester), ginseng-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate ), Pentaerythritol (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-ginseng (3-mercaptobutyryloxyethyl) -1 , 3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, trimethylolpropane (3-mercaptobutyrate), and trimethylolethane (3 -Mercaptobutyrate), but is not limited to these examples.

As the aforementioned multifunctional thiol compound, Karenz MT (registered trademark) PE1, NR1, BD1, TPMB, TEMB (manufactured by Showa Denko Corporation), TMMP, TEMPIC, PEMP, EGMP-4, DPMP, TMMP can be used. Commercial products such as II-20P, PEMP II-20P (above SC Organic Chemicals).

The content of the component (c) of the photocurable composition for imprinting of the present invention is 5 to 30 parts by mass based on 100 parts by mass of the total of the component (a) and the component (b). If the content of the component (c) is less than 5 parts by mass, the warpage of the support will be increased. If it is more than 30 parts by mass, the mechanical properties of the lens will be poor, so the reflow soldering step will cause Deformation of the lens.

The polyfunctional thiol compound of the said (c) component can be used individually by 1 type or in combination of 2 or more types.

[(d) Component: Photoradical Initiator] (1) A photoradical initiator that can be used as the component (d) of the photocurable composition for imprint of the present invention can be, for example, alkyl benzophenones, Benzophenones, Michler's ketones, acylphosphine oxides, benzoyl benzoates, oxime esters, tetramethylthiuram monosulfide Thioxanthone and thioxanthone, especially photo-radical type photoradical polymerization initiators are preferred.

As the aforementioned photoradical initiator, IRGACURE (registered trademark) 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24 can be used. -61, same as TPO, same as 1116, same as 1173 (above BASF Japan (stock system)), and ESACURE KIP150, same as KIP65LT, same as KIP100F, same as KT37, same as KT55, same as KTO46, and same as KIP75 (made by Lamberti) Commercially available.

The content of the component (d) of the photocurable composition for imprint of the present invention is 0.2 parts by mass to 5 parts by mass based on 100 parts by mass of the total of the component (a) and the component (b) and the component (c). It is preferably 0.5 parts by mass to 3 parts by mass. When the content of the component (c) is less than 0.2 parts by mass, the strength of the cured product obtained from the photocurable composition is reduced, and when it is more than 5 parts by mass, the strength obtained from the photocurable composition is reduced. The cured product has poor heat yellowing resistance.

The photoradical initiator of the said (d) component can be used individually by 1 type or in combination of 2 or more types.

[(e) component: phenol-based antioxidant] (1) A phenol-based antioxidant that can be used as the (e) component of the photocurable composition for imprinting of the present invention, for example, IRGANOX (registered trademark) 245, the same as 1010, the same 1035, same as 1076, same as 1135 (above BASF Japan (shares) system), SUMILIZER (registered trademark) GA-80, same GP, same MDP-S, same BBM-S, same WX-R (above Sumitomo Chemical Co., Ltd.) System), Adekastub (registered trademark) AO-20, the same AO-30, the same AO-40, the same AO-50, the same AO-60, the same AO-80, and the AO-330 (above (shares) ADEKA system).

The content of the component (e) of the photocurable composition for imprint of the present invention is 0.05 parts by mass to 1 with respect to 100 parts by mass of the total of the component (a) and the component (b) and the component (c). Parts by mass.

The phenol-based antioxidants of the component (e) may be used alone or in combination of two or more.

[(f) Component: Phosphite-based Antioxidant] (i) Phosphite-based antioxidant that can be used as the (f) component of the photocurable composition for imprint of the present invention, for example, IRGAFOS (registered trademark) 168 ( (BASF Japan (share) system), Adekastub (registered trademark) PEP-36, same PEP-8, same HP-18, same HP-10, same 2112, same 2112RG, same 1178, same 1500, same C, same 135A, Same as 3010, same as TPP (above (shares) ADEKA system).

The content of the component (f) of the photocurable composition for imprinting of the present invention is 0.1 parts by mass to 3 parts by mass based on 100 parts by mass of the total of the component (a) and the component (b) and the component (c). Serving.

