JP2010242033A - Energy-curable optical material and optical element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an energy-curable optical material which contains inorganic fine particles of even low concentration but does not become clouded and in which the inorganic fine particles excellent in scattering ratio and shape stability are dispersed and to provide an optical element obtained by using the energy-curable optical material. <P>SOLUTION: The energy-curable optical material contains surface-treated inorganic fine particles, a monomer, an initiator and an additive. The content of the surface-treated inorganic fine particles is 1-10 vol.%, the additive consists of the mono-vinyl ester monomer shown by RCOOCH<SB>2</SB>=CH<SB>2</SB>(wherein R is a ≥5C organic group), and the content of the additive is 0.5-10 vol.%. The optical element is obtained by using the energy-curable optical material. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an energy curable optical material and an optical element, and more particularly to a fine particle dispersed optical material using nano-inorganic fine particles and an optical element using the same.

A method of uniformly dispersing nano-particles such as inorganic oxides in a resin is eagerly desired in various technical fields in order to exhibit a desired effect. For example, when the refractive index is controlled and used for an optical material with little light scattering at the film thickness to be used, inorganic oxide nanoparticles such as TiO ₂ , ZrO ₂ , Al ₂ O ₃ and ITO are uniformly distributed in the resin. An optical material dispersed in is desirable. In order to uniformly disperse the nanoparticles, there are mechanical mixing and dispersion using a general mixer such as a ball mill and a homogenizer, and a method of modifying the surface of the nanoparticles to prevent the dispersed particles from reaggregating. Performed in combination.

  The modification of the surface of the fine particles will be described. By modifying the surface of the fine particles, the affinity between the fine particles and the material to be dispersed and the fine particles can be increased, particularly in the case of nano fine particles. As a result, the fine particle dispersion and the dispersion material are stabilized.

  Usually, there are methods for modifying the surface of the fine particles, such as (1) chemically modifying the surface of the fine particles, and (2) adsorbing a dispersant on the surface of the fine particles. Usually, since the surface of the metal oxide fine particles is strongly hydrophilic, the surface of the fine particles is treated with a coupling agent type or organic acid type treatment agent or dispersant.

In addition, for example, Patent Document 1 and Patent Document 2 disclose that dispersion of fine particles is improved by adding a hydrophilic group such as a hydroxyl group or a carboxyl group to a dispersion polymer.
Usually, high molecular weight dispersants also have a hydrophilic group that surrounds the surface of fine particles by a similar mechanism and a non-hydrophilic group that maintains affinity with ordinary polymers. I keep it.

JP 2000-336278 A JP 2001-64439 A

  When fine particles are dispersed using a dispersant, when the concentration of the dispersant is 10 v% or more, the affinity between the monomer and the inorganic fine particles with the dispersant attached to the surface is maintained due to the influence of the excess dispersant. Inorganic fine particles exist in a uniform state in the monomer.

  However, when the affinity between the monomer and the dispersant is not completely the same, when the concentration of the inorganic fine particles to be mixed is less than 10 v%, the concentration of excess dispersant not adsorbed on the surface of the fine particles decreases. As a result, the affinity between the monomer and the inorganic fine particles having the dispersant attached to the surface is drastically reduced. As a result, the inorganic fine particles having the dispersant attached to the surface aggregate at room temperature, become non-uniform, and become cloudy. Therefore, it cannot be used as an optical material for energy curing.

  As a method for preventing the inorganic fine particles from becoming cloudy, it is possible to select a monomer having affinity for the dispersant adhering to the surface of the inorganic fine particles. However, if the monomer is changed, the physical properties such as viscoelasticity, glass transition point, transferability, and shape stability have changed greatly, making it impossible to create optical elements, or to greatly change the preparation conditions. It may be necessary.

  There is also a method of improving the problem of white turbidity of inorganic fine particles by using a dispersant having a low concentration. However, when the concentration of the dispersant increases with a low concentration of inorganic fine particles, the dispersant precipitates on the surface over time, and viscoelasticity, glass transition point, transferability, and shape stability are the same as when the previous monomer is changed. There is a possibility that the physical physical properties such as the property greatly change, making it impossible to produce the optical element, or to greatly change the production conditions.

  The present invention has been made in view of such a background art, and an energy-curing optical material in which inorganic fine particles having good scattering rate and shape stability are dispersed without causing cloudiness even when the concentration of inorganic fine particles is low, and The optical element used is provided.

An energy curable optical material that solves the above-described problem is an energy curable optical material that includes surface-treated inorganic fine particles, a monomer, an initiator, and an additive, and the content of the surface-treated inorganic fine particles is 1 v%. and not more than 10v% or less, the content of the additive RCOOCH ₂ = _{CH 2} (R is. showing a 5 or more organic groups having a carbon number) a monovinyl ester monomer represented by, and the additive is 0 It is characterized by being 5 v% or more and 10 v% or less.

  An optical element that solves the above-described problems is an optical element formed of the energy-curable optical material.

  According to the present invention, it is possible to provide an energy curable optical material in which inorganic fine particles having good scattering rate and shape stability are dispersed without causing clouding even when the concentration of inorganic fine particles is low, and an optical element using the same.

