Curable composition, cured product, and method for producing curable composition

Abstract

To provide a curable composition that yields a cured product having a high refractive index, intra-system uniformity, and transparency in combination.SOLUTION: A curable composition contains an oligomer complex. The oligomer complex is formed by coordinating a ligand to a metal alkoxide oligomer, and the number average molecular weight of the metal alkoxide oligomer is 500 or more.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a curable composition, a cured product, and a method for producing a curable composition.

Background Art

[0002] In optical products, there are many technologies that utilize light reflection and refraction, and the refractive index has a significant impact on the characteristics due to the refraction effect. The refractive index is the value obtained by dividing the speed of light in a vacuum by the speed of light in a substance, and it serves as an index for comparing the progress of light in a substance. When light moves between substances with different refractive indices, a phenomenon occurs where the traveling direction changes (refracts) at the boundary (Snell's law).

[0003] As technologies that utilize such refraction phenomena, there are known technologies such as using a laminated structure that gradually eliminates the refractive index difference between air and a substrate as an antireflection coating for display devices such as displays, technologies for thinning optical lenses such as microlens arrays by using high refractive index materials, and technologies for improving the light collection rate of optical transceivers, etc. (for example, Patent Documents 1 to 3).

[0004] Furthermore, high refractive index materials are expected to be applied to various optical devices such as AR (augmented reality) and VR (virtual reality), and many development studies are being conducted. As such high refractive index materials, a technology of dispersing metal oxide nanoparticles in a resin is known (for example, Patent Document 4).

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0006] In the conventional design method of high refractive index organic materials, an organic-inorganic composite method in which high refractive index metal nanoparticles are blended with a resin binder is generally used. However, the interfacial energy increases significantly due to the mixing of the resin and the nano metal, and it becomes thermodynamically unstable, so aggregation easily occurs, and problems often arise such as becoming opaque by forming a heterogeneous system and generating a refractive index distribution.

[0007] In addition, as another method, a sol-gel reaction using metal alkoxide can be mentioned. The refractive index increases by forming a titanoxane structure through a hydrolysis-condensation reaction (sol-gel reaction). However, it has been reported that metal alkoxide has high reactivity and becomes heterogeneous and opaque due to the rapid progress of the sol-gel reaction (Miyuki Harada, Hideaki Kuraya, Koichi Ochi, "Network Polymer" Vol.26 No.2 (2005) 91-97).

[0008] In addition, as a method for suppressing the transparency and refractive index distribution of a cured product using a sol-gel reaction, a sol-gel reaction using a metal alkoxide monomer complex in which a ligand is coordinated to a metal alkoxide monomer can be mentioned. By complexation, the sol-gel reaction can be suppressed due to the reduction of the sol-gel reaction points and the steric hindrance of the ligand, and it is a great advantage of complex formation that the sol-gel reactivity can be controlled by the equivalent of the ligand with respect to the central metal element. However, as a result of the inventor's study, it has been found that when a ligand is introduced under the condition of sufficiently improving the refractive index of the resin binder with a metal alkoxide monomer complex, the sol-gel reactivity is too high and a heterogeneous system is likely to be formed.

[0009] An object of the present invention is to provide a curable composition capable of obtaining a cured product that achieves both high refractive index, in-system uniformity, and permeability.

Means for Solving the Problems

[0010] One aspect of the present invention provides a curable composition comprising an oligomer complex, wherein the oligomer complex is formed by coordinating a ligand to a metal alkoxide oligomer and the number average molecular weight of the metal alkoxide oligomer is 500 or more.

Advantages of the Invention

[0011] According to the present invention, it is possible to provide a curable composition capable of obtaining a cured product that achieves both high refractive index, in-system uniformity, and transparency.

[0012] Hereinafter, embodiments of the present invention will be described in detail.

[0013] <Curable Composition> The curable composition according to an embodiment of the present invention contains an oligomer complex.

[0014] In this specification, a curable composition refers to a composition that cures upon application of energy (e.g., heat and / or light energy) from the outside. An oligomer complex refers to a complex having a repeating unit structure within the molecule. Here, a complex is a compound in which a ligand is coordinately bonded to a central atom or ion, but it may also be a complex (cluster complex) containing two or more central atoms or ions.

