JP2009249591A - Optical material composition and optical element using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical material composition which has moderate abnormal dispersibility and, at the same time, is easily worked, and to provide an optical element. <P>SOLUTION: The optical material composition comprises: fine particles (A) of antimony oxide (III) of 5 mass% to 50 mass%; an organic compound (B) having at least one polymerizable functional group in a molecule, of 49 mass% to 94 mass%; and a polymerization initiator (C) of 0.05 mass% to 5 mass%. The optical element using the optical material composition is also provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to an optical material composition suitable for forming an optical element and an optical element using the cured product thereof, and in particular, a material composition having an anomalous dispersion and a cured product of the material composition. The present invention relates to an optical lens made of an object.

  In recent years, downsizing and high performance of optical systems used in cameras, video cameras, camera-equipped mobile phones, videophones and other imaging modules have become major issues. Therefore, in order to correct various aberrations in these optical systems, aspherical lenses and lenses made of anomalous dispersion glass have been frequently used. Anomalous dispersion glass is used for reducing chromatic aberration, particularly for correcting secondary spectra. An optical material having anomalous dispersion is a very useful optical material because the optical system of an optical apparatus can be reduced in size and performance.

Conventionally, the abnormal as a dispersion glass, fluorophosphate _{phosphate, B 2 O 3 -Al 2 O} 3 -PbO _{based, SiO 2 - B 2 O 3} -ZrO 2 -Nb 2 and O ₅ based optical glass such as is known Yes. Grinding and polishing are required to use these anomalous dispersion glasses as optical elements such as lenses.
In recent years, anomalous dispersion glass having a low melting point has been developed, and it has become possible to obtain an optical element by press molding at a high temperature. In addition, an optical material having anomalous dispersibility in which TiO ₂ that is inorganic oxide nanoparticles is dispersed in an ultraviolet curable resin or N-polyvinylcarbazole has been proposed. (For example, Patent Document 1)

In addition, conventional anomalous dispersion glass requires grinding and polishing in order to obtain an optical element having a desired shape, and it takes time to process. There was a problem in workability such as discoloration of the surface.
On the other hand, anomalous dispersion glass having a low melting point capable of being press-molded at a high temperature sometimes causes devitrification and dust during molding at a high temperature. Further, in the optical material proposed in Patent Document 1, the anomalous dispersion is so large that it is likely to be excessively corrected in the optical system, and the place where it can be effectively applied is limited, and the resin and inorganic oxide used There was a problem that the nano-particles were highly colored and the transparency was poor.
JP 2006-145823 A

  It is an object of the present invention to provide an optical material composition and an optical element that have appropriate anomalous dispersibility and are easy to process. It is an object of the present invention to provide an optical material composition having good properties and an optical element using the cured product thereof.

The present invention relates to an antimony (III) oxide fine particle (A) 5 mass% to 50 mass% and an organic compound (B) 49 mass% to 94 mass% having one or more polymerizable functional groups in one molecule. And a polymerization initiator (C) that is 0.05% by mass or more and 5% by mass or less.
In a cured product of a material composition comprising antimony (III) oxide fine particles (A), an organic compound (B) having one or more polymerizable functional groups in one molecule, and a polymerization initiator (C) , D-line refractive index nd, Abbe number νd, a material composition that satisfies the following conditions: 15 ≦ νd ≦ 60 and 1.45 ≦ nd ≦ 1.70.
In a cured product of antimony (III) oxide fine particles (A), an organic compound (B) having one or more polymerizable functional groups in one molecule, and a material composition which is a polymerization initiator (C), A material composition satisfying the conditions of 15 ≦ νd ≦ 60 and −0.015 ≦ ΔθgF ≦ 0.075, where Abbe number νd, F-line and g-line anomalous dispersion ΔθgF.

The organic compound (B) is the material composition having at least one functional group selected from a vinyl group, an acryloyl group, a methacryloyl group, an isocyanate group, an epoxy group, and an oxetane group.
The organic compound (B) is composed of an organic compound (B1) having one polymerizable functional group in one molecule and an organic compound (B2) having two or more material functional groups in one molecule, and the mass ratio (B1 ) / (B2) is the material composition that satisfies the condition of 0.10 to 100.
The organic compound (B) is the above-described material composition containing at least one compound having at least one functional group selected from an aromatic ring, a condensed polycycle, a carbazole ring, and a fluorene ring.

Antimony (III) oxide fine particles (A) 5 mass% or more and 50 mass% or less, organic compound (B) having one or more material functional groups in one molecule 49 mass% or more and 94 mass% or less, polymerization initiation Agent (C) is an optical element comprising a cured product of a material composition that is 0.05% by mass or more and 5% by mass or less.
Further, it comprises a cured product of a material composition having antimony (III) oxide fine particles (A), an organic compound (B) having one or more polymerizable functional groups in one molecule, and a polymerization initiator (C). The optical element satisfies the following conditions: 15 ≦ νd ≦ 60 and −0.015 ≦ ΔθgF ≦ 0.075, where Abbe number νd of the cured product and anomalous dispersion ΔθgF of the F-line and g-line.
In the above optical element, the optical element is a composite optical element in which a cured product of an optical material composition is laminated on the surface of an optical substrate by a photocuring reaction.

  The cured product obtained by curing the optical material composition of the present invention has a suitable anomalous dispersion required for an optical element, and is a molded product obtained by filling a mold with a material composition and polymerizing the mold. Alternatively, an optical element formed on the surface of another optical substrate by a photocuring reaction can be provided.

  The present invention focuses on antimony (III) oxide having a low refractive index and low anomalous dispersion among metal oxides, and by using a specific polymerizable compound together with antimony (III) oxide fine particles, It has been found that an optical element obtained by curing has appropriate anomalous dispersibility and good workability.

As the antimony (III) oxide fine particles, those produced by polymerizing an antimony alkoxide represented by the following chemical formula 1 or a hydrolyzate thereof can be used.
Chemical formula 1 R ¹ _a Sb (OR ² ) _3-a
Where R ¹ is an organic group, an alkyl group, a halogenated alkyl group, an aryl group, a halogenated aryl group, or a cycloalkyl group, R 2 is an alkyl group or aryl group having 1 to 6 carbon atoms, and a is 0 or 1 is there.

Here, examples of the alkyl group for R ¹ include a methyl group, an ethyl group, an isopropyl group, a normal butyl group, and an isobutyl group. Examples of the halogenated alkyl group include a trichloromethyl group, a trifluoromethyl group, and a pentachloroethyl group. Examples of the aryl group include a phenyl group and a styryl group. A methyl group and a phenyl group are preferable. Examples of the alkyl group or aryl group for R ² include a methyl group, an ethyl group, an isopropyl group, a normal butyl group, an isobutyl group, and a phenyl group.
a is 0 or 1; More preferably, a = 0 which exhibits the characteristics of antimony (III) oxide efficiently.