It is explanatory drawing explaining the preparation method of the sample for a scattering rate measurement in ultraviolet curable resin. It is explanatory drawing explaining the preparation method of the sample for a scattering rate measurement in ultraviolet curable resin under a heating. It is a figure which shows the scattering rate of the hardened | cured material of ultraviolet curable resin A-1 of Example 1. FIG. It is explanatory drawing explaining the preparation method of the polymer of an ultraviolet curable resin using a metal mold | die. It is a figure which shows the scattering rate of the hardened | cured material of the ultraviolet curable resin H-1 of the comparative example 1. FIG. It is a figure which shows the scattering rate of the hardened | cured material of the ultraviolet curable resin H-2 of the comparative example 2. FIG. It is a figure which shows the scattering rate of the hardened | cured material of the ultraviolet curable resin H-3 of the comparative example 3. It is a figure which shows the scattering rate of the hardened | cured material of ultraviolet curable resin A-2 of Example 2. FIG. It is a figure which shows the scattering rate of the hardened | cured material of ultraviolet curable resin A-3 of Example 3. FIG. It is a figure which shows the scattering rate of the hardened | cured material of the ultraviolet curable resin A-4 of Example 4. FIG. It is a figure which shows the scattering rate of the hardened | cured material of ultraviolet curable resin A-5 of Example 5. FIG. It is a figure which shows the scattering rate of the hardened | cured material of ultraviolet curable resin A-6 of Example 6. FIG. It is a figure which shows the scattering rate of the hardened | cured material of ultraviolet curable resin A-7 of Example 7. FIG. It is a figure which shows the scattering rate of the hardened | cured material of ultraviolet curable resin A-8 of Example 8. FIG. It is a figure which shows the scattering rate of the hardened | cured material of ultraviolet curable resin Z-1 of Example 9. FIG. FIG. 10 is a schematic diagram showing a method for producing a multilayer diffractive optical element A-1-4 in Example 10. It is a figure which shows the diffraction efficiency of multilayer diffractive optical element A-1-4 in Example 10. FIG.

Hereinafter, embodiments of the present invention will be described in detail.
The energy curable optical material according to the present invention is an energy curable optical material containing surface-treated inorganic fine particles, a monomer, an initiator, and an additive, and the content of the surface-treated inorganic fine particles is 1 v% or more and 10 v or more. %, And the additive is composed of a monovinyl ester monomer represented by RCOOCH ₂ = CH ₂ (R represents an organic group having 5 or more carbon atoms), and the content of the additive is 0.5 v. % Or more and 10 v% or less.

In the energy curable optical material of the present invention, the surface-treated inorganic fine particles are uniformly dispersed.
Examples of the inorganic fine particles used in the present invention include oxides such as Si, Ti, Zr, Al, In, and Sn. For the purpose of increasing the Abbe number and increasing the refractive index, aluminum oxide ( Al ₂ O ₃ ) and zirconia oxide (ZrO ₂ ) are preferable.

  The inorganic fine particles are surface-treated with a dispersant, and the dispersant includes a silane coupling agent, alcohols, organic carboxylic acid, etc., and has a polyester system in the main chain in consideration of stability and versatility. A dispersant is preferred.

The average particle size of the inorganic fine particles is 5 nm to 60 nm, preferably 5 nm to 30 nm.
The content of the surface-treated inorganic fine particles contained in the energy curable optical material of the present invention is 1 v% or more and 10 v% or less by volume percentage. If it is less than 1 v%, changes in optical properties and other physical properties are not clear. Further, when the amount is more than 10 v%, the ratio of the excess dispersant is increased and stable, so that it is not particularly necessary to add an additive.

Additives used in the present invention, RCOOCH ₂ = _{CH 2} (R is. Showing a 5 or more organic groups having a carbon number) monovinyl ester monomers represented by is used. The monovinyl ester monomer contains one vinyl ester (—COOCH ₂ ═CH ₂ ) group. The monovinyl ester monomer has affinity for both the surface-treated inorganic fine particles and the monomer, and uniformly disperses the inorganic fine particles.

RCOOCH 2 ₌ R in monovinyl ester monomer represented by CH ₂ linear carbon atoms of 5 or more, the branch is preferably an organic group comprising a cyclic hydrocarbon group. When R has 4 or less carbon atoms or 2 or more vinyl ester groups, the affinity for the surface-treated inorganic fine particles decreases, and the inorganic fine particles aggregate at room temperature.

  Specific examples of the monovinyl ester monomer as the additive are preferably vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl cyclohexanecarboxylate or vinyl cinnamate.

  The content of the monovinyl ester monomer contained in the energy curable optical material of the present invention is 0.5 v% to 10 v%, preferably 1 v% to 5 v% by volume. If the content of the monovinyl ester monomer is less than 0.5 v%, the affinity with the surface-treated inorganic fine particles decreases, and the inorganic fine particles aggregate at room temperature. If the content exceeds 10 v%, the inorganic fine particles do not aggregate, but the elastic modulus. Mechanical properties such as moldability and environmental durability change greatly.

