JP6589151B2 - Photocurable resin composition and high refractive resin cured body - Google Patents

Description

  The present invention relates to a photocurable resin composition and a highly refractive resin cured product obtained by photocuring the photocurable resin composition.

  In order to control the path of light with a small curvature, the photo-curing plastic obtained by photo-curing photo-curing resin, which is widely used in optical parts, is used to reduce the thickness of optical parts and increase the resolution. Increasing the refractive index of the photocurable resin is an important issue.

  In order to achieve a high refractive index of the photocurable resin, phenylphenol ethoxyacrylate is blended (for example, Patent Document 1), and bifunctional (meth) acrylate having a fluorene skeleton is blended in the photocurable resin (for example, , Patent Document 2), and a method of further blending inorganic particles with these photocurable resins (for example, Patent Document 3) is disclosed.

JP 2001-124904 A JP 2003-322706 A JP 2008-133379 A

However, the photocurable resins disclosed in Patent Documents 1 and 2 have a problem from the viewpoint of industrial mass high-speed productivity of optical components because the viscosity increases while the refractive index is increased.
In addition, when inorganic particles are added to these photocurable resins in order to improve high refraction, the viscosity is further increased. Therefore, it is necessary to lower the viscosity using a solvent for industrial handling. There is a problem in the manufacture of a three-dimensional optical component that must be avoided.

The present invention is a photocurable resin composition having a low viscosity and improved refractive index without blending a solvent, and
It is an object to provide a highly refractive resin cured body obtained by photocuring the photocurable resin composition.

The present invention
[1] A photocurable resin composition comprising a (meth) acrylate compound, metal-containing nanoparticles and a photopolymerization initiator,
The (meth) acrylate compound has the following formula (1):

(Wherein R ¹ is a hydrogen atom or a methyl group, and a is a number from 0 to 4) and / or benzyl acrylate,
In the (meth) acrylate compound, the total content of the compound represented by the formula (1) and / or benzyl acrylate is 60 to 100% by mass,
A photocurable resin composition having a refractive index of 1.60 or more (hereinafter also referred to as the present invention 1),
[2] A photocurable resin composition comprising a (meth) acrylate compound, metal-containing nanoparticles and a photopolymerization initiator,
The (meth) acrylate compound is a photocurable resin composition (hereinafter also referred to as the present invention 2) containing a compound represented by the formula (1) described in [1] above, and
[3] A highly refractive resin cured product (hereinafter also referred to as the present invention 3) obtained by molding and curing the photocurable resin composition according to [1] or [2].

  According to the present invention, a photocurable resin composition having a low viscosity and an improved refractive index without blending a solvent, and a high refractive index obtained by molding and photocuring the photocurable resin composition. A cured resin body can be provided.

[Invention 1]
Invention 1 is a photocurable resin composition comprising a (meth) acrylate compound (hereinafter referred to as Compound A), metal-containing nanoparticles (hereinafter referred to as Compound B) and a photopolymerization initiator (hereinafter referred to as Compound C). There,
Compound A includes a compound represented by Formula (1) (hereinafter referred to as Compound A1) and / or benzyl acrylate (hereinafter referred to as Compound A2),
In compound A, the total content of compound A1 and / or compound A2 is 60 to 100% by mass,
The refractive index of the photocurable resin composition is 1.60 or more.

(Compound A1)
Compound A1 is represented by the following formula (1):

(Wherein R ¹ is a hydrogen atom or a methyl group, and a is a number of 0 to 4).

  Compound A1 is an ester of phenoxybenzyl alcohol and (meth) acrylic acid or an oxyethylene adduct thereof, and is available as, for example, a commercial product (product name “POB-A”) from Kyoeisha Chemical Co., Ltd.

  Compound 1 not only has a high refractive index of itself, but even if compound B is added to the present invention 1 in order to further improve the refractive index of the present invention 1, the increase in the viscosity of the present invention 1 is suppressed. it can.

From the viewpoint of improving the curing rate and the refractive index of Invention 1, R ¹ is hydrogen and / or a is 0 to 2 (preferably 0 to 1, more preferably 0).

(Compound A2)
Compound A2 is benzyl acrylate and can be obtained, for example, as a commercial product (product name “FA-BZA”) from Hitachi Chemical.