In the case of using fine particles produced from antimony alkoxide, molecular weight related to particle diameter, refractive index and dispersion can be adjusted by appropriately adjusting the type, amount, reaction temperature and time of the diluent solvent or catalyst in the condensation polymerization reaction of antimony alkoxide. The crystallinity and density involved can be adjusted.
Alternatively, a metal alkoxide other than antimony and a halide may be added and polymerized to form an antimony (III) oxide composite compound containing antimony (III) oxide as a main component.

Antimony (III) oxide particles can be prepared by reacting antimony (III) oxide with an alkali, dissolving it by adding hydrogen peroxide, and then adding an acid, in addition to the method of producing it by hydrolysis of antimony alkoxide. It can manufacture by the method of manufacturing in a liquid phase, such as a gas phase method using plasma, arc, or the like, or a pulverizing method of pulverizing large particles in a solid phase.
The antimony (III) oxide fine particles are preferably blended in the material composition after the surface is treated with a silane coupling agent such as methacrylpropyltrimethoxysilane in a state of being dispersed in the liquid.

  The blending amount of antimony (III) oxide is preferably 5% by mass or more and 50% by mass or less in the optical material composition. If the amount is less than 5% by mass, a material composition having a sufficient Abbe number and anomalous dispersion cannot be obtained. If the amount exceeds 50% by mass, the fluidity of the material composition is lost, and the processing of the optical element becomes difficult. .

  Further, the size (primary particle size) of the fine particles of the antimony oxide compound (A) is preferably an average particle size of 20 nm or less and a 90% particle size of 30 nm or less. More preferably, the average particle size is 15 nm or less and the 90% particle size is 20 nm or less. Here, the particle diameter is determined by a dynamic light scattering method. The average particle diameter is a central value of the particle diameter distribution, and the 90% particle diameter is a particle diameter in a range including 90% of all particles. To tell. If it is larger than any particle size, the transmittance and light scattering become large. That is, even if the average particle size is 20 nm or less, light scattering increases if particles having a wide particle size distribution and a particle size larger than 30 nm are present in excess of 10% of the total particles. become.

  The polymerizable functional group in the organic compound (B) may be a functional group that polymerizes to form a cured product. A vinyl group, an acryloyl group, a methacryloyl group, an isocyanate group, an epoxy group, and an oxetane group are preferable. A vinyl group, an acryloyl group, and a methacryloyl group are more preferable from the viewpoint of easy curing and the degree of freedom in selecting a compound.

  Further, those having not only the polymerizable functional group but also having a condensed polycycle such as an aromatic ring, a naphthalene ring or an anthracene ring, a carbazole ring or a fluorene ring in the molecule are particularly preferred. These organic compounds having a cyclic structure have been found to have an Abbe number and an anomalous dispersibility different from those of organic compounds having a linear or saturated cyclic structure due to a unique electron density distribution in the molecule.

  Specific examples include methacrylic acid, acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, and nonyl. Phenyl (meth) acrylate, 2-hydroxypropyl methacrylate, 2-ethylhexyl (meth) acrylate, dimethylol tricyclodecane dimethacrylate, isobornyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, nonylphenyl (meth) acrylate, Cyclohexyl (meth) acrylate, bisphenol A di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-phenyl-phenyl (meth) acrylate , Condensed polycyclic (meth) acrylates such as 1-acryloyloxy-4-methoxynaphthalene and 10-acryloyloxy-10-methylbenzyldianthrone, 9-fluorenyl acrylate and 9,9-bis [4- (2 -(Acryloyloxyethoxy) phenyl] fluorene rings such as (meth) acrylates, carbazole (meth) acrylates such as allylcarbazole, urethane acrylates, epoxy acrylates, 3-ethyl-3- (methacryloyloxymethyl) oxetane and 3- Examples include oxetane such as ethyl-3- (methacryloyloxymethyl) oxetane, vinylbenzene, divinylbenzene, vinyl 9-anthracenecarboxylate, 2-methacryloyloxyethyl isocyanate. That.

  In addition, (meth) acrylate means what contains at least one of acrylate and methacrylate. One or a plurality of components may be selected from these substances and mixed for use. These may be monomers or oligomers.

  The content of the organic compound (B) is preferably 49% by mass or more and 94% by mass or less. When the amount is less than 49% by mass, the content of antimony oxide (III) (A) is increased, making it difficult to process the optical element. It becomes difficult to obtain a material composition having sufficient anomalous dispersion that can correct chromatic aberration.

  The organic compound (B) is composed of an organic compound (B1) having one polymerizable functional group in one molecule and an organic compound (B2) having two or more polymerizable functional groups in one molecule. The ratio (B1) / (B2) is preferably 0.10 or more and 100 or less. The rate of polymerization reaction can be adjusted by the number of polymerizable functional groups, and the degree of cure, strength, and heat resistance of the resulting cured product can be changed.

  The cured product needs to have a degree of curing, strength, heat resistance, and durability suitable for an optical element. If the degree of cure or heat resistance is too low, strength is not obtained because it is in a soft state, and problems such as deforming due to changes in temperature and humidity and maintaining the shape of the optical surface arise. On the other hand, if the degree of curing is too high, the stress tends to accumulate, and the lens may break due to changes in temperature and humidity, resulting in poor durability and non-uniform optical characteristics.

  In order to obtain a cured product having an appropriate degree of curing and heat resistance and good durability, it is an effective means to blend a plurality of types of organic compounds having different numbers of polymerizable functional groups. Particularly in the case of a composite optical element laminated on an optical substrate, there are differences in properties such as deformation due to changes in strength, heat resistance, temperature and humidity between the cured product of the material composition of the present invention and the optical substrate. Therefore, the mass ratio (B1) / (B2) becomes important in order to ensure the strength, heat resistance, and durability of the optical element.

  In the organic compound (B1) having one polymerizable functional group in one molecule, the polymer chain of the cured product has a two-dimensional structure, and the degree of cure, strength, and heat resistance of the cured product are improved. Although lowering, there is an effect of reducing stress due to curing and increasing durability. On the other hand, in the organic compound (B2) having two or more polymerizable functional groups in one molecule, the polymer chain of the cured product has a three-dimensional structure, the degree of cure and strength of the cured product, It has the effect of increasing heat resistance, and deformation due to temperature change is also reduced. Therefore, practicality as a lens material may be obtained.

  In order to obtain characteristics suitable for use as an optical element, the mass ratio (B1) / (B2) is preferably 0.10 or more and 100 or less. More preferably, the mass ratio (B1) / (B2) is 0.10 or more and 10 or less. If it is greater than 100, the degree of cure, strength, and heat resistance of the cured product will be low, and if it is less than 0.10, the stress due to curing will be too great, and the durability due to changes in temperature and humidity will deteriorate.