  The monomer used in the present invention is not particularly limited as long as it has one or more double bonds or triple bonds in the molecule, and examples thereof include the monomers shown below. Specific examples of the monomer or oligomer of the unsaturated group-containing compound include 1,4-divinylcyclohexane, 1,4-cyclohexanedimethanol divinyl ether, 4,4-dimethyl-hept-1-ene-6-in, Divinylbenzene, 1,6-divinylnaphthalene, N-vinylpyrrolidone, N-vinylcaprolactam, ethoxylated bisphenol A divinyl ether, propoxylated bisphenol A divinyl ether, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, Monofunctional acrylates and methacrylates such as phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene di (meth) acrylate, trimethylolethanetri (meth ) Acrylate, neoventyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol di (meth) acrylate, tri (acryloyl) (Roxyethyl) isocyanurate, polyhydric alcohols such as glycerin and trimethylolethane, and then (meth) acrylate after addition of ethylene oxide or propylene oxide, Japanese Patent Publication No. 50-6034, Japanese Patent Publication No. 51-37193 Urethane acrylates as described in each publication, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, and JP-B-52-30490, Carboxymethyl resin and (meth) polyfunctional acrylates or methacrylates such as epoxy acrylates obtained by reacting an acrylic acid. A monomer can be used by 1 type (s) or 2 or more types.

  Among the above monomers, a tricyclodecane dimethanol acrylate, neopentyl glycol-modified trimethylolpropane diacrylate or dimethylol dicyclopentane has a refractive index of 1.51 or more when cured and a large Appe number. It is preferable to use diacrylate.

The content of the monomer contained in the energy curable optical material of the present invention is 80% to 98% by volume, preferably 85% to 97% by volume.
The monomer is energy-cured, but as an energy curing method, it is possible to polymerize the initiator by stimulating it with energy such as plasma treatment, heat treatment, radioactivity, and ultraviolet rays. Photocuring is preferred.

  The initiator used in the present invention is a photopolymerization initiator that can be specifically used, for example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 1-hydroxy- Cyclohexyl-phenyl-ketone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 4-phenylbenzophenone, 4-phenoxybenzophenone, 4,4′-diphenylbenzophenone, 4,4′-diphenoxybenzophenone, etc. Can be mentioned as suitable. In consideration of the transparency of the cured resin, it is preferable to use 1-hydroxy-cyclohexyl-phenyl-ketone which is cured by ultraviolet rays.

The content of the initiator contained in the energy curable optical material of the present invention is 0.1 v% or more and 10 v% or less, preferably 0.5 v% or more and 5 v% or less in volume percentage.
The optical element of the present invention comprises a cured product obtained by polymerizing the above energy curable optical material. It is possible to develop a highly efficient function by finely adjusting the optical characteristics of the energy curable optical material by a polymerization method and in the optical element.

  Examples of the optical element of the present invention include a diffractive optical element and an aspherical lens formed by replica molding.

  15.31 g of a mixture of 98 parts by weight of tricyclodecane dimethanol acrylate and 2 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone, aluminum oxide fine particle dispersion / xylene solution (15.04 w% aluminum oxide, 2.76 w% A polyester-based dispersant was used as a dispersant and a dispersant.) 22.70 g was mixed. Then, after removing xylene with an evaporator, 0.64 g of vinyl caprate was mixed to obtain an optical material made of an ultraviolet curable resin A-1 in which 17.08 w% of aluminum oxide was dispersed. Table 3 shows the weight percentage (wt%) and the volume percentage (Vol%) of sample (ultraviolet curable resin) A-1.

  The particle size distribution in the aluminum oxide fine particle dispersion / xylene solution (15.04 w% aluminum oxide, 2.76 w% dispersant) was measured with a particle size distribution meter (DT-1200: manufactured by Dispersion Technology). The average particle size was 25 nm.

<Verification of stability>
As shown in FIG. 1, the ultraviolet curable resin A-1 was sandwiched between two substrates 1 and 2 made of a glass (BK7) flat plate having a thickness of 1 mm at room temperature. The surface of one substrate 1 is subjected to a coupling process 4. The ultraviolet curable resin A-1 was irradiated with ultraviolet rays 50 J / cm ² through the substrate 1 to be cured, and released from the ultraviolet curable resin film 6 to prepare an ultraviolet cured sample. The measurement sample is designated as A-1-1.

As shown in FIG. 2, the ultraviolet curable resin A-1 is sandwiched between two substrates 1 and 2 made of glass (BK7) flat plates having a thickness of 1 mm at room temperature, and the ultraviolet curable resin A-1 is placed at 50 ° C. Heated to. The surface of one substrate 1 is subjected to a coupling process 4. The other substrate 2 is heated by a hot plate 13 and adjusted to 50 ° C. The ultraviolet curable resin A-1 was irradiated with ultraviolet rays 50 J / cm ² through the substrate 1 and cured, and then released to prepare an ultraviolet curable sample composed of the ultraviolet curable resin film 16. Let the sample be A-1-2.

  The scattering rates of samples A-1-1 and A-1-2 were measured with a spectrophotometer U4000 (Hitachi). In the measurement method, the sample was attached to the incident light portion of the integrating sphere, and the back of the integrating sphere was removed to allow the transmitted light to pass through and only the scattered light was measured. The measurement conditions are that the wavelength of incident light is 400 to 700 nm, and the thickness of the sample is 10 to 20 μm (after measuring the scattering rate, the film thickness is measured). The measurement results are shown in FIG.