  The compound A2 has been used as an auxiliary agent in the compound A for the purpose of suppressing the viscosity of the photocurable resin composition. However, when compounded in combination with the compound B, the compound A2 is used as the main agent in the compound A. In order to suppress the thickening of the present invention 1 even if blended in a large amount, the effect of improving the refractive index of the present invention 1 is unpredictable from the past.

(Compound A other than Compounds A1 and A2)
As the compound A other than the compounds A1 and A2, a bifunctional (meth) acrylate having a fluorene skeleton known as a (meth) acrylate having a high refractive index and phenylphenol ethoxyacrylate can be preferably used. For example, Patent Documents 1 and 2 describe these details.

  From the viewpoint of improving the adhesive strength of the invention 3 which is the photocured material of the invention 1 to the constituent material in the optical component, it is preferable that the invention 1 is blended with a (meth) acrylate monomer.

  As such a (meth) acrylate monomer, it is preferable to include (meth) acrylates having different functional numbers from the viewpoint of achieving both rapid curing and low curing shrinkage, and monofunctional (meth) acrylate and polyfunctional It is more preferable that (meth) acrylate of this is included.

  Monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) ) Acrylate, t-butyl (meth) acrylate, 2-methylbutyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, 2-methylhexyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, 2-butylhexyl (meth) acrylate, isooctyl (meth) acrylate, isopentyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, isobornyl (meth) Acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxy (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, lauryl (meth) acrylate, hexadecyl (meth) acrylate, stearyl ( (Meth) acrylate, morpholin-4-yl (meth) acrylate, etc. 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate , Tetrahydrofurfuryl (meth) acrylate, 2- (meth) acryloyloxyethyl-succinic acid.

  Bifunctional (meth) acrylates include bisphenol F-EO-modified di (meth) acrylate, bisphenol A-EO-modified di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol (meth) acrylate, and tricyclodecanedi. Examples include methylol di (meth) acrylate and dicyclopentadiene (meth) acrylate.

  Examples of the trifunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, trimethylolpropane PO-modified (meth) acrylate, and isocyanuric acid EO-modified tri (meth) acrylate.

  As tetrafunctional or higher functional (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraacrylate, polyfunctional polyurethane is included in the skeleton. (Meth) acrylate (hereinafter also referred to as polyfunctional urethane (meth) acrylate) and the like.

  From the viewpoint of improving the brittleness of Invention 3 which is the photocured product of Invention 1, it is preferable to incorporate (meth) acrylate oligomer in Invention 1.

As such (meth) acrylate oligomer, in view of fast curing and low cure shrinkage, (meth) acrylate preferably contains at least one selected from the group consisting of polyisoprene, polybutadiene and polyurethane in the skeleton. It contains at least one oligomer.
The (meth) acrylate oligomer can be used alone or in combination of two or more.

The (meth) acrylate oligomer containing polyisoprene in the skeleton is also called (meth) acryl-modified polyisoprene. The weight average molecular weight of the (meth) acrylate oligomer having polyisoprene as a skeleton is preferably 1000 to 100,000, more preferably 10,000 to 60,000.
As a commercially available product of a (meth) acrylate oligomer having a polyisoprene as a skeleton, for example, “UC-1” (weight average molecular weight 25000) manufactured by Kuraray Co., Ltd. may be mentioned.

The (meth) acrylate oligomer containing polybutadiene in the skeleton is also called (meth) acryl-modified polybutadiene. The weight average molecular weight of the (meth) acrylate oligomer containing polybutadiene in the skeleton is preferably 500 to 100,000, more preferably 1000 to 60,000.
Examples of commercially available (meth) acrylate oligomers containing polybutadiene in the skeleton include “TE2000” (weight average molecular weight 2000) manufactured by Nippon Soda Co., Ltd.

The (meth) acrylate oligomer containing polyurethane in the skeleton is also called (meth) acryl-modified polyurethane. The weight average molecular weight of the (meth) acrylate oligomer containing polyurethane in the skeleton is preferably 1000 to 100,000, more preferably 10,000 to 60000.
As a commercial item of the (meth) acrylate oligomer containing a polyurethane in the skeleton, for example, “UN-7700” manufactured by Negami Kogyo Co., Ltd. may be mentioned.