  The content of the polymerization initiator is preferably 0.05% by mass or more and 5% by mass or less. If it is less than 0.05% by mass, a material composition having sufficient curability cannot be obtained, resulting in a cured product having a low degree of curing. If it exceeds 5% by mass, the transparency of the cured product is lowered, and problems such as yellowing due to sunlight increase.

  As the polymerization initiator, either a thermal polymerization initiator or a photopolymerization initiator can be used, but a photopolymerization initiator is preferable. The photopolymerization initiator does not require a time-consuming process such as heating, and can be efficiently cured, and also occurs when heating a composite optical element with another optical member. Less susceptible to problems.

  Specific examples of photopolymerization initiators include 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ester, alkoxyacetophenone, benzyldimethyl ketal, benzophenone and benzophenone derivatives, alkyl benzoylbenzoate, bis (4-dialkylaminophenyl). ) Ketones, benzyl and benzyl derivatives, benzoin and benzoin derivatives, benzoin alkyl ethers, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, thioxanthone and thioxanthone derivatives, 2,4,6-trimethylbenzoyldiphenylphosphine And oxides. These photopolymerization initiators can be used alone or in combination of two or more.

  Of these photopolymerization initiators, it is sufficient to use acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and phenylbis (2,4,6-trimethylbenzoyl) -phosphine oxide. Is particularly preferable since it provides excellent curability and transparency of the cured product.

  In addition to the above components, the optical material composition of the present embodiment can be further improved in durability by adding an ultraviolet absorber.

  Examples of ultraviolet absorbers include salicylic acid esters such as phenyl salicylate, p-tertiary butylphenyl salicylate, p-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-acetoxyethoxybenzophenone, 2-hydroxy- 4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy Benzophenone series such as -4,4'-dimethoxy-5,5'-disulfobenzophenone disodium salt, 2 (2'-hydroxy-5'-methylphenyl) benzotriazole, 2 (2'-hydroxy-3) ', 5' -Tributylbutyl) benzotriazole, 2 (2′-hydroxy-3′-tertiarybutyl-5′-methylphenyl) -5-chlorobenzotriazole, 2 (2′-hydroxy-3 ′, 5′-ditertiary Butylphenyl) -5-chlorobenzotriazole, 2 (2′-hydroxy-3 ′, 5′-ditertiary amylphenyl) benzotriazole, 2 (2′-hydroxy-5′-tertiarybutylphenyl) benzotriazole, 2 (2'-hydroxy-5'-tertiaryoctylphenyl) benzotriazole and other benzotriazoles, 2 ', 4'-ditertiarybutylphenyl-3,5-ditertiarybutyl-4-hydroxybenzoate and other benzoates Ethyl-2-cyano-3,3- Examples thereof include cyanoacrylate-based compounds such as diphenyl acrylate and aminobenzoic acid-based compounds such as butyl p-aminobenzoate. One or more of these can be selected and mixed for use.

  Furthermore, in addition to the above components, the optical material composition of the present embodiment is further added with a hindered phenol-based, hindered amine-based, phosphate ester-based, or sulfur-based antioxidant for durability. May be improved.

  As a method for preparing the material composition of the present embodiment, an antimony (III) oxide fine particle (A) is added to an organic compound (B) and a polymerization initiator (C), and a bead mill, a ball mill, a jet mill, a homogenizer, etc. A method of obtaining a material composition by uniformly dispersing all components with a known dispersion apparatus. The dispersion state of the material composition is adjusted by setting the material and size of the media such as beads and balls used for dispersion and the conditions of the dispersion device. At this time, depending on the dispersion state of the material composition, a dispersant may be added as long as it is in an amount that does not impair the abnormal dispersibility and workability, and a solvent may be temporarily added. However, it is necessary to remove this solvent before finally processing as an optical element.

  As another method for preparing the material composition, the antimony (III) oxide fine particles (A) are previously treated with a particle surface modifier composed of a coupling agent such as silane or titanium, and then all of the particles are prepared by a known dispersing device. A method of obtaining a material composition by uniformly dispersing the components can be mentioned.

In the present embodiment, the value of the anomalous dispersion ΔθgF representing the degree of anomalous dispersion is calculated by the following method. That is, the respective partial dispersion ratios θgF are obtained by the following equation 1, the Abbe number (νd) is taken on the horizontal axis, the partial dispersion ratio θgF is taken on the vertical axis, and NSL7 ( νd = 60.5, θgF = 0.5346: OHARA) and PBM2 (νd = 36.3, θgF = 0.5828: OHARA) were selected as reference dispersion glasses, and the coordinates (νd, θgF) of these two types of optical glasses were selected. ) Is connected by a straight line, and the difference in ordinate (ΔθgF) between this straight line and the coordinates indicating θgF and νd of the glass to be compared is defined as the degree of anomalous dispersion, that is, the degree of anomalous dispersion.
θgF = (ng−nF) / (nF−nC) Equation 1
(Ng: refractive index for g line, nF: refractive index for F line, nC: refractive index for C line)

When the Abbe number is νd and the anomalous dispersion in the F-line and g-line is ΔθgF, the resin composition of the present embodiment is 15 ≦ νd ≦ 60 and −0.015 ≦ ΔθgF ≦ 0 in the cured product. .075
Is preferred. In other words, as the resin composition of the present embodiment, the cured product is preferably a resin composition that satisfies the above conditions. In this way, chromatic aberration can be effectively reduced in a wide visible light range from C line to g line.

  In the graph in which the cured product of the existing resin composition, the organic compound, and the optical glass all have a partial dispersion ratio θgF on the vertical axis and the Abbe number νd on the horizontal axis, the Abbe number νd is 55 or less in a uniform region. However, the degree of anomalous dispersion tends to increase. Since the range of anomalous dispersion that can be selected as an optical material when designing an optical system is narrowed, correction of chromatic aberration cannot be performed effectively, limiting the reduction in size and weight or performance.

  The cured product comprising the material composition of the present embodiment is a hybrid material of antimony (III) (A) and an organic compound having different Abbe numbers and anomalous dispersion, and antimony (III) (A) By adjusting the content of the organic compound, the Abbe number and the anomalous dispersion can be adjusted to desired values that can effectively correct the chromatic aberration of the optical system. Further, it is possible to realize Abbe number and anomalous dispersion which are not possessed by conventional organic compounds alone and optical glass, and it is possible to realize a small, light and high performance optical system which has never been achieved. In addition, even with an Abbe number and anomalous dispersion similar to those of conventional optical glass, it is possible to realize excellent workability that cannot be realized with optical glass.

  If the Abbe number νd is less than 10, the effect of reducing chromatic aberration becomes excessive in the wavelength range from the C line to the F line, which is not preferable. When the Abbe number νd is larger than 55, the effect of reducing chromatic aberration is small in the wavelength range from the C line to the F line, which is not preferable.