[0015] In this embodiment, the oligomer complex is a coordination compound formed by coordinating a ligand to a metal alkoxide oligomer. Here, "coordinating a ligand to a metal alkoxide oligomer" means that the ligand is coordinately bonded to the metal in the metal alkoxide oligomer.

[0016] The metal alkoxide oligomer is represented by, for example, the following formula (1).

[0017]

Chemical formula

[0018] Further, the reaction of coordinating a ligand to a metal alkoxide oligomer to form an oligomer complex is represented by, for example, the following formula (2).

[0019] [Chemical formula]

[0020] As a result of the inventors' intensive studies, by using a metal alkoxide oligomer complex in which a ligand is coordinated to a metal alkoxide oligomer for the metal alkoxide, a cured product that achieves both high refractive index, in-system uniformity, and permeability can be obtained due to the reduction of reaction points by the oligomer and the hydrolysis inhibitory effect by the complex.

[0021] In the above formulas (1) and (2), M is a metal element (central metal). R is an alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 3 to 4 carbon atoms. For example, an n-isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, etc. may be mentioned. Also, each R may be the same or different. O is oxygen, and OR is an alkoxide. n is an integer of 1 or more. Note that a complex having an alkyl group smaller than this has high hydrolysis condensation reactivity and is difficult to control the reaction. On the other hand, a complex having an alkyl group that is too large has low hydrolysis condensation reactivity and there is a possibility that a cured product cannot be obtained.

[0022] Also, in the above formula (2), L is a ligand.

[0023] The metal element constituting the metal alkoxide oligomer is not particularly limited, but is, for example, a transition metal, preferably a transition metal of Groups 4, 5, 13, 14, and 15, and more preferably titanium (Ti). Note that the metal element may also form a metal cluster containing two or more identical or different metals.

[0024] In this embodiment, the number average molecular weight of the metal alkoxide oligomer is 500 or more. Note that the number average molecular weight of the metal alkoxide oligomer is preferably 500 or more and 10,000 or less, more preferably 500 or more and 3,000 or less, and even more preferably 1,000 or more and 3,000 or less, in terms of maintaining the liquid viscosity when a complex obtained from the metal alkoxide oligomer is blended and the uniformity within the system during the sol-gel reaction. When the number average molecular weight is less than 500, it becomes difficult to control the sol-gel reaction, and the uniformity of the cured film deteriorates. Examples of the method for calculating the number average molecular weight include gel permeation chromatography (GPC).

[0025] The type of ligand constituting the metal alkoxide oligomer complex is not particularly limited, and it may be either an inorganic mineral or an organic compound, and may be either a monodentate ligand or a polydentate ligand with two or more coordination sites.

[0026] One type or two or more types of ligands may coordinate. From the viewpoint of stability, polydentate ligands are preferred as ligands, and among them, bidentate ligands are even more preferred. Examples of bidentate ligands include various carboxylic acids, various acrylates, various carboxyacrylates, and various β-diketones.

[0027] The content of the ligand is not particularly limited, but is preferably 0.1 molar times or more and 3 molar times or less, more preferably 0.3 molar times or more and 2.5 molar times or less, and even more preferably 0.5 molar times or more and 2 molar times or less, relative to the metal element in the oligomer complex. When the content of the ligand exceeds 3 molar times, the refractive index of the entire blend decreases. Also, when the ligand content is less than 0.1 molar times, the amount of complex formation with the metal alkoxide oligomer is small, so the uniformity of the cured film due to the rapid sol-gel reaction deteriorates.

[0028] The content of the oligomer complex is not particularly limited, but is preferably 5% by mass or more and 90% by mass or less, more preferably 10% by mass or more and 85% by mass or less, and still more preferably 15% by mass or more and 80% by mass or less in the curable composition. When the content of the oligomer complex exceeds 90% by mass, the film-forming property deteriorates due to the large amount of alcohol-eliminating components by the sol-gel reaction. When the oligomer complex content is less than 5% by mass, the influence of the metal alkoxide oligomer is small, so the refractive index of the formulation decreases.