In addition, since the film thicknesses of the measurement samples are slightly different, the film thickness was converted to a film thickness of 10 μm and compared by the following formula (1).
Scattering rate (10 μm) = (measured scattering rate / sample film thickness μm) × 10 μm (1)
The scattering rate was 1.2% at a measurement wavelength of 400 nm, and almost no difference was observed between the measurement samples A-1-1 and A-1-2.
Table 2 shows the scattering rate of the measurement sample A-1-1.

<Refractive index>
The refractive index (ng, nF, ne, nd, nC) was measured with a refractometer KPR-20V (manufactured by Shimadzu Device Manufacturing Co., Ltd.). Thereby, dispersion (νd = (nd−1) / (nF−nC)) was calculated. The results are shown in Table 1. The refractive index (ng, nF, ne, nd, nC = 1.5508, 1.5451, 1.5405, 1.5381, 1.5351) and the Abbe number (νd = 53.37).

<Shape stability (surface distortion)>
As shown in FIG. 4, the ultraviolet curable resin A-1 was sandwiched between two substrates 1 and 21 made of a glass (BK7) flat plate having a thickness of 1 mm at room temperature. The surface of one substrate 1 is subjected to a coupling process 4. The other substrate 21 is formed in a 15 μm lattice shape. The ultraviolet curable resin A-1 was irradiated with ultraviolet rays 50 J / cm ² through the substrate 1 to be cured, and then released to prepare an ultraviolet cured 15 μm lattice-shaped sample comprising the ultraviolet curable resin film 26. The transferability of the sample was measured with New view 5000 (manufactured by zygo).
The results are shown in Table 2 as “surface distortion”. The shape transferability of the molding surface is good, and the shape deformation is 20 nm or less.

Comparative Example 1
15.95 g of a mixture of 98 parts by weight of tricyclodecane dimethanol acrylate and 2 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone and aluminum oxide fine particle dispersion / xylene solution (15.04 w% aluminum oxide, 2.76 w% dispersion) Agent) After mixing with 22.70 g, xylene was removed by an evaporator to obtain an optical material composed of an ultraviolet curable resin H-1 in which 17.08 w% (5.41 v%) of aluminum oxide was dispersed.
Unlike Example 1, the vinyl caprate additive was not added.

<Verification of stability>
A sample obtained by curing the ultraviolet curable resin H-1 at room temperature by the same method as that shown in FIG. The measurement sample is designated as H-1-1.
The ultraviolet curable resin H-1 was heated to 50 ° C., and an ultraviolet cured sample was prepared in the same manner as the method shown in FIG. The measurement sample is designated as H-1-2.

The scattering rates of the measurement samples H-1-1 and H-1-2 were measured with a spectrophotometer U4000. The result is shown in FIG. Since the film thickness of the measurement sample is slightly different, the film thickness was converted into a film thickness of 10 μm using the formula (1) and compared.
The scattering rate of H-1-1 was 4% at a measurement wavelength of 400 nm, and the scattering rate of H-1-2 was 1.5%. In Sample H-1-1 molded at room temperature, fine particles aggregate and the scattering rate is large.

<Measurement of refractive index>
The refractive index (ng, nF, ne, nd, nC) was measured with a refractometer. At this time, since the sample of H-1-1 was highly scattered and could not be measured, measurement was performed with H-1-2. The results are shown in Table 1. The refractive index (ng, nF, ne, nd, nC = 1.5519, 1.5463, 1.5416, 1.5392, 1.5362) and the Abbe number (νd = 53.22).

<Shape stability (surface distortion)>
As shown in FIG. 4, it was molded in a 15 μm lattice shape, and its transferability was measured with New view 5000 (manufactured by zygo). The results are shown in Table 2. The shape transferability of the molding surface is good, and the shape deformation (surface distortion) is 20 nm or less.

Comparative Example 2
11.95 g of a mixture of 98 parts by weight of tricyclodecane dimethanol acrylate and 2 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone and aluminum oxide fine particle dispersion / xylene solution (15.04 w% aluminum oxide, 2.76 w% dispersion) Agent) After mixing 22.70 g, after removing xylene with an evaporator, 4.00 g of vinyl caprate is mixed, and from UV curable resin H-2 in which 17.08 w% (5.42 v%) of aluminum oxide is dispersed. An optical material was obtained.

  Unlike Example 1, the monovinyl ester monomer as an additive is vinyl caprate, and the content in the resin is 10 v% or more.

<Verification of stability>
A sample obtained by curing the ultraviolet curable resin H-2 at room temperature by the same method as that shown in FIG. The measurement sample is designated as H-2-1.
The ultraviolet curable resin H-2 was heated to 50 ° C., and an ultraviolet cured sample was prepared by the same method as that shown in FIG. The measurement sample is designated as H-2-2.

The scattering rate of the measurement samples H-2-1 and H-2-2 was measured with a spectrophotometer U4000. The result is shown in FIG. Since the film thickness of the measurement sample is slightly different, the film thickness was converted into a film thickness of 10 μm using the formula (1) and compared.
The scattering rate is 1.3% at a measurement wavelength of 400 nm, and there is almost no difference between the measurement samples H-2-1 and H-2-2.