  Further, in order to make the anomalous dispersion ΔθgF smaller than less than −0.015, the addition amount of antimony (III) oxide is required to be more than 50% by mass, and the viscosity of the material composition becomes high. It is not preferable. When the anomalous dispersion ΔθgF is larger than 0.075, the anomalous dispersion is too large, which is not preferable because excessive correction is performed in the optical system.

  Next, an example using the material composition of the present embodiment and a comparative example not using are shown. In the examples, the cured product of the material composition of the present embodiment is used as an optical element, and this optical element is used in an optical system.

  FIGS. 1A and 1B are cross-sectional views along the optical axis showing an optical configuration at the time of focusing on an object point at infinity, in which FIG. 1A is a wide angle end, FIG. 1B is an intermediate focal length state, and FIG. FIG. The numbers in r1, r2,... And the numbers in d1, d2,... Described in the lens cross-sectional views correspond to the numbers in the surface number column in the numerical data described later.

  2A and 2B are diagrams showing spherical aberration, astigmatism, distortion aberration, and chromatic aberration of magnification at the time of focusing on an object point at infinity in a usage example, where (a) is a wide angle end, (b) is an intermediate focal length state, ( c) shows a state at the telephoto end. FIY represents the image height.

  In this use example, the cured product of the material composition of the present embodiment is used for the fifth lens from the object side. In this usage example, the Abbe number νd of the fifth lens is 23, and the anomalous dispersion ΔθgF is 0.061. Due to the appropriate anomalous dispersion of the material composition (cured product) of this embodiment, axial chromatic aberration and lateral chromatic aberration are suppressed to a small level, and a high-quality optical system is realized.

  Next, FIG. 3 shows a cross-sectional view along the optical axis in the conventional optical system. FIG. 4 shows spherical aberration, astigmatism, distortion, and lateral chromatic aberration. The aberration diagrams in the conventional example show a state in which various aberrations are satisfactorily corrected.

  The lens configuration of the optical system shown in FIG. 3 is the same as the optical system of the usage example shown in FIG. The specifications such as the focal length, F number, and zoom ratio are the same as those of the optical system shown in FIG. However, the fifth lens from the object side is different from the optical system of the usage example in that the lens is changed to S-NPH2 (manufactured by OHARA INC.) Of optical glass. In the conventional example, S-NPH2 has an Abbe number νd of 18.9 and an anomalous dispersion ΔθgF of 0.032. Thus, since S-NPH2 satisfies the above conditions, it can be said that it has appropriate anomalous dispersion. As can be seen from FIG. 4, it can be said that this is a high-quality optical system in which axial chromatic aberration and lateral chromatic aberration are suppressed to a small level. However, the thickness of the lens is thicker than in the usage example.

  Here, the aberration diagram of the usage example (FIG. 2) and the aberration diagram of the conventional example (FIG. 4) will be compared. Then, also in the usage example, the aberration is corrected satisfactorily to the extent that it is comparable to the conventional example. Thus, even when the cured product of the material composition of the present embodiment is used in an optical system, an optical system in which conventional aberrations are favorably corrected can be realized.

  Next, numerical data of the above usage examples and comparative examples will be listed. In each numerical data, the r column represents the radius of curvature of each lens surface, the d column represents the thickness or air spacing of each lens, the nd column represents the refractive index of each lens at the d-line, and the νd column represents each lens. Represents the Abbe number. Also, * indicates an aspheric surface.

The aspherical shape is expressed by the following equation when the optical axis direction is z, the direction orthogonal to the optical axis is y, the conical coefficient is K, and the aspherical coefficients are A4, A6, A8, and A10. .
z = (y ² / r) / [1+ {1− (1 + K) (y / r) ² } ^1/2 ]
+ A4y ⁴ + A6y ⁶ + A8y ⁸ + A10y ¹⁰ ...
Here, in the aspheric data, E represents a power of 10. In addition, when the aspheric coefficient is not described, the value of the aspheric coefficient is zero.

(Example of use)
Surface data Surface number rd nd νd
Object INF INF
1 26.4564 0.9000 1.84666 23.78
2 ^* 10.0742 3.0000
3 INF 12.0000 1.80610 40.92
4 INF 0.2000
5 ^* 34.9519 2.4000 1.80610 40.92
6 -24.2855 0.9999
7 ^* -26.2710 0.6000 1.74320 49.34
8 ^* 10.2309 0.9000 1.63494 23.22
9 ^* 34.1807 11.9143
10 (Aperture) INF 8.6026
11 ^* 11.4252 4.0000 1.83481 42.71
12 -7.3175 0.6000 1.80810 22.76
13 -24.0548 2.3393
14 12.3855 1.0000 1.84666 23.78
15 6.3411 1.5001
16 ^* 11.3148 2.0000 1.49700 81.54
17 24.7330 2.7930
18 INF 1.5000 1.54771 62.84
19 INF 0.8000
20 INF 0.7500 1.51633 64.14
21 INF 1.3601
Image plane INF

Aspheric data 2nd surface
K = -0.3690, A2 = 0.0000E + 00, A4 = 2.9951E-05, A6 = 5.3453E-07, A8 = 0.0000E + 00, A10 = 0.0000E + 00
5th page
K = -0.3428, A2 = 0.0000E + 00, A4 = 6.9553E-06, A6 = 1.0625E-07, A8 = 0.0000E + 00, A10 = 0.0000E + 00
7th page
K = -0.2849, A2 = 0.0000E + 00, A4 = -3.0138E-04, A6 = 4.0578E-06, A8 = 0.0000E + 00, A10 = 0.0000E + 00
8th page
K = -0.0281, A2 = 0.0000E + 00, A4 = 6.9302E-04, A6 = -3.1732E-05, A8 = 0.0000E + 00, A10 = 0.0000E + 00
9th page
K = -0.1005, A2 = 0.0000E + 00, A4 = -5.3088E-04, A6 = 1.1655E-05, A10 = 0.0000E + 00, A10 = 0.0000E + 00
11th page
K = 0.0728, A2 = 0.0000E + 00, A4 = -2.2619E-04, A6 = -4.6980E-08, A8 = 0.0000E + 00, A10 = 0.0000E + 00
16th page
K = -1.5301, A2 = 0.0000E + 00, A4 = 1.1271E-04, A6 = 4.0725E-06, A8 = 0.0000E + 00, A10 = 0.0000E + 00

Various data Zoom ratio 3.00
Wide angle Medium telephoto Focal length 5.99960 10.40020 17.99975
F number 2.8002 3.3565 4.7748
Angle of view 31.6 ° 17.7 ° 10.3 °
Image height 3.320 3.320 3.320
Total lens length 60.1593 60.1589 60.1593
BF 1.36009 1.36009 1.36009
d6 0.99985 8.01310 11.51443
d9 11.91428 4.90098 1.39971
d10 8.60265 6.26147 1.19997
d13 2.33934 1.73193 0.80014
d15 1.50009 4.50020 11.23470
d17 2.79301 2.74144 2.00025