[0029] In the curable composition of the present embodiment, other components other than the oligomer complex may be further contained according to the purpose. Examples of the other components include resins (excluding metal alkoxide oligomers and oligomer complexes), initiators, inhibitors, surfactants, builders, pH adjusters, solvents, defoamers, bactericides, preservatives, colorants, fragrances, and the like.

[0030] The resin is not particularly limited, and examples thereof include (meth)acrylic resins, (meth)acrylamide resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, silicone resins, urethane resins, and the like.

[0031] Such resins can use polymerizable monomers. Specific examples of polymerizable monomers include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, glycerin dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, ethylene oxide adduct methacrylate of bisphenol A, trimethylolpropane trimethacrylate, tricyclodecane dimethanol dimethacrylate, glycerin dimethacrylate, trimethylolpropane trimethacrylate, ethoxylated isocyanuric acid triacrylate, ε-caprolactone-modified tris-(2-acryloxyethyl) isocyanurate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol polyacrylate, dipentaerythritol hexaacrylate, triallyl isocyanurate, triallyl cyanurate, divinylbenzene, divinyl isophthalate, N-phenyl-maleimide, N-phenyl-methylmaleimide, N-phenyl-chloromaleimide, N-p-chlorophenyl-maleimide, N-p-methoxyphenyl-maleimide, N-p-methylphenyl-maleimide, N-p-nitrophenyl-maleimide, N-p-phenoxyphenyl-maleimide, N-p-phenylaminophenyl-maleimide, N-p-phenoxycarbonylphenyl-maleimide, 1-maleimide-4-acetoxysuccinimide-benzene, 4-maleimide-4'-acetoxysuccinimide-diphenylmethane, 4-maleimide-4'-acetoxysuccinimide-diphenyl ether, 4-maleimide-4'-acetamido-diphenyl ether, 2-maleimide-6-acetamido-pyridine, 4-maleimide-4'-acetamido-diphenylmethane and N-p-phenylcarbonylphenyl-maleimide N-ethylmaleimide, N-2.Examples include 6-xylylmaleimide, N-cyclohexylmaleimide, N-2,3-xylylmaleimide, xylylmaleimide, 2,6-xylenemaleimide, 4,4'-bismaleimidodiphenylmethane, and the like.

[0032] These polymerizable monomers may be used alone or in combination of two or more. Among these, (meth)acrylate (meaning both acrylate and methacrylate) is preferable from the viewpoint of the moldability of the resin, and more preferably a polyfunctional (meth)acrylate having high thermal stability of the cured product.

[0033] The content of the resin is not particularly limited, but is preferably 1% by mass or more and 90% by mass or less, more preferably 5% by mass or more and 85% by mass or less, and still more preferably 10% by mass or more and 80% by mass or less in the curable composition. When the content of the resin in the curable composition is less than 1% by mass, the main polymerization reaction becomes only the metal alkoxide oligomer, and the film-forming property deteriorates due to the large amount of the alcohol elimination component by the sol-gel reaction. On the other hand, when the content of the resin in the curable composition exceeds 90% by mass, the influence of the metal alkoxide oligomer is small, so the refractive index of the formulation decreases.

[0034] The initiator is a compound (also referred to as a polymerization initiator) added to initiate a polymerization reaction for synthesizing a polymer from the resin (polymerizable monomer) contained in the curable composition. The type of the initiator is not particularly limited, and either a thermal polymerization initiator or a photo-polymerization initiator may be used.

[0035] Examples of the thermal polymerization initiator include peroxides such as benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, di-t-butyl peroxide, t-butyl cumyl peroxide, α,α-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, dicumyl peroxide, di-t-butyl peroxyisophthalate, t-butyl peroxybenzoate, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di(trimethylsilyl)peroxide, and trimethylsilyl triphenylsilyl peroxide. These thermal polymerization initiators may be used alone or in combination of two or more.