  Among these, the (meth) acrylate oligomer is preferably a (meth) acrylate oligomer containing at least one selected from the group consisting of polyisoprene and polybutadiene in the skeleton.

The weight average molecular weight is measured based on GPC, and is preferably measured under the following conditions:
Measuring device: GPC system manufactured by Shimadzu Corporation;
Column type: organic solvent SEC column (manufactured by Tosoh Corporation);
Solvent type: tetrahydrofuran (THF).

(Compound B)
The metal-containing nanoparticles that are compound B are metal-containing particles having an average particle diameter of 1 to 100 nm.

The average particle size is diluted with a solvent capable of dispersing Compound B to a concentration suitable for measurement, and measured with a dynamic light scattering particle size distribution analyzer LB500 (manufactured by Horiba, Ltd.).
The arithmetic average particle diameter obtained by measuring the apparent arithmetic average particle diameter was used as the average particle diameter of Compound B.
In the calculation of the apparent arithmetic average particle diameter, the refractive index of the nanometal-containing particles as the raw material is input, and the refractive index of the solvent is that of the diluted solvent at the time of measurement.
Ignore the effects of surface modification.
Sampling and measurement should be performed as soon as possible after adjustment of the sample solution.

  The average particle diameter can be measured by, for example, a laser diffraction / scattering particle size distribution measuring apparatus, and specifically, LA-920 manufactured by Horiba, Ltd. can be used.

  The particle size distribution of Compound B preferably shows a single peak when measured by the above measurement method.

From the viewpoint of improving the refractive index of the invention 1, the average particle size of the compound B is
Preferably it is 3-50 nm, More preferably, it is 5-30 nm, More preferably, it is 5-15 nm.

  Examples of the compound B include metal, semiconductor, metal oxide and the like.

The metal-containing compound constituting the compound B is preferably from the viewpoint of improving the refractive index when combined with the compound A1 and / or the compound A2,
Aluminum, cadmium, cerium, chromium, cobalt, copper, gallium, germanium, gold, indium, iron, iridium, lead, mercury, nickel, platinum, palladium, silicon, silver, tin, zinc, zirconium, aluminum arsenide, aluminum nitride , Aluminum phosphide, cadmium selenide, cadmium sulfide, cadmium telluride, gallium arsenide, gallium nitride, gallium phosphide, gallium selenide, gallium sulfide, indium arsenide, indium phosphide, indium nitride, indium selenide, sulfide Indium, indium telluride, lead selenide, lead sulfide, lead telluride, mercury selenide, mercury sulfide, mercury telluride, zinc selenide, zinc sulfide, zinc telluride, aluminum oxide, cadmium oxide, cerium oxide, chromium oxide , Oxidized oxide DOO, indium oxide, indium tin oxide, iron oxide, lead oxide, nickel oxide, silicon dioxide, tin oxide, titanium oxide, at least one compound selected from the group consisting of zinc oxide and zirconium oxide, and more preferably,
At least one compound selected from the group consisting of tin oxide, titanium oxide, zinc oxide and zirconium oxide, more preferably
At least one compound selected from the group consisting of titanium oxide and zirconium oxide, more preferably zirconium oxide.

(Compound C)
Compound C is a photopolymerization initiator (preferably a photoradical polymerization initiator), and a compound that has activity with respect to the wavelength of the light source to be used is mixed to generate an appropriate active species. Moreover, only one type of photopolymerization initiator may be used, or two or more types may be used.

Since compound C irradiates light through a substrate or a mold that forms an imprint, it is necessary to select the time appropriate for the wavelength that these substrate and mold transmit, but the curing speed is fast and Those having excellent compatibility and little yellowing after curing are preferred.
Those having a fast curing rate are preferable from the viewpoint of mass production by a roll-to-roll method or the like because they can be cured by a low energy light beam.
Those having excellent compatibility are preferably each from the viewpoints that precipitation of an initiator due to crystallization or the like hardly occurs, and those having little yellowing are excellent in transparency.