Zoom lens group data Group Start focal length
1 1 29.87719
2 7 -17.20296
3 11 9.65903
4 14 -16.60629
5 16 39.98504

[Glass material refractive index table] ... List of refractive indices by wavelength of medium used in this use Glass 587.56 656.27 486.13 435.83 404.66
L10 1.547710 1.545046 1.553762 1.558428 1.562261
L5 1.634940 1.627290 1.654640 1.672908 1.689875
L11 1.516330 1.513855 1.521905 1.526214 1.529768
L9 1.496999 1.495136 1.501231 1.504507 1.507205
L2, L3 1.806098 1.800248 1.819945 1.831174 1.840781
L6 1.834807 1.828975 1.848520 1.859548 1.868911
L4 1.743198 1.738653 1.753716 1.762047 1.769040
L7 1.808095 1.798009 1.833513 1.855904 1.876580
L1, L8 1.846660 1.836488 1.872096 1.894189 1.914294

(Conventional example)
Surface data Surface number rd nd νd
Object INF INF
1 27.3626 0.9000 1.84666 23.78
2 ^* 10.1121 3.0000
3 INF 12.0000 1.80610 40.92
4 INF 0.2000
5 ^* 34.1036 2.4000 1.80610 40.92
6 -24.1842 0.9999
7 ^* -19.6695 0.6000 1.74320 49.34
8 13.9199 1.3000 1.92286 18.903
9 28.1720 11.9098
10 (Aperture) INF 8.5816
11 ^* 11.6806 4.0000 1.83481 42.71
12 -7.0606 0.6000 1.80810 22.76
13 -22.4815 2.3411
14 14.0648 1.0000 1.84666 23.78
15 6.7601 1.5001
16 ^* 10.6451 2.0000 1.49700 81.54
17 21.4972 2.8264
18 INF 1.5000 1.54771 62.84
19 INF 0.8000
20 INF 0.7500 1.51633 64.14
21 INF 1.3601
Image plane INF

Aspheric data 2nd surface
K = -0.4019, A2 = 0.0000E + 00, A4 = 2.8028E-05, A6 = 7.9587E-07, A8 = 0.0000E + 00, A10 = 0.0000E + 00
5th page
K = -0.3464, A2 = 0.0000E + 00, A4 = 3.5796E-06, A6 = 1.4808E-07, A8 = 0.0000E + 00, A10 = 0.0000E + 00
7th page
K = -0.2881, A2 = 0.0000E + 00, A4 = 3.7992E-05, A6 = -1.0002E-06, A8 = 0.0000E + 00, A10 = 0.0000E + 00
11th page
K = 0.0773, A2 = 0.0000E + 00, A4 = -2.2695E-04, A6 = -2.0319E-07, A8 = 0.0000E + 00, A10 = 0.0000E + 00
16th page
K = -1.5302, A2 = 0.0000E + 00, A4 = 8.9552E-05, A6 = 6.6136E-06, A8 = 0.0000E + 00, A10 = 0.0000E + 00

Various data Zoom ratio 3.00
Wide angle Medium telephoto Focal length 5.99921 10.40005 17.99950
F number 2.8002 3.2959 4.6552
Angle of view 31.9 ° 17.8 ° 10.3 °
Image height 3.320 3.320 3.320
Total lens length 60.5689 60.5692 60.5689
BF 1.36013 1.36013 1.36013
d6 0.99987 8.02133 11.51068
d9 11.90975 4.88919 1.39897
d10 8.58156 6.29409 1.20000
d13 2.34114 1.76093 0.80033
d15 1.50010 4.46452 11.24871
d17 2.82637 2.72871 2.00010

Zoom lens group data Group Start focal length
1 1 29.23916
2 7 -17.11132
3 11 9.60458
4 14 -16.40287
5 16 39.98276

[Glass Material Refractive Index Table] ... List of refractive indexes by wavelength of medium used in this conventional example Glass 587.56 656.27 486.13 435.83 404.66
L10 1.547710 1.545046 1.553762 1.558428 1.562261
L11 1.516330 1.513855 1.521905 1.526214 1.529768
L9 1.496999 1.495136 1.501231 1.504507 1.507205
L2, L3 1.806098 1.800248 1.819945 1.831174 1.840781
L6 1.834807 1.828975 1.848520 1.859548 1.868911
L4 1.743198 1.738653 1.753716 1.762047 1.769040
L7 1.808095 1.798009 1.833513 1.855904 1.876580
L5 1.922860 1.909158 1.957996 1.989717 2.019763
L1, L8 1.846660 1.836488 1.872096 1.894189 1.914294

The optical element and the composite optical element will be described below with reference to the drawings. The optical element and the composite optical element are made of a cured product of the material composition of the present embodiment.
FIG. 5 is a diagram illustrating an example of a molding apparatus for molding an optical element.
In addition, an optical element is an element comprised only from the hardened | cured material which superposed | polymerized the material composition of this embodiment as mentioned above. An optical element molding apparatus 1 includes a cylindrical metal barrel mold 2, a metal upper mold 3 having a desired optical surface 3a, a lower mold 4 made of glass that transmits ultraviolet light having a desired optical surface 4a, and an upper mold. 3 is provided with a drive rod 5 for driving 3 up and down, and a release cylinder 6 for releasing the cured optical element from the lower mold 4.

  The cylindrical metal barrel mold 2 is provided with an inlet 7 for injecting a material composition and an outlet 8 for discharging an excess material composition. The drive rod 4 slides up and down the upper die 3 in the metal barrel die 2 by a drive source (not shown). The release ring 6 slides up and down in contact with the inner peripheral surface of the metal barrel mold 2. A molding chamber 9 for molding an optical element is formed by the optical surfaces of the upper mold 3 and the lower mold 4 and the inner peripheral surface of the metal barrel mold 2.

  The optical element is molded by the following procedure. The metal upper mold 3 and the glass lower mold 4 are placed in the metal barrel mold 2 so that the optical surfaces 3a and 4a face each other. At this time, the upper die 3 is held at a predetermined height in the first stage by the drive rod 5. The predetermined height in the first stage is a height at which the upper mold 3 is located above the discharge port 8. By holding the upper die 3 at this height, a molding chamber 9 is formed.

  Next, the material composition of the present invention containing a photopolymerization initiator is injected from the injection port 7 and filled into the molding chamber 9. At this time, if the inside of the molding chamber 9 is set to a negative pressure, it is possible to prevent entrainment of bubbles during injection of the material composition and air remaining in the molding chamber. The temperature may be adjusted so that the viscosity of the material composition can be easily injected. When the material composition overflows from the discharge port 8, it is determined that the molding chamber 9 is filled, and the injection of the material composition is stopped.