The photocurable composition for imprint of the present invention may contain any one of the component (e) and the component (f), but it is preferable to contain both. If the content of the (e) component and / or the (f) component is less than the lower limit of the above range, a change in transmittance may occur in the step of being exposed to the temperature at which the solder melts (about 260 ° C). If it is higher than the upper limit of the above range, the color will change to green when the use environment is exposed to strong light such as sunlight.

The phosphite-based antioxidants of the component (f) may be used alone or in combination of two or more.

[Other additives] Furthermore, as long as the effect of the present invention is not impaired, the photocurable composition for imprinting of the present invention may contain a monofunctional thiol compound, a disulfide compound, and an α-methyl group if necessary. Selected chain transfer agents, UV absorbers, light stabilizers, leveling agents, rheology modifiers, silane coupling agents (adhesives), pigments, dyes, and defoamers selected from the group of styrene dimers Wait.

Examples of the monofunctional thiol compound include methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, 3-methoxybutyl 3-mercaptopropionate, and 3 -Mercapto carboxylic acid esters such as n-octyl mercaptopropionate and stearyl 3-mercaptopropionate; ethyl mercaptan, 2-methylpropane-2- mercaptan, n-dodecyl mercaptan, 2 , 3,3,4,4,5-hexamethylhexane-2-thiol (tert-dodecyl mercaptan), ethane-1,2-dithiol, propane-1,3-di Alkyl mercaptans such as mercaptans and benzyl mercaptan; benzene mercaptan, 3-methylbenzene mercaptan, 4-methylbenzene mercaptan, naphthalene-2-thiol, pyridine-2-thiol, benzene Aromatic mercaptans such as benzimidazole-2-thiol and benzothiazole-2-thiol; mercapto alcohols such as 2-mercaptoethanol and 4-mercapto-1-butanol; and 3- (trimethoxy Silane-containing mercaptans such as silyl) propane-1-thiol and 3- (triethoxysilyl) propane-1-thiol.

As the aforementioned monofunctional thiol compound, THIOKALCOL (registered trademark) 08, same as 20 (above Kao (stock)), BMPA, MPA-80, EHMP, NOMP, MBMP, STMP (above SC organic chemical (stock)) ), KBM-802, KBM-803 (above manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and the like.

Examples of the disulfide compound include diethyl disulfide, dipropyl disulfide, diisopropyl disulfide, dibutyl disulfide, di-tert-butyl disulfide, and disulfide. Amyl disulfide, diisopentyl disulfide, dihexyl disulfide, dicyclohexyl disulfide, didecyl disulfide, bis (2,3,3,4,4,5-hexamethyl Hexane-2-yl) disulfide (di-tert-dodecyldisulfide), bis (2,2-diethoxyethyl) disulfide, bis (2-hydroxyethyl) Alkyl disulfides such as disulfide, dibenzyl disulfide; diphenyl disulfide, di-p-tolyl disulfide, bis (pyridin-2-yl) pyridine disulfide, di Aromatic disulfides such as (benzimidazol-2-yl) disulfide, bis (benzothiazol-2-yl) disulfide; and tetramethylthiuram disulfide, tetraethyl autumn Thiuram disulfides such as rum disulfide, tetrabutyl thiuram disulfide, and bis (pentamethylene) thiuram disulfide.

When the photocurable composition for imprinting of the present invention includes a chain transfer agent selected from the group consisting of the aforementioned monofunctional thiol compound, disulfide compound, and α-methylstyrene dimer, The content is 0.1 to 3 parts by mass based on 100 parts by mass of the total of the component (a), the component (b), and the component (c). When the content of the chain transfer agent is more than 3% by mass, the mechanical strength of the cured product obtained from the photocurable composition is reduced.

<Method for preparing photocurable composition for imprint> The method for preparing the photocurable composition for imprint of the present invention is not particularly limited. As the modulation method system, for example, (a) component, (b) component, (c) component and (d) component, and (e) component and / or (f) component are mixed in a predetermined ratio, and according to a desired A method of adding and mixing the aforementioned other additives to prepare a uniform solution.