<Measurement of refractive index>
The refractive index (ng, nF, ne, nd, nC) was measured with a refractometer. The results are shown in Table 1. The refractive index (ng, nF, ne, nd, nC = 1.5446, 1.5391, 1.5346, 1.5322, 1.5293) and the Abbe number (νd = 54.16).

<Shape stability (surface distortion)>
As shown in FIG. 4, it was molded in a 15 μm lattice shape, and its transferability was measured with New view 5000 (manufactured by zygo). The results are shown in Table 2. The shape transferability of the molding surface is poor, and the shape deformation (surface distortion) is 100 nm or more.

Comparative Example 3
15.31 g of a mixture of 98 parts by weight of tricyclodecane dimethanol acrylate and 2 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone and aluminum oxide fine particle dispersion / xylene solution (15.04 w% aluminum oxide, 2.76 w% dispersion) Agent) After mixing 22.70 g, after removing xylene with an evaporator, unlike Example 1, 0.64 g of divinyl adipate having a carbon chain R other than ester group and vinyl group of 4 was mixed; An optical material made of an ultraviolet curable resin H-3 in which 08 w% (5.42 v%) aluminum oxide was dispersed was obtained.

<Verification of stability>
A sample obtained by curing the ultraviolet curable resin H-3 at room temperature by the same method as that shown in FIG. The measurement sample is designated as H-3-1.
The ultraviolet curable resin H-3 was heated to 50 ° C., and an ultraviolet cured sample was prepared by the same method as that shown in FIG. The measurement sample is designated as H-3-2.

  The scattering rates of the measurement samples H-3-1 and H-3-2 were measured with a spectrophotometer U4000. The result is shown in FIG. Since the film thickness of the measurement sample is slightly different, the film thickness was converted into a film thickness of 10 μm using the formula (1) and compared.

  The scattering rate of Sample H-3-1 was 4.7% at a measurement wavelength of 400 nm, and the scattering rate of Sample H-3-2 was 1.5%. In Sample H-3-1 molded at room temperature, fine particles aggregate and the scattering rate is large.

<Measurement of refractive index>
The refractive index (ng, F, ne, nd, nC) was measured with a refractometer. At this time, since Sample H-3-1 was not able to be measured due to large scattering, measurement was performed using Sample H-3-2. The results are shown in Table 1. The refractive index (ng, nF, ne, nd, nC = 1.5508, 1.5451, 1.5405, 1.5381, 1.5351) and the Abbe number (νd = 53.37). .

<Shape stability (surface distortion)>
As shown in FIG. 4, it was molded in a 15 μm lattice shape, and its transferability was measured with New view 5000 (manufactured by zygo). The results are shown in Table 2. The shape transferability of the molding surface is good, and the shape deformation (surface distortion) is 20 nm or less.

  15.31 g of a mixture of 98 parts by weight of neopentyl glycol-modified trimethylolpropane diacrylate and 2 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone, aluminum oxide fine particle dispersion / xylene solution (15.04 w% aluminum oxide, 2 .76w% dispersant) After mixing with 22.70g, after removing xylene with an evaporator, 0.64g vinyl caprate is mixed and 17.08w% (5.42v%) aluminum oxide dispersed in UV curable resin An optical material consisting of A-2 was obtained.

<Verification of stability>
A sample obtained by ultraviolet-curing the ultraviolet-curing resin A-2 at room temperature by the same method as that shown in FIG. The measurement sample is designated as A-2-1.
The ultraviolet curable resin A-2 was heated to 50 ° C., and an ultraviolet cured sample was prepared in the same manner as the method shown in FIG. The measurement sample is designated as A-2-2.

The scattering rates of the measurement samples A-1-1 and A-1-2 were measured with a spectrophotometer U4000. The result is shown in FIG.
Since the film thickness of the measurement sample is slightly different, the film thickness was converted into a film thickness of 10 μm using the formula (1) and compared. The scattering rate is 1.4% at a measurement wavelength of 400 nm, and there is almost no difference between the measurement samples A-2-1 and A-2-2.

<Measurement of refractive index>
The refractive index (ng, F, ne, nd, nC) was measured with a refractometer. The results are shown in Table 1. The refractive index (ng, nF, ne, nd, nC = 1.5495, 1.5438, 1.5392, 1.5368, 1.5338) and the Abbe number (νd = 53.24).

<Shape stability (surface distortion)>
As shown in FIG. 4, it was molded in a 15 μm lattice shape, and its transferability was measured with New view 5000 (manufactured by zygo). The results are shown in Table 2. The shape transferability of the molding surface is good, and the shape deformation (surface distortion) is 20 nm.

  15.31 g of a mixture of 98 parts by weight of dimethylol dicyclopentane diacrylate and 2 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone, aluminum oxide fine particle dispersion / xylene solution (15.04 w% aluminum oxide, 2.76 w % Dispersant) 22.70 g was mixed, xylene was removed by an evaporator, 0.64 g of vinyl caprate was mixed, and 17.08 w% (5.40 v%) aluminum oxide was dispersed in UV curable resin A An optical material consisting of -3 was obtained.