  The inlet 7 is closed, and the upper die 3 is pressed downward to the second stage height. At this time, an excessive material composition flows out from the discharge port 8. Next, the material composition is cured by irradiating ultraviolet rays from below the lower mold 4. In addition, although the ultraviolet irradiation device is arrange | positioned under the mold release ring 6, illustration is abbreviate | omitted. The upper mold 3 is slowly moved downward in accordance with the shrinkage accompanying the curing of the material composition. By lowering the upper mold 3 in conjunction with the shrinkage, the internal stress of the cured optical element can be reduced. After the material composition is sufficiently cured, the drive rod 5 is raised to release the upper mold 3. Next, the release ring 6 is moved upward to release the cured product from the lower mold 4. In this way, a cured product of the material composition can be taken out as an optical element having a desired shape.

  In FIG. 5, a spherical lens is used if both of the optical surfaces 3a and 4a are spherical, and an aspheric lens is used if either or both of the optical surfaces 3a and 4a are aspheric. Alternatively, if both are diffractive surfaces, each diffractive lens can be manufactured as an optical element.

  In addition, the composite optical element can be manufactured by curing the above-described material composition placed on the surface of the optical base material and laminating the optical base material and a cured product of the material composition. it can. This composite optical element is a composite optical element in which the interface between the optical substrate and the cured product of the material composition is a spherical surface, an aspherical surface, a free-form surface, or a diffractive surface.

  As an optical base material used for the composite optical element, ordinary optical glass, optical resin, or transparent ceramic that does not cause problems such as chipping, surface discoloration, devitrification, or turbidity when processed into a desired shape is used. be able to. Examples of the optical glass include quartz, BK7 (SCHOOT), BACD11 (HOYA), BAL42, LAH53 (Ohara). Examples of optical resins include amorphous polyolefins such as Zeonex (Nippon Zeon), ARTON (JSR), Appel (Mitsui Chemicals), acrylic resins such as Acrypet (Mitsubishi Rayon) and Delpet (Asahi Kasei). it can.

  The optical material composition of the present embodiment is placed on the surface of the optical substrate by a method such as coating, and the mold is brought into contact with the upper surface so as to have a desired shape. The mold used at this time may be made of metal or glass. However, when the material composition is cured by irradiating ultraviolet rays from the opposite surface of the optical substrate, a glass mold is used. When a metal mold is used, the material composition is cured by irradiating ultraviolet rays from the side of the optical substrate.

  By such a method, for example, a composite optical element as shown in FIG. 6 can be manufactured. In the composite optical element 10 shown in FIG. 6, a cured product 13 of the material composition is integrally formed on the surface of the optical substrate 11.

Hereinafter, a method for manufacturing the composite optical element will be described.
FIG. 7 is a diagram for explaining an example of a composite optical element manufacturing apparatus, and the left side of the optical axis shows a cross section. The composite optical element manufacturing apparatus 20 includes a support frame (not shown), a support base 21, a receiving portion 22, and a holding cylinder 23. The support base 21 is supported by a support frame. The receiving portion 22 has a cylindrical shape and is attached to the support base 21. The receiving portion 22 is provided with a bearing 24 with a built-in bearing.

  The holding cylinder 23 is attached to the receiving portion 22 via the bearing 24, and the holding cylinder 23 is rotatable with respect to the receiving portion 22 by the action of the bearing 24. In addition, the holding cylinder 23 is provided with an annular engagement edge 25 that receives the outer edge portion of the optical base material 11 at the upper part of the inner periphery thereof. In addition, a pulley 26 is formed in the lower part of the holding cylinder 23.

  On the other hand, a motor 27 is fixed below the support base 21. A pulley 29 is attached to the drive shaft 28 of the motor 27. A belt 30 is wound around the pulley 29 and the pulley 26. Thus, a rotating mechanism for rotating the holding cylinder 23 is configured.

  The bearing 24 is fixed by pressing rings 31 and 32, respectively. That is, the holding ring 31 is screwed with the screw portion 22 a of the receiving portion 22, and the holding ring 32 is screwed with the screw portion 23 a of the holding cylinder 23. Thereby, the bearing 24 can be fixed between the receiving portion 22 and the holding cylinder 23.

  A support means 35 is provided above the support base 21. The support means 35 moves the upper mold 3 up and down, and the support column 36 of the support means 35 that supports the upper mold 3 at a desired position is fixed to the upper surface of the support base 21. A cylinder 37 is provided. A cylinder rod 38 is attached to the cylinder 37. Further, the upper die 3 is attached to the tip of the cylinder rod 38. Further, the upper mold 3 is supported so that the optical axis 39 of the optical base 11 and the axis of the upper mold 3 coincide with each other with the optical base 11 placed on the engaging edge 25 of the holding cylinder 23. ing.

A composite optical element manufacturing method using the composite optical element manufacturing apparatus described above will be described.
The optical substrate 11 made of a lens having desired optical characteristics is placed so as to be positioned by the engagement edge 25 of the holding cylinder 23. In addition, you may perform the coupling process for improving the adhesiveness of a material composition and the glass-made optical base material to the material composition formation surface of the surface 11a of the optical base material 11. FIG. Next, a required amount of the material composition 12 is discharged onto the surface 11a of the optical substrate 11 by a discharge means (not shown). At this time, it is preferable to adjust the temperature so that the viscosity of the material composition can be easily discharged.

  Next, the cylinder 35 is operated to lower the upper mold 3, and the optical surface 3 a of the upper mold 3 is brought into contact with the material composition 12 discharged onto the surface 11 a of the optical substrate 11. By continuing further lowering, the material composition 12 is spread into a predetermined shape. In addition, before extending to a predetermined shape, the lowering of the upper mold 3 is stopped. In this state, the optical base 11 is rotated at least once by operating the motor 27 and rotating the holding cylinder 23.

FIG. 8 is a diagram illustrating a spread state of the material composition.
The upper mold 3 is pressed against the material composition 12 placed on the surface 11a of the optical substrate 11 so that the optical axis 39 of the optical substrate 11 and the axis of the upper mold 3 coincide with each other, so that the optical substrate 11 side is Make at least one revolution. By doing in this way, the material composition 12 extends uniformly in the space between the surface 11a of the optical base material 11 and the upper mold | type 3, and a material composition layer is formed.

  Thereafter, the cylinder 37 is operated again, and the upper die 3 is lowered again. When the layer of the material composition 12 reaches a desired thickness and diameter and reaches a predetermined shape, the lowering of the upper mold 3 is stopped, and an ultraviolet irradiation device (not shown) is applied from the lower side of the optical substrate 11. Irradiate with ultraviolet rays.