[0036] Examples of the photopolymerization initiator include benzophenone, benzyl, Michler's ketone, thioxanthone derivatives, benzoin ethyl ether, diethoxyacetophenone, benzyldimethylketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, acylphosphine oxide derivatives, 2-methyl-1-{4-(methylthio)phenyl}-2-morpholinopropan-1-one, 4-benzoyl-4'-methyldiphenyl sulfide, 2,4,6-trimethylbenzoyl-diphenylphosphine, etc. These photopolymerization initiators may be used alone or in combination of two or more.

[0037] The content of the initiator is not particularly limited. However, when the content of the initiator in the curable composition is 0.1% by mass or more and 10% by mass or less, the polymerization proceeds sufficiently.

[0038] In the curable composition of the present embodiment, as described above, by including an oligomer complex in which a ligand is coordinated to a metal alkoxide oligomer having a number average molecular weight of 500 or more, the refractive index of the resulting cured product can be increased. Further, when the complexed oligomer is cured to obtain a cured product, the sol-gel reaction points are reduced and aggregation is suppressed as compared with the complex monomer, so that the uniformity within the system can be maintained. As a result, the resulting cured product can improve the refractive index and the transmittance.

[0039] Further, in the curable composition of the present embodiment, as described above, when the content of the oligomer complex is 5% by mass or more and 90% by mass or less, titanium oxide aggregates that cause non-uniform formation are not generated when the curable composition is cured, and a sufficient amount of the oligomer complex having a stable sol-gel reactivity is contained in the curable composition, so that the uniformity within the system is surely increased. As a result, the resulting cured product can surely increase the transmittance while surely maintaining a high refractive index.

[0040] Further, in the curable composition of the present embodiment, as described above, since a stable oligomer complex can be formed in the curable composition by the content of the ligand being 0.1 molar times or more and 3 molar times or less with respect to the metal element in the metal alkoxide oligomer, the uniformity within the system can be made even more surely high. As a result, the cured product obtained from the curable composition can more surely increase the transmittance while more surely maintaining a high refractive index.

[0041] Further, in the curable composition of the present embodiment, as described above, by further containing a resin in addition to the oligomer complex, excellent moldability of the resin can be imparted, and wide application development of resinous materials is expected.

[0042] <Cured product> The cured product according to the embodiment of the present invention is obtained by curing the curable composition of the present embodiment described above. That is, the cured product of the present embodiment is a cured product obtained by curing a curable composition containing an oligomer complex in which a ligand is coordinated to a metal alkoxide oligomer having a number average molecular weight of 500 or more.

[0043] The obtained cured product may be either one obtained by curing a curable composition not containing a resin or one obtained by curing a curable composition containing a resin.

[0044] For example, when curing a curable composition not containing a resin, since the oligomer complex forms a three-dimensional crosslinked structure alone, a cured film can be formed. Also, when curing a curable composition containing a resin, as described above, by optionally adding an initiator or the like and heating or irradiating with light, a cured product can be formed.

[0045] Since the cured product of the present embodiment is one obtained by curing the curable composition of the present embodiment in this way, the effects of the curable composition of the present embodiment can be obtained.

[0046] That is, in the cured product of the present embodiment, by curing a curable composition containing an oligomer complex in which a ligand is coordinated to a metal alkoxide oligomer having a number average molecular weight of 500 or more, the refractive index of the cured product obtained by the hydrolysis polycondensation reaction of the metal alkoxide becomes high. Also, when the complex-formed oligomer cures to obtain a cured product, the sol-gel reaction points decrease and aggregation is suppressed, so that the in-system uniformity improves. As a result, the obtained cured product has a high transmittance while maintaining the refractive index.

[0047] <Method for producing a curable composition> The method for producing a curable composition according to an embodiment of the present invention includes a step of mixing a metal alkoxide oligomer having a number average molecular weight of 500 or more and a ligand to prepare a curable composition containing an oligomer complex. The oligomer complex contained in the curable composition is one in which a ligand is coordinated to the metal alkoxide oligomer. In the method for producing a curable composition according to the present embodiment, the curable composition of the present embodiment described above is obtained.

[0048] In the method for producing the curable composition, as shown in the above formula (2), a reaction proceeds in which a ligand is coordinated to a metal alkoxide oligomer to form an oligomer complex. The conditions for the reaction to form the oligomer complex are arbitrary. For example, a metal alkoxide oligomer such as titanium butoxide oligomer and a ligand such as acetylacetone are placed in a container under an inert atmosphere and stirred.

