JP2019104884A - Cured product, optical element, optical instrument, and method of producing optical element - Google Patents

Abstract

To provide: a cured product whose refractive index has a high dispersion characteristic (Abbe number (ν)) and a high secondary dispersion characteristic (θg, F), and which has excellent adhesion; and an optical element based on the cured product.SOLUTION: The cured product is characterized in that a compound represented by general formula (1) is polymerized or copolymerized, or dispersed in a polymeric material. [In the formula, Rand Reach represent a pyridine derivative, thiophene derivative or furan derivative.]SELECTED DRAWING: None

Description

  The present invention relates to a cured product, an optical element and an optical apparatus using a compound having high refractive index dispersion characteristics and secondary dispersion characteristics (θg, F).

Generally, the refractive index of an optical material made of a glass material (glass material), an organic resin or the like gradually increases as the wavelength becomes shorter. The Abbe number (dispersion characteristic) (ν _d ), the second-order dispersion characteristic (θg, F), and the like can be given as an index indicating the wavelength dispersion of the refractive index. The Abbe number and the θg and F values are values unique to the respective optical materials, but in many cases, they fall within a certain range. FIG. 2 is a view showing the relationship between the secondary dispersion characteristics of the conventional optical material (glass material and organic material) and the Abbe number.

  In the refractive optical system, it is possible to reduce the chromatic aberration by appropriately combining glass materials having different dispersion characteristics. For example, in an objective lens such as a telescope, a chromatic aberration appearing on the axis is corrected by using a glass material having a small dispersion as a positive lens and a glass material having a large dispersion as a negative lens in combination. However, when the lens configuration and the number of lenses are limited or when the glass material to be used is limited, it may be difficult to sufficiently correct the chromatic aberration. As one of the methods for solving such problems, there is a method of utilizing a glass material having anomalous dispersion characteristics, and design of optical elements using this method is carried out.

  In addition, when manufacturing an optical element that is excellent in the function of correcting chromatic aberration and whose shape is aspheric or the like, a method is known in which an organic material is formed on a glass material such as spherical glass rather than using only a glass material. It is done. When this method is used, there is an advantage that an optical element excellent in mass productivity, moldability, shape freedom, and lightness can be manufactured. However, as shown in FIG. 2, the optical characteristics of the conventional organic material fall within a limited fixed range (second-order dispersion characteristics [θg, F] of 0.700 or less), and the unique dispersion characteristics Very little organic material is shown.

  Patent Document 1 proposes a compound having a sulfone (meth) acrylate and having a secondary dispersion property (high θg, F property) and an optical element using this compound.

  Patent Document 2 proposes that the heteroaromatic compound has not only a general-purpose organic material but also secondary dispersion characteristics higher than Patent Document 1.

JP, 2012-167019, A Unexamined-Japanese-Patent No. 2011-136961

  However, although the organic materials disclosed in Patent Document 1 have θg and F values higher than those of conventional general-purpose organic materials, the adhesion between the glass substrate and the organic material is low, and therefore cracking occurred during molding. The organic material disclosed in Patent Document 2 has very high θg and F values, but has very low transmittance.

The present invention has been made in view of the background art described above, and has high refractive index dispersion characteristics (Abbe number ( _{d d} )) and second-order dispersion characteristics (θg, F) and high internal transmittance. The present invention provides a cured product, an optical element using the cured product, and the like.

  In the cured product of the present invention, the compound represented by the following general formula (1) is polymerized or copolymerized, or the compound represented by the following general formula (1) is dispersed in a polymer material It is characterized by

(In General Formula (1), R ₁ and R ₂ are one selected from the following General Formulas (2) to (5), and they may be the same or different from each other.