  As a result, the material composition between the upper mold 3 and the optical substrate 11 is cured, and a cured product 13 of the material composition can be formed on the surface 11a of the optical substrate 11 in a body. At this time, an optical surface to which the optical surface 3a of the upper mold 3 is transferred is formed on the surface of the cured product 13 of the material composition. A composite optical element having a desired shape can be obtained by releasing the cured product from the optical surface 3a of the upper mold 3 from the surface of the cured product 13 of the material composition.

Examples 1-1 to 1-4
(Preparation of composition)
100 g of methyl methacrylate as an organic compound (B1) having one polymerizable functional group and 0.2 g of a photopolymerization initiator bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide as a polymerization initiator (C) at 25 ° C. The mixture was stirred for 30 minutes, and antimony (III) oxide fine particles having a number average particle diameter of 10 nm were adjusted to 5, 10, 30, 50 mass% with respect to the total amount with the obtained polymerizable composition. The composition was prepared by mixing and dispersing at 30 ° C. in a wet bead mill. Each composition is shown in Table 1 in mass%.

(Production of optical elements)
The material composition was molded into a size of 20 mm in diameter and 1 mm in thickness, irradiated with ultraviolet rays at a wavelength of 400 nm for 100 seconds at an illuminance of 100 mW / cm ² , and further heated at 80 ° C. for 1 hour to prepare a cured product. The obtained cured product was measured for refractive index, and Abbe number νd, partial dispersion ratio θgF and anomalous dispersion ΔθgF were determined by the following methods. The results are shown in Table 2.

(1) Measurement of refractive index The refractive index of the cured product at d-line, C-line, F-line, and g-line is measured at 20 ° C and 60% RH using a precision refractometer (KPR-200 manufactured by Shimadzu Device Manufacturing Co., Ltd.). Measured with
(2) Calculation of Abbe number νd The refractive indexes for the d-line, C-line, F-line, and g-line obtained by measurement are nd,
The Abbe number νd was calculated from the following equation 2 when nC, nF, and ng.
νd = (nd−1) / (nF−nC) Equation 2
(3) Calculation of partial dispersion ratio θgF When the refractive indexes for the d-line, C-line, F-line, and g-line obtained by measurement are nd, nC, nF, and ng, respectively, the partial dispersion ratio θgF is Calculated from Equation 3.
θgF = (ng−nF) / (nF−nC) (Formula 3)
(4) Calculation of anomalous dispersion ΔθgF By the above formulas 2 and 3, the Abbe number νd and partial dispersion ratio θgF of each cured product are obtained, the Abbe number νd is plotted on the horizontal axis, and the partial dispersion ratio θgF is plotted on the vertical axis. Among normal optical glasses that do not exhibit anomalous dispersion, NSL7 (νd = 60.5, θgF = 0.5346: OHARA) and PBM2 (νd = 36.3, θgF = 0.5828: OHARA) standard dispersion glass The coordinates (νd, θgF) of these two types of optical glass are connected by a straight line, and the difference in ordinate (ΔθgF) from the coordinates indicating θgF and νd of the cured product to be compared with this straight line is defined as the anomalous dispersion. .
That is, the relationship between the straight lines connecting the two types of reference dispersion glass is expressed by Equation 4 when the Abbe number νd ₀ and the partial dispersion ratio θgF ₀ are used. When the Abbe number of the cured product obtained from Equation 2 is νd and the partial dispersion ratio of the cured product obtained from Equation 3 is θgF, the anomalous dispersion ΔθgF is obtained from Equation 5.
θgF ₀ = −0.001989 × νd ₀ +0.6551 Equation 4
ΔθgF = θgF−θgF ₀
= ΘgF − (− 0.001989 × νd + 0.6551) …… Formula 5

(Production of composite optical elements)
A composite optical element having a shape as shown in FIG. 6 was prepared using a molding apparatus shown in FIG. 7 with a base material composed of the material composition and BK7 (manufactured by SCH00T) glass. In either case, ultraviolet light at a wavelength of 400 nm was irradiated for 100 seconds at an intensity of 100 mW / cm ² , and further heated at 80 ° C. for 1 hour to produce a composite optical element having the shape shown in FIG.
In FIG. 6, the glass lens of the base material has a radius of curvature R1 = 16 mm, a radius of curvature R2 = 16 mm, L1 = 20 mm, and L3 = 5 mm. A composite optical element was fabricated on this substrate so that the curvature radius R3 = 26 mm and the aperture L2 = 16 mm. The fabricated composite optical element was evaluated for processability by the following method.

(5) Evaluation of workability Processability is measured by measuring the radius of curvature of the cured surface of the composite optical element material composition using a surface shape roughness measuring machine (Form Talysurf PGI Plus, manufactured by Taylor Hobson). Then, the deformation amount with respect to the target curvature radius R3 was obtained. If the deformation amount was within ± 2 μm, it was judged “good”, and if it was more than that, it was judged “bad”.

Examples 2-1 to 2-4
Except that N- (β-acryloyloxyethyl) carbazole was blended as an organic compound (B1) having one polymerizable functional group instead of methyl methacrylate used in Examples 1-1 to 1-4 In the same manner as in Examples 1-1 to 1-4, material compositions having the blending ratios listed in Table 1 were prepared.
Next, the characteristics of an optical element produced by curing in the same manner as in Example 1-1 were evaluated, and the results are shown in Table 2. In the preparation of the composition and the production process of the optical element, the work was performed by heating to 70 ° C.

Examples 3-1 to 3-4
Example 1-1 to Example 1-1 except that trimethylolpropane triacrylate was blended as an organic compound (B1) having one polymerizable functional group instead of methyl methacrylate used in Examples 1-1 to 1-4. A composition was prepared in the same manner as in 1-4.
Next, the characteristics of an optical element produced by curing in the same manner as in Example 1-1 were evaluated, and the results are shown in Table 2.

Examples 4-1 to 4-4
Instead of methyl methacrylate used in Examples 1-1 to 1-4, N-allylcarbazole and 2 polymerizable functional groups were used as a compound having one organic compound (B1) having one polymerizable functional group. Example 1 except that 100 g of 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene blended at the blending ratio shown in Table 1 was used as the organic compound component (B2) having at least one. A material composition was prepared in the same manner as in -1 to 1-4.
Next, the characteristics of an optical element produced by curing in the same manner as in Example 1-1 were evaluated, and the results are shown in Table 2. In the preparation of the composition and the production process of the optical element, the work was performed by heating to 60 ° C.