As compound C, BASF's,
Irgacure (registered trademark) series such as Irgacure 184, Irgacure 819,
Darocur (registered trademark) series such as Darocur 1173,
Lucirin (registered trademark) series such as Lucirin TPO,
Examples include ESACURE 1001M (1- [4-benzoylphenylsulfanyl] phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one manufactured by ESACUR Nippon Siebel Hegner.

(Other compounds)
In addition to the compounds A, B and C, the present invention 1 can contain other compounds as long as the effects of the present invention 1 are not impaired.

  Examples of other compounds include compounds that can be polymerized by photoreaction with compound A, and examples include epoxy oligomers, phenolic resins, oxetane compounds, and the like.

This invention 1 can contain various additives as an arbitrary component as needed.
For example, antioxidant, UV absorber, light stabilizer, silane coupling agent, polymerization inhibitor, leveling agent, surfactant, colorant, storage stabilizer, plasticizer, lubricant, filler, anti-aging agent, wettability Improving agents, release agents and the like can be included.

  When the present invention 1 includes a solvent, for example, when molding a lens using a mold or when two glasses are bonded, the solvent remains in the cured body as it is so as not to cause brittleness of the cured body. In addition, the present invention 1 is preferably suppressed to an amount of solvent that volatilizes during the production process of the cured product, and more preferably does not contain a solvent.

(Photocurable resin composition)
The present invention 1 is a photocurable resin composition comprising Compound A, Compound B and Compound C,
Compound A includes Compound A1 and / or Compound A2,
In the compound A, the total content of the compound A1 and / or the compound A2 is 60 to 100% by mass, and the refractive index of the photocurable resin composition inhibitor 1 is 1.60 or more.

The present invention 1 is from the viewpoint of improving the refractive index while suppressing the thickening of the present invention 1, and from the viewpoint of improving the adhesive strength and brittleness to the constituent material in the optical component,
In the compound A, the total content of the compound A1 and / or the compound A2 is preferably 60 to 90% by mass, more preferably 65 to 80% by mass, still more preferably 65 to 75% by mass,
In the compound A, the compound A other than the compound A1 and / or the compound A2 is preferably a (meth) acrylate monomer and / or a (meth) acrylate oligomer.

  When the compound A1 and the compound A2 are used in combination, the mass ratio (A1 / A2) between the compound A1 and the compound A2 is preferably 10/90 to 90/10, more preferably 20/80 to 80/20, still more preferably 30/70 to 70/30, more preferably 40/60 to 60/40.

From the viewpoint of improving the refractive index while suppressing the thickening of the present invention 1,
Compound B is preferably 30 to 90 parts by mass, more preferably 40 to 80 parts by mass, and still more preferably 50 to 70 parts by mass with respect to 100 parts by mass of compound A.

From the viewpoint of normal strength, durability strength and curability of the cured product of the present invention 1,
The compound C is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, and still more preferably 0.7 to 3 parts by mass with respect to 100 parts by mass of the compound A.

From the viewpoint of improving the refractive index while suppressing the thickening of the present invention 1, and from the viewpoint of the normal strength, durability strength and curability of the cured product of the present invention 1,
In the present invention 1, the total content of Compound A, Compound B and Compound C is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass.

This invention 1 considers the suitable aspect which mentioned above the compound A, the compound B, and the compound C,
The refractive index is adjusted to 1.60 or more, preferably 1.61 or more, and more preferably 1.62 or more.

This invention 1 considers the suitable aspect which mentioned above the compound A, the compound B, and the compound C,
The viscosity is preferably adjusted to 10 to 10000 mPa · s, more preferably 20 to 5000 mPa · s, and still more preferably 50 to 4000 mPa · s.
[Invention 2]
The present invention 2 is a photocurable resin comprising a (meth) acrylate compound (hereinafter referred to as compound A ′), a metal-containing nanoparticle (hereinafter referred to as compound B ′) and a photopolymerization initiator (hereinafter referred to as compound C ′). It is a composition (hereinafter referred to as photocurable resin composition 2), and the compound A ′ contains the compound A1.

  From the viewpoint of improving the refractive index while suppressing the thickening of the present invention 2, the present invention 2 includes the above-described aspect of the present invention 1.

  In the present invention 2, when the compound A ′ is composed of a (meth) acrylate compound other than the compound A1, the viscosity of the present invention 2 can be reduced and the refractive index can be improved by including the compound A1.