The photocurable composition for imprinting of the present invention prepared as a solution is preferably used after being filtered using a filter having a pore size of 0.1 to 5 μm.

<Hardened object> (1) The hardened object can be obtained by exposing (light curing) the photocurable composition for imprinting of the present invention, and the present invention also targets this hardened object. Examples of the exposure light include ultraviolet rays, electron rays, and X-rays. As a light source used in the ultraviolet irradiation, for example, sunlight, 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. In addition, in order to stabilize the physical properties of the cured product after exposure, post-baking may be performed. The post-baking method is not particularly limited, but it is usually performed in a range of 50 ° C. to 260 ° C. for 1 minute to 24 hours using a hot plate, an oven, or the like.

By photocuring the photocurable composition for imprinting of the present invention, the Abbe coefficient ν _D of the obtained cured product is as high as 53 or more, and the refractive index n _D at a wavelength of 589 nm (D line) is 1.50 or more. Also, no yellowing caused by heating was found. Therefore, the photocurable composition system for imprints of the present invention can be suitably used as a resin lens.

<Molded Article> 光 The light-curable composition for imprinting of the present invention can easily produce various molded articles in parallel with the formation of a cured product by using, for example, an imprint molding method. As a method of manufacturing a molded article, for example, a method including the step of filling the photocurable composition of the present invention into a space between a supporting body and a mold which are in contact with each other, or an internal space of a divisible mold. Steps of exposing and photo-curing the composition filled in the space, steps of taking out and demolding the obtained photo-cured material, and performing the photo-cured material before, during, or after performing the demolding step. Steps of heating.

The above-mentioned steps of performing exposure and photo-hardening can be applied to the conditions for obtaining a cured product. Furthermore, the conditions for the step of heating the photocured material are not particularly limited, but are usually appropriately selected from the range of 50 ° C. to 260 ° C. for 1 minute to 24 hours. The heating means is not particularly limited, but examples thereof include a hot plate and an oven. The molding system manufactured by such a method can be suitably used as a lens for camera modules. [Example]

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples. In the following examples, the devices and conditions used for the preparation of samples and analysis of physical properties are as follows.

(1) Stirrer defoamer device: Spiny-revolution mixer made by Thinky Co., Ltd. debubbling kentaro (registered trademark) ARE-310 (2) UV exposure device: Batch-type UV irradiation device by Eyegraphics (High-pressure mercury lamp 2kW × 1 lamp) (3) Transmittance device: UV-Vis near-infrared spectrophotometer V-670 made by JASCO Corporation Control group: Quartz (4) refractive index n _D , Abbe coefficient ν _D device : Multi-wavelength refractometer Abbemat MW manufactured by Anton-Paar company Measurement temperature: 23 ° C Intermediate liquid for adhering the sample to the substrate: Monobromide (5) warpage measurement, lens height measurement device: Mitaka Optical Device Non-contact surface property measurement device PF-60 (6) Lens molding device: Nano-imprinter NH0801HB made by Mingchang Machinery Co., Ltd. Light source: Short arc high-pressure mercury lamp with i-line bandpass filter HB0365 (Asahi Spectroscopy Co., Ltd.) for exposure molding conditions: pressing pressure 150N, 20mW / cm ² × 300 seconds

The supply ends of the compounds used in the examples and comparative examples are as follows. HBPE4: Trade name of Daiichi Kogyo Pharmaceutical Co., Ltd .: New Frontier (registered trademark) HBPE-4 FA513AS: Trade name of Hitachi Chemical Co., Ltd .: Fancryl (registered trademark) FA-513AS PET-30: Japanese chemical medicine (Stock) trade name: KAYARAD (registered trademark) PET-30 PE1: Showa Denko (share) trade name: Karenz (registered trademark) MT PE1 TMMP: SC organic chemistry (share) trade name: TMMP II -20P DPMP: trade name of SC Organic Chemicals (stock): DPMP I184: trade name of BASF: Irgacure (registered trademark) 184 245I245: trade name of BASF: irganox (registered trademark) 245 1500: (share ) Trade name made by ADEKA: Adekastub (registered trademark) 1500 DDT: trade name made by Kao (share): THIOKALCOL (registered trademark) 20 A-DCP: trade name made by Shin Nakamura Chemical Industry (stock): NK Ester A- DCP