[0049] The molar ratio of the metal alkoxide oligomer to the ligand is arbitrary, but for example, it is 1:9 to 9:1, preferably 1:4 to 4:1, and more preferably 2:3 to 3:2.

[0050] The temperature during stirring is arbitrary, but for example, it is 5 to 50 °C, preferably 10 to 40 °C, and more preferably 20 to 30 °C. Also, the stirring time is arbitrary, but for example, it is 1 to 36 hours, preferably 3 to 24 hours, and more preferably 6 to 12 hours.

[0051] In the method for producing the curable composition according to the present embodiment, since the curable composition of the present embodiment is obtained in this way, the effects of the curable composition of the present embodiment can be obtained from the obtained curable composition.

[0052] That is, in the method for producing the curable composition according to the present embodiment, since a curable composition containing an oligomer complex in which a ligand is coordinated to a metal alkoxide oligomer having a number average molecular weight of 500 or more is obtained, the refractive index of the obtained cured product becomes high. In addition, since a sufficient amount of oligomer complex having a stable sol-gel reactivity that does not generate titanoxane aggregates that cause non-uniform formation when the complexed oligomer cures is contained in the curable composition, the system uniformity is improved. As a result, the obtained cured product has a high transmittance while maintaining the refractive index.

Examples

[0053] Hereinafter, the present embodiment will be further described using experimental examples. Also, various tests and evaluations follow the following methods. In the following, "parts" or "%" are based on mass unless otherwise specified.

[0054] <Synthesis of Oligomer Complex> [Synthesis Example 1] 6.5 g (11.8 mmol) (converted as titanium tetrabutoxide monomer) of Ti butoxide oligomer (manufactured by Matsumoto Fine Chemical Co., Ltd., PC-200) as a metal alkoxide oligomer and 0.6 g (11.8 mmol) of acetylacetone (manufactured by Tokyo Chemical Industry Co., Ltd.) as a ligand were added to a vial under an inert atmosphere and stirred at room temperature overnight to obtain Compound 1 (oligomer complex). As a result of measuring PC-200 by gel permeation chromatography (GPC), the number average molecular weight (Mn) was 1753.

[0055] Compound 1 was measured using a Fourier transform infrared spectrometer (FT-IR) (manufactured by Thermo Fisher Scientific, Nicolet iS10). The peak near 1710 cm -1 derived from the carbonyl stretching vibration of the ketone group observed before coordination disappeared, and a new peak at 1520 cm -1 derived from the C-O stretching vibration after coordination was observed, confirming the success of the synthesis.

[0056] [Synthesis Example 2] 6.5 g (11.8 mmol) (converted as titanium tetrabutoxide monomer) of Ti butoxide oligomer (manufactured by Matsumoto Fine Chemical Co., Ltd., PC-200) as a metal alkoxide oligomer and 2.7 g (11.8 mmol) of 2-methacryloyloxyethyl succinate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-SA) as a ligand were added to a vial under an inert atmosphere and stirred at room temperature overnight to obtain Compound 2 (oligomer complex).

[0057] Compound 2 was measured using FT-IR (manufactured by Thermo Fisher Scientific, Nicolet iS10). The peak near 1710 cm -1 derived from the carbonyl stretching vibration of the carboxy group observed before coordination disappeared, and a new peak at 1550 cm -1 derived from the C-O stretching vibration after coordination was observed, confirming the success of the synthesis.

[0058] [Synthesis Example 3] 4.0 g (11.8 mmol) of Ti tetrabutoxide monomer (molecular weight: 340.32, manufactured by Tokyo Chemical Industry Co., Ltd.), which is a metal alkoxide monomer, and 1.2 g (11.8 mmol) of acetylacetone (manufactured by Tokyo Chemical Industry Co., Ltd.) as a ligand were added to a vial under an inert atmosphere and stirred at room temperature overnight to obtain Compound 3 (oligomer complex).