  In the present invention 2, the compound A2 is preferably included as a (meth) acrylate compound other than the compound A1 in the compound A ′, and more preferably includes the compound A2 and a (meth) acrylate monomer and / or a (meth) acrylate oligomer. preferable.

In addition to the compounds A, B and C, the present invention 1 can contain other compounds as long as the effects of the present invention 1 are not impaired.
Examples of the other compound include other compounds that can be included in the present invention 1.

  In the present invention 2, the content of the compound A1 in the compound A ′ is preferably 10 to 90% by mass, more preferably 20 to 85% by mass, still more preferably 40 to 80% by mass, and further preferably 60 to It is 80 mass%, More preferably, it is 65-75 mass%.

  In the present invention 2, the compound A2 is preferably included as a (meth) acrylate compound other than the compound A1 in the compound A ′, and more preferably includes the compound A2 and a (meth) acrylate monomer and / or a (meth) acrylate oligomer. preferable.

  From the viewpoint of improving the refractive index while suppressing the thickening of the present invention 2, the compound B ′ is preferably 30 to 90 parts by mass, more preferably 40 to 80 parts by mass with respect to 100 parts by mass of the compound A ′. More preferably, it is 50-70 mass parts.

  From the viewpoint of normal strength, durability strength and curability of the cured product of the present invention 2, the compound C ′ is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 100 parts by mass of the compound A ′. -7 parts by mass, more preferably 0.7-3 parts by mass.

From the viewpoint of improving the refractive index while suppressing the thickening of the present invention 2, and from the viewpoint of normal strength, durability strength and curability of the cured product of the present invention 2,
In the present invention 1, the total content of compound A ′, compound B ′ and compound C ′ is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and still more preferably. Is 95 to 100% by mass.

In the present invention 1, in consideration of the preferred embodiments described above for Compound A ′, Compound B ′ and Compound C ′,
The refractive index is preferably adjusted to 1.60 or more, more preferably adjusted to 1.61 or more, and further preferably adjusted to 1.62 or more.

This invention 1 considers the suitable aspect which mentioned above the compound A, the compound B, and the compound C,
The viscosity is preferably adjusted to 10 to 10000 mPa · s, more preferably 20 to 5000 mPa · s, and still more preferably 50 to 4000 mPa · s.

[Invention 3]
The present invention 3 is a highly refractive resin cured product obtained by curing the present invention 1 or the present invention 2.

  In the invention 3, the refractive index is preferably adjusted to 1.64 or more, more preferably 1.65 or more in consideration of the conditions of suitable molding and curing described later in the invention 1 or the invention 2. preferable.

  The present invention 3 can be produced by molding the present invention 1 or the present invention 2 into a shape suitable for the purpose, irradiating the molded body with light and curing it by a curing reaction.

  The present invention 3 may be, for example, a one-dimensional or two-dimensional cured body such as a three-dimensional cured body, a cured film, or a cured pattern, or a dot or dot-shaped cured body.

  The molding of the present invention 1 or the present invention 2 may be performed, for example, by forming the film-like body of the present invention 1 or the present invention 2 on a base material, or filling a mold according to the application to form a three-dimensional mold. .

  Examples of the method for forming the film-like body of the present invention 1 or 2 on a substrate include, for example, a flow coating method, a spin coating method, a spray coating method, a screen printing method, a casting method, a bar coating method, and a curtain coating method. , Roll coating method, gravure coating method, dipping method, slit method and the like.

When the present invention 3 is in the form of a film or a sheet, the thickness of the present invention 3 is preferably about 0.01 μm to 10 mm, depending on the use of the cured body.
In the case of a photoresist, it is preferably 0.05 to 10 μm, more preferably 0.1 to 5 μm,
In the case of a printed wiring board, it is preferably 10 μm to 5 mm, more preferably 100 μm to 1 mm,
In the case of an optical thin film, it is preferably 0.1 to 100 μm, and more preferably 0.3 to 50 μm.

  In the case of the present invention 3 for lens use, the present invention 3 is preferably in a form in which both surfaces have a convex inclination or a form in which one surface is a convex inclination and the other surface is in close contact with a substrate such as glass. .