<Verification of stability>
A sample obtained by ultraviolet-curing the ultraviolet-curing resin A-3 at room temperature by the same method as that shown in FIG. The measurement sample is designated as A-3-1.
The ultraviolet curable resin A-3 was heated to 50 ° C., and an ultraviolet curable sample was prepared by the same method as that shown in FIG. The measurement sample is designated as A-3-2.

The scattering rates of the measurement samples A-3-1 and A-3-2 were measured with a spectrophotometer U4000. The result is shown in FIG. Since the film thickness of the measurement sample is slightly different, the film thickness was converted into a film thickness of 10 μm using the formula (1) and compared.
The scattering rate is 1.4% at a measurement wavelength of 400 nm, and there is almost no difference between the measurement samples A-3-1 and A-3-2.

<Measurement of refractive index>
The refractive index (ng, nF, ne, nd, nC) was measured with a refractometer. The results are shown in Table 1. The refractive index (ng, nF, ne, nd, nC = 1.5493, 1.5435, 1.5390, 1.5367, 1.5337) and the Abbe number (νd = 54.64).

<Shape stability (surface distortion)>
As shown in FIG. 4, it was molded in a 15 μm lattice shape, and its transferability was measured with New view 5000 (manufactured by zygo). The results are shown in Table 2. The shape transferability of the molding surface is good, and the shape deformation (surface distortion) is 23 nm.

  15.31 g of a mixture of 98 parts by weight of tricyclodecane dimethanol acrylate and 2 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone, aluminum oxide fine particle dispersion / xylene solution (15.04 w% aluminum oxide, 2.76 w% Dispersant) After mixing 22.70 g, after removing xylene with an evaporator, 0.64 g of vinyl caproate was mixed, and UV curing resin A- in which 17.08 w% (5.42 v%) aluminum oxide was dispersed was dispersed. An optical material consisting of 4 was obtained.

<Verification of stability>
A sample obtained by curing the ultraviolet curable resin A-4 at room temperature by the same method as that shown in FIG. The measurement sample is designated as A-4-1.
The ultraviolet curable resin A-4 was heated to 50 ° C., and an ultraviolet cured sample was prepared by the same method as that shown in FIG. The measurement sample is designated as A-4-2.

The scattering rates of the measurement samples A-4-1 and A-4-2 were measured with a spectrophotometer U4000. The result is shown in FIG. Since the film thickness of the measurement sample is slightly different, the film thickness was converted into a film thickness of 10 μm using the formula (1) and compared.
The scattering rate is 1.3% at a measurement wavelength of 400 nm, and there is almost no difference between the measurement samples A-4-1 and A-4-2.

<Measurement of refractive index>
The refractive index (ng, nF, ne, nd, nC) was measured with a refractometer. The results are shown in Table 1. The refractive index (ng, nF, ne, nd, nC = 1.5111, 1.5453, 1.5408, 1.5385, 1.5353) and the Abbe number (νd = 53.41).

<Shape stability (surface distortion)>
As shown in FIG. 4, it was molded in a 15 μm lattice shape, and its transferability was measured with New view 5000 (manufactured by zygo). The results are shown in Table 2. The shape transferability of the molding surface is good, and the shape deformation (surface distortion) is 21 nm.

  15.31 g of a mixture of 98 parts by weight of tricyclodecane dimethanol acrylate and 2 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone, aluminum oxide fine particle dispersion / xylene solution (15.04 w% aluminum oxide, 2.76 w% Dispersant) After mixing 22.70 g, xylene was removed by an evaporator, 0.64 g of vinyl caprylate was mixed, and UV curing resin A- in which 17.08 w% (5.42 v%) aluminum oxide was dispersed was dispersed. An optical material consisting of 5 was obtained.

<Verification of stability>
A sample obtained by UV-curing the UV-curable resin A-5 at room temperature was prepared in the same manner as the method shown in FIG. The measurement sample is designated as A-5-1.
The ultraviolet curable resin A-5 was heated to 50 ° C., and an ultraviolet cured sample was prepared by the same method as that shown in FIG. The measurement sample is designated as A-5-2.

The scattering rate of the measurement samples A-5-1 and A-5-2 was measured with a spectrophotometer U4000. The result is shown in FIG. Since the film thickness of the measurement sample is slightly different, the film thickness was converted into a film thickness of 10 μm using the formula (1) and compared.
The scattering rate is 1.4% at a measurement wavelength of 400 nm, and there is almost no difference between the measurement samples A-5-1 and A-5-2.

<Measurement of refractive index>
The refractive index (ng, nF, ne, nd, nC) was measured with a refractometer. The results are shown in Table 1. The refractive index (ng, nF, ne, nd, nC = 1.506, 1.5450, 1.5404, 1.5380, 1.5348) and the Abbe number (νd = 52.58).

<Shape stability (surface distortion)>
As shown in FIG. 4, it was molded in a 15 μm lattice shape, and its transferability was measured with New view 5000 (manufactured by zygo). The results are shown in Table 2. The shape transferability of the molding surface is good, and the shape deformation (surface distortion) is 23 nm.

  15.31 g of a mixture of 98 parts by weight of tricyclodecane dimethanol acrylate and 2 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone, aluminum oxide fine particle dispersion / xylene solution (15.04 w% aluminum oxide, 2.76 w% Dispersant) After mixing 22.70 g, after removing xylene by an evaporator, 0.64 g of vinyl laurate was mixed, and UV curing resin A- in which 17.08 w% (5.42 v%) aluminum oxide was dispersed was dispersed. An optical material consisting of 6 was obtained.