[Example 1] (1) HBPE4, which is (a) the di (meth) acrylate compound represented by the aforementioned formula (1), and (c), PE1, which is a polyfunctional thiol compound having 2 to 6 mercapto groups in the molecule. (d) I184 as a photoradical initiator, (e) I245 as a phenolic antioxidant, (f) 1500 as a phosphite antioxidant, and DDT of a monofunctional thiol compound as another additive, Each of them was prepared in the proportions described in Table 1 below, and the mixture was stirred and mixed at 50 ° C. for 3 hours using the above-mentioned stirring and defoaming machine. Furthermore, by using the same apparatus and stirring and defoaming for 10 minutes, the photocurable composition 1 for imprint was prepared. In addition, "part" in the following Table 1 means "mass part."

[Example 2] (1) HBPE4 (a) as the di (meth) acrylate compound represented by the aforementioned formula (1), and (c) PE1, which is a polyfunctional thiol compound having 2 to 6 mercapto groups in the molecule. (d) I184 as a photoradical initiator, (e) I245 as a phenolic antioxidant, (f) 1500 as a phosphite antioxidant, and DDT of a monofunctional thiol compound as another additive, Each of them was prepared in the proportions described in Table 1 below, and the mixture was stirred and mixed at 50 ° C. for 3 hours using the above-mentioned stirring and defoaming machine. Furthermore, by using the same apparatus and stirring and defoaming for 10 minutes, the photocurable composition 2 for imprint was prepared.

[Example 3, Example 4, Example 7 and Example 8] (1) HBPE4, (b) which is a di (meth) acrylate compound represented by the aforementioned formula (1), is monofunctional or polyfunctional ( FA513AS or PET-30 of a meth) acrylate compound, (c) PE1, TMMP or DPMP as a polyfunctional thiol compound having 2 to 6 thiol groups in the molecule, (d) as a photoradical initiator I184, (e) I245 as a phenol-based antioxidant, (f) 1500 as a phosphite-based antioxidant, and DDT of a monofunctional thiol compound as another additive, according to the ratios shown in Table 1 below, respectively. The mixture was prepared, and the mixture was stirred and mixed at 50 ° C. for 3 hours using the aforementioned stirring and defoaming machine. Furthermore, by using the same apparatus and stirring and defoaming for 10 minutes, the photocurable compositions 3, 4, 7, and 8 for imprinting were prepared. This embodiment is a FA-513AS or PET-30 containing the component (b), and is different from the first and second embodiments of the present invention.

[Example 5 and Example 6] 513 FA513AS using (a) HBPE4, which is a di (meth) acrylate compound represented by the aforementioned formula (1), and (b), which is a monofunctional or polyfunctional (meth) acrylate compound. Or PET-30, (c) PE1 as a polyfunctional thiol compound having 2 to 6 thiol groups in the molecule, I184 (d) as a photoradical initiator, and I245 as a phenolic antioxidant And (f) 1500, which is a phosphite-based antioxidant, were formulated at the ratios described in Table 1 below, and were stirred and mixed at 50 ° C. for 3 hours using the agitating defoamer. Furthermore, by using the same apparatus and stirring and defoaming for 10 minutes, the photocurable compositions 5 and 6 for imprinting were prepared. This embodiment does not include DDT of other additives, and is different from Examples 3, 4, 7, and 8 of the present invention.