  The light to be irradiated or exposed may be, for example, ultraviolet light or visible light, depending on the photopolymerization initiator, but the color tone of the present invention 3 is suppressed to improve transparency, and preferably to improve colorless transparency. Therefore, ultraviolet rays are more preferable.

  From the viewpoint of improving the transparency by suppressing the fast curing and the color of the present invention 3, and preferably improving the colorless transparency, the wavelength of light is preferably 150 to 450 nm, and preferably 200 to 400 nm. More preferred is 300 to 400 nm.

From the viewpoint of sufficiently proceed the curing reaction, irradiation light amount varies depending on the thickness of the coating film is preferably 1500~10000mJ / cm ^2, more preferably 2000~9000mJ / cm ^2, 3000~9000mJ / Cm ² is more preferable, and 4000 to 7000 mJ / cm ² is more preferable.

  The light source can be selected according to the type of light beam to be exposed. For example, in the case of ultraviolet rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a deuterium lamp, a halogen lamp, laser light (helium-cadmium laser, Excimer laser etc.) can be used.

The molded invention 1 or invention 2 is heated after light irradiation or with light irradiation as necessary, but is often performed after light irradiation.
The heating temperature is preferably 60 to 250 ° C, more preferably 100 to 200 ° C,
The heating time is preferably 1 minute to 2 hours, more preferably 10 minutes to 1 hour, further preferably 20 minutes to 1 hour, and further preferably 30 minutes to 1 hour. .

  When a pattern or an image is formed (for example, when a printed wiring board is manufactured), the coating film formed on the substrate may be subjected to pattern exposure, and this pattern exposure may be performed by scanning with a laser beam. Alternatively, light irradiation may be performed through a photomask.

A pattern or an image can be formed by developing (or dissolving) a non-irradiated region (unexposed portion) generated by pattern exposure with a developer.
When the coating is heated after the exposure, the development step may be performed before the heating step or after the heating step.

  Since these methods can form a fine and high-precision pattern on a base material even with a small exposure amount, they are suitable for applications that require a precise pattern, for example, printed wiring boards for electronic devices. .

When an optical thin film is formed, a plurality of layers of the present invention 1 or the present invention 2 may be formed on a substrate.
Moreover, after forming another functional layer etc. on a base material, you may form the layer formed by this invention 1 or this invention 2 on the functional layer.

  The material of the base material is selected according to the application. For example, in the case of a printed wiring board or an optical thin film, a semiconductor such as silicon, gallium arsenide, gallium nitride, or silicon carbide, a metal such as aluminum or copper, zirconium oxide, Ceramics such as titanium oxide and PZT, transparent inorganic materials (glass, quartz, magnesium fluoride, calcium fluoride, etc.), transparent resins (polymethyl methacrylate, polymethyl acrylate, polystyrene, etc.), etc. are used.

  Since the present invention 3 can have a high refractive index of 1.6 or higher, various lenses such as a Fresnel lens, a lenticular lens, a prism lens, and a microlens, a high refractive index layer of an antireflection film such as a liquid crystal display, It is preferably used for optical applications such as optical thin films such as reflectors, optical fiber core materials, clad materials, optical waveguides, holograms, etc., and various lenses such as Fresnel lenses, lenticular lenses, prism lenses, micro lenses, etc. It is more preferable to use it.

Compound raw materials
(1) Compound A1: Compound represented by formula (1) (R ¹ is hydrogen, a = 0) (POB-A, Kyoeisha Chemical Co., Ltd.)
(2) Compound A2: benzyl acrylate (FA-BZA, Hitachi Chemical Co., Ltd.)
(3) Compound a1 (Compound A or A ′ other than Compounds A1 and A2): Ethoxy o-phenylphenol acrylate (A-LEN-10, Kyoeisha Chemical Company)
(4) Compound a2 (Compound A or A ′ other than Compounds A1 and A2): Fluorene acrylate (EA-0200, Osaka Gas Chemical Company)
(5) Compound a3 (compound A or A ′ other than compounds A1 and A2): fluorene acrylate compounded product (EA-F5710, Osaka Gas Chemical Company)
(6) Compound B or B ′: Zirconium oxide nanoparticles (average particle diameter 11 nm) 70 wt% MEK dispersion (AX-ZP-153-A, Nippon Shokubai Co., Ltd.)
(7) Compound C or C ′: 1-hydroxy-cyclohexyl-phenyl-ketone (I-184, BASF)