[0059] Compound 3 was observed using FT-IR (Nicolet iS10, manufactured by Thermo Fisher Scientific Inc.) at 1710 cm -1 near the peak derived from the carbonyl stretching vibration of the ketone group observed before coordination disappeared, and a new peak at 1520 cm -1 derived from the C-O stretching vibration after coordination was newly observed, confirming the success of the synthesis.

[0060] [Preparation of Curable Composition and Cured Product] [Example 1] 80 parts of Compound 1 as an oligomer complex, 20 parts of tricyclodecane dimethanol dimethacrylate (DCP-M, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a resin, 0.03 part of 2-hydroxy-2-methylpropiophenone (Omnirad (registered trademark) 1173, manufactured by IGM Resins B.V.) as an initiator, and 0.03 part of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (Omnirad (registered trademark) TPO H, manufactured by IGM Resins B.V.) were blended to prepare a solution (curable composition). The formulation of Example 1 is shown in Table 1.

[0061] Using the prepared solution, a UV irradiation device (Eye Graphicx ECS-401GX, manufactured by Eye Graphicx Co., Ltd.) equipped with a high-pressure mercury lamp (H04-L41, manufactured by Eye Graphicx Co., Ltd.) was used to irradiate at an illuminance of 2 J / cm 2 After irradiation, heat treatment was performed at 120 °C for 60 minutes using a thermostatic and humidistatic chamber (STPH-101, manufactured by Espec Co., Ltd.) to prepare a cured film (cured product). The obtained cured film was prepared and evaluated on a slide glass (S9111, manufactured by Matsunami Glass Industry Co., Ltd.) with a thickness of 4 μm.

[0062] [Transmittance and haze value] Measurement was carried out using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., NDH 7000SP). It was evaluated as good when the transmittance was 90% or more and the haze value was 1% or less. As a result of the measurement, the total light transmittance was 90% or more and the haze value was 1% or less, indicating sufficient transparency (good). The results are shown in Table 1.

[0063] [Refractive index] The refractive index was measured using a refractometer (manufactured by Metricon Japan Co., Ltd., Prism Coupler 2010 / M). It was evaluated as good when the refractive index was higher than that of Comparative Example 3 (an example containing DCP-M alone as the resin). As a result of the measurement, it increased compared to the refractive index of the resin alone (good). The results are shown in Table 1.

[0064] [Homogeneity within the system] A secondary electron image at 50,000 times magnification was taken and observed using FE-SEM (manufactured by Thermo Fisher Scientific, Helios5 UC DualBeam). The homogeneity within the system was evaluated as good when it was confirmed that there were no aggregates. As a result of the observation, no aggregates were confirmed (good). The results are shown in Table 1.

[0065] [Example 2] 50 parts of Composition 1 as the oligomer complex, 50 parts of tricyclodecane dimethanol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., DCP-M) as the resin, 0.03 part of 2-hydroxy-2-methylpropiophenone (manufactured by IGM Resins B.V., Omnirad® 1173), and 0.03 part of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (manufactured by IGM Resins B.V., Omnirad® TPO H) as the initiator were blended to prepare a solution (curable composition). The cured film (cured product) was prepared in the same manner as in Example 1. The formulation of Example 2 is shown in Table 1.

[0066] Similar to Example 1, as a result of measurement with a haze meter, the total light transmittance was 90% or more and the haze value was 1% or less, indicating sufficient transparency (good). Also, as a result of measuring the refractive index with a refractometer, the refractive index increased compared to that of the resin alone (good). Furthermore, as a result of taking and observing a secondary electron image at 50,000 times magnification with FE-SEM, no aggregates were confirmed (system uniformity: good).

[0067] [Example 3] 20 parts of Composition 1 as an oligomer complex, 80 parts of tricyclodecane dimethanol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., DCP-M) as a resin, 0.03 part of 2-hydroxy-2-methylpropiophenone (manufactured by IGM Resins B.V., Omnirad (registered trademark) 1173, denoted as "PI1173" in Table 1), and 0.03 part of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (manufactured by IGM Resins B.V., Omnirad (registered trademark) TPO H) were blended to prepare a solution (curable composition). The cured film (cured product) was prepared in the same manner as in Example 1. The formulation of Example 3 is shown in Table 1.