[Example 9] 513 FA513AS, (c) using (a) HBPE4 as a di (meth) acrylate compound represented by the aforementioned formula (1), (b) as a monofunctional or polyfunctional (meth) acrylate compound PE1 as a polyfunctional thiol compound having 2 to 6 thiol groups in the molecule, I184 (d) as a photoradical initiator, and DDT of a monofunctional thiol compound as other additives are shown in the following tables, respectively. The mixture was prepared at the ratio described in 1 and was stirred and mixed at 50 ° C. for 3 hours using the aforementioned stirring degassing machine. Furthermore, by using the same apparatus and stirring and defoaming for 10 minutes, the photocurable composition 9 for imprint was prepared. This embodiment does not include (e) component and (f) component, and is different from Example 3, Example 4, Example 7 and Example 8 of the present invention.

[Comparative Example 1] (1) HBPE4 (a) as the di (meth) acrylate compound represented by the aforementioned formula (1), I184 (d) as the photoradical initiator, and (e) as the phenolic antioxidant I245, (f) 1500 as a phosphite-based antioxidant, and DDT of a monofunctional thiol compound as another additive were prepared in the proportions described in Table 1 below, and the aforementioned stirring defoamer was used. The mixture was stirred and mixed at 50 ° C for 3 hours. Furthermore, the photocurable composition 10 was prepared by defoaming with stirring using the same apparatus for 10 minutes. This comparative example does not include a component (c), and is different from Examples 1 and 2 of the present invention.

[Comparative Example 2] (1) HBPE4 (a) as the di (meth) acrylate compound represented by the aforementioned formula (1), PE1 (c) as the polyfunctional thiol, and (d) as the photoradical initiator I184, (e) I245 as a phenol-based antioxidant, (f) 1500 as a phosphite-based antioxidant, and DDT of a monofunctional thiol compound as another additive are each according to the ratios described in Table 1 below. It mix | blended and stirred at 50 degreeC for 3 hours using the said stirring defoamer. Furthermore, by using the same apparatus and stirring and defoaming for 10 minutes, the photocurable composition 11 for imprint was prepared. This comparative example is the content of the component (c), which is an upper limit of more than 5 to 30 parts by mass relative to 100 parts by mass of the component (a), and is the same as that of Examples 1 and 2 of the present invention. different.

[Comparative Example 3] (1) A-DCP, which is (b) a monofunctional or polyfunctional (meth) acrylate compound, (c), PE1, which is a polyfunctional thiol compound having 2 to 6 mercapto groups in the molecule, ( c) I184 as a photoradical initiator, (d) I245 as a phenolic antioxidant, (e) 1500 as a phosphite antioxidant, and DDT of a monofunctional thiol compound as other additives, respectively It prepared at the ratio shown in the following Table 1, and stirred and mixed at 50 degreeC for 3 hours using the said stirring degassing machine. Furthermore, the photocurable composition 12 was prepared by defoaming by stirring for 10 minutes using the same apparatus. This comparative example does not contain (a) component, and is different from Example 3, Example 4, Example 7, and Example 8 of this invention.

[Production of cured film] Each of the photocurable compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 3 was held together with a 500 μm-thick silicone rubber spacer on two glass substrates. This glass substrate is subjected to a mold release treatment by coating and drying Novec (registered trademark) 1720 (manufactured by 3M Japan). Using the aforementioned UV irradiation device, this held photocurable composition was exposed to UV at 300 mW / cm ² through an i-line band-pass filter (manufactured by Asahi Kasei Corporation) for 300 seconds. The cured product obtained after the exposure was peeled from the glass substrate subjected to the release treatment, and then heated on a hot plate at 100 ° C. for 10 minutes to produce a cured film having a diameter of 3 cm and a thickness of 0.5 mm.

[Evaluation of transmittance and heat yellowing resistance] The transmittance of the cured film produced by the aforementioned method at a wavelength of 410 nm was measured using the aforementioned ultraviolet-visible near-infrared spectrophotometer. The results are shown in Table 2 below. The cured film was further placed on a silicon wafer, and the silicon wafer was heated on a hot plate heated to 260 ° C. for 3 minutes through the silicon wafer to perform a heat resistance test. The aforementioned ultraviolet-visible near-infrared spectrophotometer was used to measure the transmittance of the cured film after the heat resistance test at a wavelength of 410 nm, and the heat yellowing resistance was evaluated from the change in transmittance before and after heating. The results are combined and shown in Table 2 below.