<Verification of stability>
A sample obtained by UV-curing the UV-curable resin A-6 at room temperature was prepared in the same manner as the method shown in FIG. The measurement sample is designated as A-6-1.
The ultraviolet curable resin A-6 was heated to 50 ° C., and an ultraviolet curable sample was prepared by the same method as that shown in FIG. The measurement sample is designated as A-6-2.

The scattering rate of the measurement samples A-6-1 and A-6-2 was measured with a spectrophotometer U4000. The result is shown in FIG. Since the film thickness of the measurement sample is slightly different, the film thickness was converted into a film thickness of 10 μm using the formula (1) and compared.
The scattering rate is 1.3% at a measurement wavelength of 400 nm, and there is almost no difference between the measurement samples A-6-1 and A-6-2.

<Measurement of refractive index>
The refractive index (ng, nF, ne, nd, nC) was measured with a refractometer. The results are shown in Table 1. The refractive index (ng, nF, ne, nd, nC = 1.5044, 1.5446, 1.5401, 1.5378, 1.5346) and the Abbe number (νd = 53.34).

<Shape stability (surface distortion)>
As shown in FIG. 4, it was molded in a 15 μm lattice shape, and its transferability was measured with New view 5000 (manufactured by zygo). The results are shown in Table 2. The shape transferability of the molding surface is good, and the shape deformation (surface distortion) is 25 nm.

  15.31 g of a mixture of 98 parts by weight of tricyclodecane dimethanol acrylate and 2 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone, aluminum oxide fine particle dispersion / xylene solution (15.04 w% aluminum oxide, 2.76 w% Dispersant) After mixing 22.70 g, after removing xylene with an evaporator, 0.64 g of vinylcyclohexanecarboxylate was mixed, and UV curing resin A in which 17.08 w% (5.42 v%) aluminum oxide was dispersed An optical material consisting of -7 was obtained.

<Verification of stability>
A sample obtained by ultraviolet-curing the ultraviolet-curing resin A-7 at room temperature by the same method as shown in FIG. The measurement sample is designated as A-7-1.
The ultraviolet curable resin A-7 was heated to 50 ° C., and an ultraviolet cured sample was prepared by the same method as that shown in FIG. The measurement sample is A-7-2.

The scattering rate of the measurement samples A-7-1 and A-7-2 was measured with a spectrophotometer U4000. The result is shown in FIG. Since the film thickness of the measurement sample is slightly different, the film thickness was converted into a film thickness of 10 μm using the formula (1) and compared.
The scattering rate is 1.2% at a measurement wavelength of 400 nm, and there is almost no difference between the measurement samples A-7-1 and A-7-2.

<Measurement of refractive index>
The refractive index (ng, nF, ne, nd, nC) was measured with a refractometer. The results are shown in Table 1. The refractive index (ng, nF, ne, nd, nC = 1.5510, 1.5454, 1.5407, 1.5383, 1.5352) and the Abbe number (νd = 53.12).

<Shape stability (surface distortion)>
As shown in FIG. 4, it was molded in a 15 μm lattice shape, and its transferability was measured with New view 5000 (manufactured by zygo). The results are shown in Table 2. The shape transferability of the molding surface is good, and the shape deformation (surface distortion) is 20 nm.

  15.31 g of a mixture of 98 parts by weight of tricyclodecane dimethanol acrylate and 2 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone, aluminum oxide fine particle dispersion / xylene solution (15.04 w% aluminum oxide, 2.76 w% Dispersant) After mixing 22.70 g, after removing xylene with an evaporator, 0.64 g of vinyl cinnamate was mixed, and UV curing resin A- in which 17.08 w% (5.42 v%) of aluminum oxide was dispersed was dispersed. An optical material consisting of 8 was obtained.

<Verification of stability>
A sample obtained by curing the ultraviolet curable resin A-8 at room temperature by the same method as that shown in FIG. The measurement sample is designated as A-8-1.
The ultraviolet curable resin A-8 was heated to 50 ° C., and an ultraviolet cured sample was prepared by the same method as that shown in FIG. The measurement sample is A-8-2.

The scattering rates of the measurement samples A-8-1 and A-8-2 were measured with a spectrophotometer U4000. The result is shown in FIG. Since the film thickness of the measurement sample is slightly different, the film thickness was converted into a film thickness of 10 μm using the formula (1) and compared.
The scattering rate is 1.3% at a measurement wavelength of 400 nm, and there is almost no difference between the measurement samples A-8-1 and A-8-2.

<Measurement of refractive index>
The refractive index (ng, nF, ne, nd, nC) was measured with a refractometer. The results are shown in Table 1. The refractive index (ng, nF, ne, nd, nC = 1.5523, 1.5465, 1.5421, 1.5396, 1.5365) and the Abbe number (νd = 53.52).

<Shape stability (surface distortion)>
As shown in FIG. 4, it was molded in a 15 μm lattice shape, and its transferability was measured with New view 5000 (manufactured by zygo). The results are shown in Table 2. The shape transferability of the molding surface is good, and the shape deformation (surface distortion) is 15 nm.