[0068] Similar to Example 1, as a result of measurement with a haze meter, the total light transmittance was 90% or more and the haze value was 1% or less, indicating sufficient transparency (good). Also, as a result of measuring the refractive index with a refractometer, the refractive index increased compared to that of the resin alone (good). Furthermore, as a result of taking and observing a secondary electron image at 50,000 times magnification with FE-SEM, no aggregates were confirmed (system uniformity: good).

[0069] [Example 4] 80 parts of Compound 2 as an oligomer complex, 20 parts of tricyclodecane dimethanol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., DCP-M) as a resin, 0.03 part of 2-hydroxy-2-methylpropiophenone (manufactured by IGM Resins B.V., Omnirad® 1173), and 0.03 part of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (manufactured by IGM Resins B.V., Omnirad® TPO H) as initiators were blended to prepare a solution (curable composition). The cured film (cured product) was prepared in the same manner as in Example 1. The formulation of Example 4 is shown in Table 1.

[0070] Similar to Example 1, as a result of measurement with a haze meter, the total light transmittance was 90% or more and the haze value was 1% or less, indicating sufficient transparency (good). Also, as a result of measuring the refractive index with a refractometer, it increased compared to the refractive index of the resin alone (good). Furthermore, as a result of photographing and observing a secondary electron image at 50,000 times with FE-SEM, no aggregates were confirmed (system uniformity: good).

[0071] [Comparative Example 1] 80 parts of Compound 3, 20 parts of tricyclodecane dimethanol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., DCP-M) as a resin, 0.03 part of 2-hydroxy-2-methylpropiophenone (manufactured by IGM Resins B.V., Omnirad® 1173), and 0.03 part of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (manufactured by IGM Resins B.V., Omnirad® TPO H) as initiators were blended to prepare a solution. The cured film was prepared in the same manner as in Example 1. The formulation of Comparative Example 1 is shown in Table 1.

[0072] Similar to Example 1, as a result of measurement with a haze meter, the total light transmittance was 90% or less and the haze value was 1% or less, indicating insufficient transparency (bad). Also, as a result of measuring the refractive index with a refractometer, it increased compared to the refractive index of the resin alone (good). Furthermore, as a result of photographing and observing a secondary electron image at 50,000 times with FE-SEM, aggregates were confirmed (system uniformity: bad).

[0073] [Comparative Example 2] 100 parts of Ti butoxide oligomer (manufactured by Matsumoto Fine Chemical Co., Ltd., PC-200, Mn: 1753), 0.03 part of 2-hydroxy-2-methylpropiophenone (manufactured by IGM Resins B.V., Omnirad (registered trademark) 1173) as a resin, and 0.03 part of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (manufactured by IGM Resins B.V., Omnirad (registered trademark) TPO H) as an initiator were blended to prepare a solution. A cured film was prepared in the same manner as in Example 1. The formulation of Comparative Example 2 is shown in Table 1.

[0074] Similar to Example 1, as a result of measurement with a haze meter, the total light transmittance was 90% or less and the haze value was 1% or more, indicating insufficient transparency (defective). Also, as a result of measuring the refractive index with a refractometer, no measured combined value was obtained (defective). Furthermore, as a result of taking and observing a secondary electron image at 50,000 times with FE-SEM, aggregates were confirmed (system uniformity: defective).

[0075] [Comparative Example 3] 100 parts of tricyclodecane dimethanol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., DCP-M), 0.03 part of 2-hydroxy-2-methylpropiophenone (manufactured by IGM Resins B.V., Omnirad (registered trademark) 1173) as a resin, and 0.03 part of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (manufactured by IGM Resins B.V., Omnirad (registered trademark) TPO H) as an initiator were blended to prepare a solution. A cured film was prepared in the same manner as in Example 1. The formulation of Comparative Example 3 is shown in Table 1.

[0076] Similar to Example 1, as a result of measurement with a haze meter, the total light transmittance was 90% or more and the haze value was 1% or less, and it was evaluated that the transparency was sufficient (good). Further, the refractive index was measured with a refractometer to confirm the refractive index of the resin alone (reference refractive index). Furthermore, as a result of photographing and observing a secondary electron image at 50,000 times with FE-SEM, no aggregates were confirmed (system uniformity: good).