一般式（２）乃至（５）中、Ｚ_１乃至Ｚ_４は、水素、炭素、酸素、硫黄、窒素又はハロゲンを結合原子とする分子量１以上２００未満の置換基であって、それぞれ同じであっても異なっていても良い。ａは１又は２であり、ａが２の場合はＺ_１、Ｚ_３、Ｚ_４は同じであっても異なっていても良い。ｂは１乃至３から選ばれるいずれかの整数であり、ｂが２又は３の場合、Ｚ_２は同じであっても異なっていても良い。）

In the general formulas (2) to (5), Z _{1 to} Z _{4 each} represent a substituent having a molecular weight of 1 or more and less than 200, each of which has hydrogen, carbon, oxygen, sulfur, nitrogen or halogen as a bonding atom. Or even different. a is 1 or 2, and when a is 2, Z ₁ , Z ₃ and Z ₄ may be the same or different. b is any integer selected from 1 to 3, and when b is 2 or 3, Z ₂ may be the same or different. )

  The optical element of the present invention is characterized in that the above-mentioned cured product is formed.

  An optical apparatus of the present invention includes the above-described optical apparatus.

  The compound of the present invention is characterized by being represented by the above general formula (1).

  The method for producing an optical element according to the present invention is characterized by comprising the step of providing the above-mentioned cured product on a substrate or between the substrates, and the step of molding the cured product. .

According to the present invention, it is possible to provide a cured product having high transmittance characteristics and high dispersion characteristics (Abbe number (( _d )) and secondary dispersion characteristics (θg, F) of refractive index.

It is the schematic which shows the example of the optical element of this invention. It is a graph which shows the relationship between the secondary dispersion characteristic of the conventional optical material, and an Abbe number.

  Hereinafter, the present invention will be described in detail.

[Optical composition, compound]
First, the optical composition of the present invention will be described. In the present specification, the optical composition refers to a composition including an uncured compound and an additive before the uncured resin is cured into a cured product. The optical composition of the present embodiment is characterized by containing at least a compound represented by the following general formula (1).

In the compound represented by the general formula (1), R ₁ and R ₂ are preferably any one substituent selected from the following general formulas (2) to (5), and each of them may be the same. It may be different. The presence of a substituent other than hydrogen at the ortho position of the aromatic substituent lowers the refractive index characteristics, and further improves the compatibility with other materials in the state of the optical composition and improves the adhesion in the state of the cured product Therefore, these substituents are preferable.

In the general formulas (2) to (5), Z _{1 to} Z _{4 each} represents a substituent having a molecular weight of 1 or more and less than 200, each of which has hydrogen, carbon, oxygen, sulfur, nitrogen, or halogen as a bonding atom. Or even different. a is 1 or 2, and when a is 2, Z ₁ , Z ₃ and Z ₄ may be the same or different. b is any integer selected from 1 to 3, and when b is 2 or 3, Z ₂ may be the same or different.

As the molecular weight of Z _{1 to} Z ₄ increases, the optical performance is lowered, and crystallization can not be performed in the purification step during production, and it becomes difficult to improve the purity as an optical material. Accordingly, Z _{1 to} Z ₄ are preferably substituents having a molecular weight of 1 or more and less than 200. When a substituent having a molecular weight of 1 or more and less than 200 is selected and a substituent having a large molecular weight is selected, in order to maintain the optical performance of the cured product, it is preferable to highly control the purity of the general formula (1) and the residual solvent. . Z _{1 to} Z ₄ may be a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a fluoromethyl group, a difluoromethyl group, a trifluoro group in view of the difficulty in production. Methyl group, methoxy group, ethoxy group, isopropoxy group, chloromethyloxy group, dichloromethyloxy group, trichloromethyloxy group, fluoromethyloxy group, difluoromethyloxy group, trifluoromethyloxy group, methylthio group, ethylthio group, Propylthio, dimethylamino, diethylamino, dipropylamino, (meth) acryloyloxymethyl, 2- (meth) acryloyloxyethoxymethyl, 3- (meth) acryloyloxypropoxymethyl, 3- (meth) Acryloyl oxy-2 Methyl propoxy methyl group, 3- (meth) acryloyloxy-2, 2-dimethyl propoxy methyl group, 4- (meth) acryloyloxy butoxy methyl group, 1- (meth) acryloyl oxyethyl group, 1- (2- (meth) ) Acryloyloxyethoxy) ethyl, 1- (3- (meth) acryloyloxypropoxy) ethyl, 1- (3- (meth) acryloyloxy-2-methylpropoxy) ethyl, 1- (4- (meth)) An acryloyloxybutoxy) ethyl group is more preferable.