[Production of Hardened Film and Evaluation of Refractive Index n _D and Abbe's Coefficient ν _D ] Using the aforementioned multi-wavelength refractometer, the refractive index n _D of the cured film produced by the above method at a wavelength of 589 nm and the Abbe's coefficient were measured. ν _D. The results are combined and shown in Table 2 below.

[Evaluation of amount of warpage] 0.010 g of each photocurable composition prepared in Examples 1 to 9 and Comparative Examples 1 to 3 was weighed on a glass substrate, and the glass substrate was coated and dried by NOVEC ( Registered trademark) 1720 (manufactured by 3M Japan). Thereafter, a 500 μm thick silicone rubber spacer was used to hold a glass substrate (1.0 cm square, 0.5 mm thick) that had been tightly treated. The glass substrate was coated with propylene glycol monomethyl ether ethyl and dried. The acid ester was diluted to a solution of 1% by mass of a bonding agent (product name: KBM-5103) manufactured by Shin-Etsu Chemical Industry Co., Ltd. and subjected to adhesion treatment. Using the aforementioned UV irradiation device, this held photocurable composition was exposed to UV at 300 mW / cm ² through an i-line band-pass filter (manufactured by Asahi Kasei Corporation) for 300 seconds. The cured product obtained after the exposure was peeled from the glass substrate subjected to the release treatment, and then heated on a hot plate at 100 ° C. for 10 minutes to produce a diameter of 0.5 cm and a thickness of 0.5 on the glass substrate subjected to the adhesion treatment. mm and mass 0.01g.

The glass substrate on which the cured film was prepared was placed on a stage of the non-contact surface property measurement device such that the glass substrate was an upper surface. The center of the glass substrate was set as the measurement starting point, and the displacement in the vertical direction (Z-axis) with respect to the stage was measured toward the four apexes of the glass substrate. The amount of displacement in the vertical direction (Z axis) between the center of the glass substrate and each vertex of the glass substrate was calculated from the measurement data, and the average value was defined as the amount of warpage. FIG. 1 is a schematic diagram showing a method for evaluating a warpage amount of a glass substrate. The glass substrate after the measurement was heated by a heating plate at 260 ° C. for 3 minutes to perform a heat resistance test, and then the measurement was performed again according to the method described above, and the amount of warpage was evaluated. The respective results are combined and shown in Table 2 below.

The transmittance of Comparative Example 1 before and after the heat resistance test was reduced to more than 3%, and the amount of warpage also showed a result of 2 μm or more. In Comparative Example 2, the film was deformed due to softening in the heat resistance test. As a result, the heat yellowing resistance could not be evaluated. Furthermore, the initial transmittance of Comparative Example 3 was as low as less than 90%, and the amount of warpage was more than 2 μm, showing a result of 10 μm or more. In contrast, the present invention exhibits good characteristics among all characteristics of initial transmittance, heat yellowing resistance, and amount of warpage, and shows suitable refractive index n _D and Abbe as a lens having a high Abbe coefficient. The coefficient ν _D can confirm the advantages of the present invention.

[Production of Lens] The photocurable composition 1 prepared in Example 1, the photocurable composition 3 prepared in Example 3, and the photocurable composition 4 prepared in Example 4 were each made of nickel. Models (arrangement of lens types with a diameter of 2mm × 300μm in 15 ways of 3 rows × 5 widths) and a nano-imprinting machine, and formed on the glass substrate of the support according to the aforementioned method for manufacturing a molded body It is a lens shape. In addition, the model used was previously demolded with NOVEC (registered trademark) 1720 (manufactured by 3M Japan). In addition, the glass substrate used was previously subjected to adhesion treatment with a bonding agent (product name: KBM-503) manufactured by Shin-Etsu Chemical Industry Co., Ltd. After the cured product is peeled from the model, the cured product is heated on a heating plate at 150 ° C. for 10 minutes, thereby producing a convex lens on the glass substrate subjected to the adhesion treatment.