  15.31 g of a mixture of 98 parts by weight of tricyclodecane dimethanol acrylate and 2 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone, zirconia oxide fine particle dispersion / xylene solution (15.00 w% zirconia oxide, 1.83 w%) (Dispersant) After mixing 34.38 g, xylene was removed by an evaporator, then 0.64 g of vinyl caprate was mixed, and UV curable resin Z- in which 23.70 w% (5.43 v%) of zirconia oxide was dispersed was dispersed. An optical material consisting of 1 was obtained.

  The particle size distribution in the zirconia oxide fine particle dispersion / xylene solution (15.04 w% aluminum oxide, 2.76 w% dispersant) was measured with a particle size distribution meter (DT-1200: manufactured by Dispersion Technology). The average particle size was 27 nm.

<Verification of stability>
A sample obtained by ultraviolet-curing the ultraviolet-curing resin Z-1 at room temperature by the same method as that shown in FIG. Let the measurement sample be Z-1-1.
The ultraviolet curable resin Z-1 was heated to 50 ° C., and an ultraviolet cured sample was prepared in the same manner as the method shown in FIG. Let the measurement sample be Z-1-2.

The scattering rate of the measurement samples Z-1-1 and Z-1-2 was measured with a spectrophotometer U4000. The result is shown in FIG. Since the film thickness of the measurement sample is slightly different, the film thickness was converted into a film thickness of 10 μm using the formula (1) and compared.
The scattering rate is 2.6% at a measurement wavelength of 400 nm, and there is almost no difference between the measurement samples Z-1-1 and Z-1-2.

<Measurement of refractive index>
The refractive index (ng, nF, ne, nd, nC) was measured with a refractometer. The results are shown in Table 1. The refractive index (ng, nF, ne, nd, nC = 1.5630, 1.5570, 1.5518, 1.5492, 1.5460) and the Abbe number (νd = 50.31).

<Shape stability (surface distortion)>
As shown in FIG. 4, it was molded in a 15 μm lattice shape, and its transferability was measured with New view 5000 (manufactured by zygo). The results are shown in Table 2. The shape transferability of the molding surface is good, and the shape deformation (surface distortion) is 15 nm.

The ultraviolet curable resin A-1 of Example 1 was formed into a lattice shape having a lattice height (step) of 11.8 μm by the method shown in FIG. This lattice-shaped sample is designated as A-1-3.
As shown in FIG. 16, 11.7 v% ITO nanoparticles are added to a fluorine-based monomer on a lattice-shaped sample A-1-3 of a substrate 33 on which a lattice-shaped sample A-1-3 (reference numeral 32) is formed. A dispersed material (refractive index after curing nd = 1.4886, νd = 20.17, θgF = 0.41) 31 is dropped, and a glass substrate 30 having a surface subjected to coupling treatment 4 is formed thereon. Placed. The fluorine-based monomer material 31 was irradiated with ultraviolet rays 50 J / cm ² through the substrate 30 and cured to produce a multilayer diffractive optical element A-1-4 (reference numeral 34).

  In FIG. 17, the diffraction efficiency of the multilayer diffractive optical element A-1-4 is calculated by comparing the diffracted light of the designed order of the element with the transmittance of the element (without the diffraction grating) having the same resin thickness as the element. Show. It can be seen that the diffraction efficiency is 99.8% or more in the visible region.

  Since the energy curable optical material of the present invention has good scattering rate and shape stability, it can be used for optical elements such as diffractive optical elements and replica-molded aspherical lenses.

1, 2 Substrate 3 UV curable resin 4 Coupling treatment 6, 16, 26 UV resin cured film 13 Hot plate 21 Substrate 23 Mold 30, 33 Substrate 31 11.7v% ITO nano-particle dispersed fluorine monomer material 32 Grid shape sample A -1-3
34 Multilayer diffractive optical element A-1-4

Claims (8)

An energy curable optical material containing surface-treated inorganic fine particles, a monomer, an initiator and an additive, wherein the content of the surface-treated inorganic fine particles is 1 v% or more and 10 v% or less, and the additive is RCOOCH ₂ = CH ₂ (R represents an organic group having 5 or more carbon atoms), and the additive content is 0.5 v% or more and 10 v% or less. An energy curable optical material characterized.   The energy-curable optical material according to claim 1, wherein the inorganic fine particles are aluminum oxide or zirconia oxide.   3. The energy curable optical material according to claim 1, wherein the surface treatment of the inorganic fine particles is performed with a polyester-based dispersant.   The energy curable optical material according to any one of claims 1 to 3, wherein the inorganic fine particles have an average particle size of 5 nm to 60 nm.   5. The energy curing according to claim 1, wherein the monomer is tricyclodecane dimethanol acrylate, neopentyl glycol-modified trimethylol propane diacrylate, or dimethylol dicyclopentane diacrylate. Optical material.   6. The energy curable optical material according to claim 1, wherein the initiator is 1-hydroxy-cyclohexyl-phenyl-ketone.   The energy according to any one of claims 1 to 6, wherein the additive is vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl cyclohexanecarboxylate or vinyl cinnamate. Curing optical material.   An optical element formed by the energy curable optical material according to claim 1.

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