[Photocurable resin composition]
To obtain the composition of the photocurable resin composition shown in Table 1, Compound A, AX-ZP-153-A and Compound C were weighed so that the total mass was 100 to 300 g, and the container (material) Filled into SUS316, 700ml capacity, Three One Motor (Shinto Kagaku) at 80 ° C under atmospheric pressure

  In addition, when mix | blending AX-ZP-153-A, 1 h evaporation is performed on the conditions of 20 Torr and 60 degreeC using the evaporator (N-N, the product made by HVC-2000 EYELA) for the photocurable resin composition. Then, methyl ethyl ketone was volatilized.

  Examples 1, 2-1, 2-2 and 3 are Invention 1 and Invention 2.

[High refractive resin cured product]
The photocurable resin compositions (0.3 g) of the examples and comparative examples shown in Table 1 were applied to a PET film 1 (manufactured by Panac, product name Lumirror 100T60, thickness 100 μm) and applied. The resin composition is coated with a PET film 2 (Panac Corporation, product name Lumirror 100T60, thickness 100 μm) from the top so that the thickness of the resin composition is 0.1 mm, and the wavelength with a metal halide lamp (ECS-301, Eye Graphics Co., Ltd.). Photocured material was obtained by irradiation with 365 nm light at 6000 mJ / cm ² .

  These photocured bodies were further heat-treated in a hot air dryer at 120 ° C. for 30 minutes to obtain photocured 0.1 mm thick cured bodies.

  The highly refractive resin cured product obtained by photocuring the photocurable resin compositions of Examples 1, 2-1, 2-2 and 3 is Invention 3.

[Measurement conditions for viscosity]
About the photocurable resin composition of the Example of Table 1, and a comparative example, it measured at 25 degreeC using the E-type viscosity meter (Toki Sangyo Co., Ltd. RE-105U).

[Measurement conditions for refractive index]
The refractive index with respect to the light of wavelength 589nm in 25 degreeC of the hardening body formed by photocuring the photocurable resin composition of an Example and a comparative example, and the photocurable resin composition of an Example and a comparative example, Abbe refractive index It was measured with a total (2T: manufactured by Atago Co., Ltd.).

  Table 1 shows the results.

  In (meth) acrylates other than compounds A1 and A2, even when compound B is not included, the viscosity of the photocurable resin composition is large (Comparative Examples 3 and 4).

When containing a certain proportion of compound B,
The photocurable resin composition of Comparative Example 1-1 has a refractive index of less than 1.60,
The photocurable resin composition of Comparative Example 1-2 has a relatively large viscosity,
The photocurable resin composition of Example 1 has a refractive index of 1.60 or more, and the viscosity is suppressed to a relatively low level.

When the amount of compound B is increased with respect to Example 1 and Comparative Examples 1-1 and 1-2,
In Example 2-1, the refractive index greatly increases, but the increase in viscosity is suppressed,
In Example 2-2, the refractive index is 1.60 or more, but the increase in viscosity is suppressed.
In Comparative Example 2, an increase in viscosity is not suppressed.

Claims (2)

A photocurable resin composition comprising a (meth) acrylate compound, metal-containing nanoparticles and a photopolymerization initiator,
The (meth) acrylate compound has the following formula (1):
(In the formula (1) , R1 is a hydrogen atom or a methyl group, and a is 0 ).
In the (meth) acrylate compound, the content of the compound represented by the formula (1) is 60 to 100% by mass,
The metal-containing nanoparticles are zirconium oxide-containing nanoparticles;
A photocurable resin composition having a refractive index of 1.666 or more (provided that the photocurable resin composition is a monomer, oligomer, or prepolymer of a photocurable compound having a silicone skeleton) And at least one compound selected from the group consisting of macromonomers, and a bifunctional (meth) acrylate compound having a fluorene skeleton represented by the formula (2):
(In formula (2), R ¹ and R ² are the same or different and do not include a hydrogen atom or a methyl group, and a and b each represent an integer of 1 to 4) .   A high refractive resin cured body obtained by photocuring the photocurable resin composition according to claim 1.