[0077] [Comparative Example 4] 66.7 parts of Ti butoxide oligomer (Mn: 1753) (manufactured by Matsumoto Fine Chemical Co., Ltd., PC-200), 33.3 parts of tricyclodecane dimethanol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., DCP-M) as a resin, and 2-hydroxy-2-methylpropiophenone (manufactured by IGM Resins B.V., Omnirad® 1173) 0.03 part and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (manufactured by IGM Resins B.V., Omnirad® TPO H) 0.03 part as initiators were blended to prepare a solution. A cured film was prepared in the same manner as in Example 1. The formulation of Comparative Example 4 is shown in Table 1.

[0078] Similar to Example 1, as a result of measurement with a haze meter, the total light transmittance was 90% or less and the haze value was 1% or more, and it was evaluated that the transparency was insufficient (poor). Further, as a result of measuring the refractive index with a refractometer, it increased compared to the refractive index of the resin alone (good). Furthermore, as a result of photographing and observing a secondary electron image at 50,000 times with FE-SEM, aggregates were confirmed (system uniformity: poor). The results are shown in Table 1.

Table 1

[0079] From Table 1, the curable composition containing an oligomer complex in which a ligand is coordinated to a metal alkoxide oligomer having a number average molecular weight of 500 or more was good in terms of the transmittance, haze value, refractive index, permeability, and system uniformity of the obtained cured product (Examples 1 to 4).

[0080] On the other hand, when the conditions of the curable composition containing an oligomer complex in which a ligand is coordinated to a metal alkoxide oligomer having a number average molecular weight of 500 or more are not satisfied, at least one of the transmittance, haze value, refractive index, permeability, and in-system uniformity is poor (Comparative Examples 1 to 4).

[0081] Hereinafter, preferred embodiments of the present invention will be appended.

[0082] (Appendix 1) A curable composition containing an oligomer complex, wherein the oligomer complex is obtained by coordinating a ligand to a metal alkoxide oligomer, and the number average molecular weight of the metal alkoxide oligomer is 500 or more. Curable composition.

[0083] (Appendix 2) The content of the oligomer complex is 5% by mass or more and 90% by mass or less, The curable composition according to Appendix 1.

[0084] (Appendix 3) The content of the ligand is 0.1 molar times or more and 3 molar times or less with respect to the metal element in the metal alkoxide oligomer, The curable composition according to Appendix 1 or 2.

[0085] (Appendix 4) Further containing a resin, The curable composition according to any one of Appendices 1 to 3.

[0086] (Appendix 5) A cured product obtained by curing the curable composition according to any one of Appendices 1 to 4.

[0087] (Appendix 6) A method for producing a curable composition, comprising a step of mixing a metal alkoxide oligomer having a number average molecular weight of 500 or more and a ligand to prepare a curable composition containing an oligomer complex in which the ligand is coordinated to the metal alkoxide oligomer.

[0088] Although the embodiments of the present invention have been described above, the present invention is not limited to specific embodiments, and various modifications and changes are possible within the scope of the invention described in the claims.

Claims

1. comprising an oligomer complex, wherein the oligomer complex is obtained by coordinating a ligand to a metal alkoxide oligomer, and the number average molecular weight of the metal alkoxide oligomer is 500 or more, a curable composition.

2. wherein the content of the oligomer complex is 5% by mass or more and 90% by mass or less, the curable composition according to claim 1.

3. the curable composition according to claim 1, wherein the content of the ligand is 0.1 molar times or more and 3 molar times or less with respect to the metal element in the metal alkoxide oligomer.

4. further containing a resin, the curable composition according to claim 1.

5. a cured product obtained by curing the curable composition according to any one of claims 1 to 4.

6. A method for producing a curable composition, comprising a step of mixing a metal alkoxide oligomer having a number average molecular weight of 500 or more and a ligand to prepare a curable composition containing an oligomer complex in which the ligand is coordinated to the metal alkoxide oligomer.

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