For the convex lens obtained on the aforementioned glass substrate, the lens height (thickness) before and after the heating test was measured using the aforementioned non-contact surface property measuring device, and the following formula "[(lens height before heating-lens height after heating) / before heating Lens height] × 100 "calculates the rate of change to evaluate the dimensional stability by heating. The presence or absence of cracks in the convex lens after the heating test was observed using a microscope attached to the non-contact surface property measurement device. The heating test refers to a test in which the convex lens obtained on the glass substrate is heated for 3 minutes on a heating plate at 260 ° C and then left to cool to room temperature (about 23 ° C). The results are shown in Table 3 below.

As shown in Table 3, the convex lens obtained from the photocurable composition for imprinting of the present invention can obtain a small change in lens height and high dimensional stability even after a thermal history of 260 ° C for 3 minutes. And the like.

Claims (10)

A photocurable composition for imprinting comprising the following (a) component, the following (b) component, which is 0 to 70 parts by mass based on 100 parts by mass of the (a) component, and ( a) The total of 100 parts by mass of the component and the (b) component is 5 to 30 parts by mass of the following (c) component, and the (a) component, the (b) component, and the (c) component The total (100 parts by mass) is 0.2 to 5 parts by mass of the following (d) component, (a): a di (meth) acrylate compound represented by the following formula (1), (In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, R ³ and R ⁴ each independently represent an alkylene group having 1 to 4 carbon atoms, and R ⁵ and R ⁶ each independently represent a hydrogen atom. Or methyl, r ¹ and r ² each independently represent an integer of 1 to 5); (b): a monofunctional or polyfunctional (meth) acrylate compound not containing an aromatic ring (but not including the aforementioned formula ( 1) a di (meth) acrylate compound); (c): a polyfunctional thiol compound having 2 to 6 mercapto groups in the molecule; (d): a photoradical initiator. The photocurable composition for imprinting according to claim 1, which further contains 0.05 parts by mass to 1 part by mass based on 100 parts by mass of the total of the component (a), the component (b), and the component (c). The following (e) component and / or the following (f) component is 0.1 to 3 parts by mass based on 100 parts by mass of the total of the aforementioned (a) component, the aforementioned (b) component, and the aforementioned (c) component, (e): phenol-based antioxidant; (f): phosphite-based antioxidant. The photocurable composition for imprinting according to claim 1 or claim 2, wherein the component (c) is a polyfunctional thiol compound represented by the following formula (2), (In the formula, R ⁷ represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms, X represents a single bond or an ester bond, and A represents a group containing at least one heteroatom or not. An organic group or heteroatom having 2 to 12 carbon atoms including a hetero atom, and r ³ represents an integer of 2 to 6). The photocurable composition for imprinting according to any one of claim 1 to claim 3, further comprising 100 parts by mass based on the total of the component (a), the component (b), and the component (c). It is 0.1 to 3 parts by mass of a monofunctional thiol compound. The photocurable composition for imprinting according to any one of claim 1 to claim 4, wherein the photocurable composition for imprinting has a refractive index n _D of a cured product at a wavelength of 589 nm of 1.50 or more and 1.55 or less. The Abbe coefficient ν _D of the cured product is 53 or more and 60 or less. A cured product of the photocurable composition for imprinting as claimed in claim 5. A method for manufacturing a resin lens, which includes a step of embossing a photocurable composition for imprinting according to any one of claims 1 to 5. A method for manufacturing a molded body, comprising: filling the photocurable composition for imprinting of any one of claim 1 to claim 5 into a space between an adjoining support and a mold, or a separable A step of the internal space of the model, and a step of exposing and photocuring the photocurable composition filled in the space. The method for manufacturing a molded article according to claim 8, further comprising a step of removing and demolding the obtained photocured material after the photocuring step, and performing the demolding step before, during, or after the demolding step. The light-hardened material is subjected to a heating step. The method for manufacturing a molded article according to claim 8 or claim 9, wherein the molded article is a lens for a camera module.