Examples 5-1 to 5-4
Instead of methyl methacrylate used in Examples 1-1 to 1-4, 1-acryloxy-4-methoxynaphthalene as an organic compound (B1) having one polymerizable functional group and two or more polymerizable functional groups A composition was prepared in the same manner as in Example 1-1 except that 100 g of dimethylol tricyclodecane diacrylate blended at a blending ratio shown in Table 1 was used as the organic compound component (B2).
Next, the characteristics of an optical element produced by curing in the same manner as in Example 1-1 were evaluated, and the results are shown in Table 2. In the preparation of the composition and the production process of the optical element, the work was performed by heating to 60 ° C.

Examples 6-1 to 6-4
Instead of methyl methacrylate used in Examples 1-1 to 1-4, 1-acryloxy-4-methoxynaphthalene as an organic compound (B1) having one polymerizable functional group and two or more polymerizable functional groups A composition was prepared in the same manner as in Example 1-1 except that 100 g of dimethylol tricyclodecane diacrylate blended at a blending ratio shown in Table 1 was used as the organic compound component (B2).
Next, the characteristics of an optical element produced by curing in the same manner as in Example 1-1 were evaluated, and the results are shown in Table 2. In the preparation of the composition and the production process of the optical element, the work was performed by heating to 60 ° C.

Comparative Example 1
Instead of methyl methacrylate used in Examples 1-1 to 1-4, N-allylcarbazole as an organic compound (B1) having one polymerizable functional group and an organic compound component having two or more polymerizable functional groups (B2) As in Example 1-1, except that 100 g of 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene blended at the blending ratio shown in Table 1 was used. A composition was prepared.
Next, the characteristics of an optical element produced by curing in the same manner as in Example 1-1 were evaluated, and the results are shown in Table 2.

The Abbe number νd and the anomalous dispersion ΔθgF of the cured product of the optical composition of the present invention in Examples 1-1 to 6-4 are both in the preferred range, and sufficient chromatic aberration can be effectively reduced. It has been found that an optical element having anomalous dispersion and an optical composition using an optical composition is excellent in workability.
On the other hand, in Comparative Example 1, the content of antimony (III) oxide was as high as 60% by mass, and there was a problem in the processability of the lens.

  Since the material composition of the present invention can be easily made into a cured product by irradiation with ultraviolet rays or the like, the productivity is high, and the cured product has sufficient anomalous dispersibility. An optical element with less can be obtained. Moreover, the obtained optical material composition is excellent in workability. The optical element made of the cured product is suitable for various optical devices, can reduce chromatic aberration of the optical system, and can be reduced in size and weight.

FIG. 1 is a cross-sectional view along the optical axis showing an optical configuration at the time of focusing on an object point at infinity. 2A and 2B are diagrams showing spherical aberration, astigmatism, distortion aberration, and chromatic aberration of magnification at the time of focusing on an object point at infinity in a usage example, where (a) is a wide angle end, (b) is an intermediate focal length state, ( c) shows a state at the telephoto end. FIG. 3 is a cross-sectional view along the optical axis showing the optical configuration of the conventional example when focusing on an object point at infinity. 4A and 4B are diagrams showing spherical aberration, astigmatism, distortion, and lateral chromatic aberration when focusing on an object point at infinity according to the related art, where FIG. 4A is a wide angle end, FIG. 4B is an intermediate focal length state, and FIG. ) Shows the state at the telephoto end. FIG. 5 is a diagram showing an example of a molding apparatus that uses, for molding, an optical element composed only of a cured product obtained by polymerizing the material composition of the present invention. FIG. 6 is a diagram illustrating an example of a composite optical element. FIG. 7 is a diagram illustrating an example of an apparatus for manufacturing a composite optical element. FIG. 8 is a diagram showing a spread state of the material composition of the present invention. FIG. 9 is a diagram showing the anomalous dispersion ΔθgF.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Optical element shaping | molding apparatus, 2 ... Metal cylinder type | mold, 3 ... Upper mold | type, 3a ... Optical surface, 4 ... Lower mold | type, 4a ... Optical surface, 5 ... Drive rod, 6 ... Release cylinder, 7 ... Injection port, DESCRIPTION OF SYMBOLS 8 ... Discharge port, 9 ... Molding chamber, 10 ... Composite type optical element, 11 ... Optical base material, 11a ... Surface, 12 ... Material composition, 13 ... Hardened | cured material composition, 20 ... Production of composite type optical element Device, 21 ... support base, 22 ... receiving part

Claims (9)

  Antimony (III) oxide fine particles (A) 5% by mass to 50% by mass, organic compound (B) 49% by mass to 94% by mass having one or more polymerizable functional groups in one molecule, polymerization The material composition characterized by being 0.05 mass% or more and 5 mass% or less of initiator (C).   In a cured product of a material composition comprising antimony (III) oxide fine particles (A), an organic compound (B) having one or more polymerizable functional groups in one molecule, and a polymerization initiator (C) A material composition characterized by satisfying the following conditions: 15 ≦ νd ≦ 60 and 1.45 ≦ nd ≦ 1.70, where d is the refractive index nd at the d-line and Abbe number νd.   In a cured product of a material composition comprising antimony (III) oxide fine particles (A), an organic compound (B) having one or more polymerizable functional groups in one molecule, and a polymerization initiator (C) And a Abbe number νd, and an anomalous dispersion ΔθgF of F-line and g-line, 15 ≦ νd ≦ 60 and −0.015 ≦ ΔθgF ≦ 0.075.   4. The material composition according to claim 1, wherein the organic compound (B) has at least one functional group selected from a vinyl group, an acryloyl group, a methacryloyl group, an isocyanate group, an epoxy group, and an oxetane group. Material composition.   5. The material composition according to claim 4, wherein the organic compound (B) is an organic compound (B1) having one polymerizable functional group in one molecule and an organic compound having two or more polymerizable functional groups in one molecule. A material composition comprising the compound (B2) and having a mass ratio (B1) / (B2) of from 0.10 to 100.   6. The material composition according to claim 4, wherein the organic compound (B) contains at least one compound having at least one functional group selected from an aromatic ring, a condensed polycycle, a carbazole ring, and a fluorene ring. A material composition characterized by the above.   Antimony (III) oxide fine particles (A) 5% by mass to 50% by mass, organic compound (B) 49% by mass to 94% by mass having one or more polymerizable functional groups in one molecule, polymerization An optical element comprising a cured product of a material composition that is 0.05% by mass or more and 5% by mass or less of an initiator (C).   In a cured product of a material composition comprising fine particles (A) of antimony (III) oxide, an organic compound (B) having one or more polymerizable functional groups in one molecule, and a polymerization initiator (C), An optical system comprising a cured product of a material composition in which Abbe number νd, f-line and g-line anomalous dispersion ΔθgF is 15 ≦ νd ≦ 60 and −0.015 ≦ ΔθgF ≦ 0.075. element.   9. The optical element according to claim 7, wherein the optical element is a composite optical element in which a cured product of an optical material composition is laminated on the surface of an optical substrate by a photocuring reaction.

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