Z _{1 to} Z ₄ are a hydrogen atom, a methyl group, a methoxy group, a methylthio group, a dimethylamino group, a (meth) acryloyloxymethyl group, a 2- (meth) acryloyloxyethoxymethyl group, in consideration of the degree of difficulty in production 3- (meth) acryloyloxypropoxymethyl group, 3- (meth) acryloyloxy-2-methylpropoxymethyl group, 3- (meth) acryloyloxy-2, 2-dimethylpropoxymethyl group, 4- (meth) acryloyl group Oxybutoxymethyl group, 1- (meth) acryloyloxyethyl group, 1- (2- (meth) acryloyloxyethoxy) ethyl group, 1- (3- (meth) acryloyloxypropoxy) ethyl group, 1- (3-) (Meth) acryloyloxy-2-methylpropoxy) ethyl group, 1- (4- (meth) a Further preferably Leroy oxy-butoxy) ethyl.

[Cured product]
Next, the hardened | cured material of this embodiment is demonstrated.

  In the cured product of this embodiment, at least the compound represented by the general formula (1) is polymerized or copolymerized, or the compound represented by the general formula (1) is dispersed in the polymer material. It features.

The cured product of the present invention is roughly classified into the following embodiments (A) to (D).
(A) A cured product in which the compound represented by the general formula (1) is polymerized.
(B) A cured product in which the compound represented by the general formula (1) and another copolymerizable polymerizable material are copolymerized.
(C) A cured product in which the compound represented by the general formula (1) is dispersed in another copolymerizable polymerizable material and these are copolymerized.
(D) A cured product in which the compound represented by the general formula (1) is dispersed in another matrix polymer.

[Method of producing a cured product]
In the method for producing a cured product of the present invention, a step of preparing an optical composition containing at least a compound represented by the general formula (1), and a step of polymerizing and curing the optical composition It is a manufacturing method of the hardened | cured material characterized by having.

  When the cured product of this embodiment is the cured product of (A), the cured product is produced by polymerizing an optical composition containing the compound represented by the general formula (1) and a polymerization initiator. Ru. The composition for optics may further contain, if necessary, a polymerization inhibitor, a photosensitizer, a light stabilizer, a heat stabilizer, an antioxidant, a mold release agent, a fungicide and the like. .

  As the polymerization initiator, those capable of generating active species such as radical species and cationic species by light irradiation and those capable of generating active species such as radical species by heat can be used.

  As a polymerization initiator which generates radical species by light irradiation, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2- Methyl-1-phenyl-propan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 4-phenylbenzophenone, 4-phenoxybenzophenone, 4,4'-diphenylbenzophenone, 4,4 ' -Diphenoxy benzophenone etc. can be used.

  Moreover, as a polymerization initiator which generate | occur | produces cationic seed | species by light irradiation, it is preferable to use iodonium (4-methylphenyl) [4- (2-methylpropyl) phenyl] hexafluorophosphate.

  As a polymerization initiator which generates radical species by heat, an azo compound such as azobis isobutyl nitrile (AIBN), benzoyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxy neohexanoate, tert-hexyl Using peroxides such as peroxy neohexanoate, tert-butyl peroxy neodecanoate, tert-hexyl peroxy neodecanoate, cumylperoxy neohexanoate, cumylperoxy neodecanoate, etc. Can.

  The addition amount of the polymerization initiator contained in the composition for optics for manufacturing the hardened | cured material of this embodiment is 0.01 mass% or more with respect to the total mass of the compound represented by General formula (1). The range of 00 mass% or less is preferable. The polymerization initiator may be used alone or in combination of two or more. The addition ratio of the polymerization initiator to the compound represented by the general formula (1) may be appropriately selected according to the light irradiation amount and further the additional heating temperature. Also, it may be adjusted according to the target average molecular weight of the resulting polymer.

  Polymerization inhibitors include hydroquinones such as hydroquinone, hydroquinone monomethyl ether, hydroquinone monoethyl ether, hydroquinone monopropyl ether, hydroquinone monobutyl ether, hydroquinone monopentyl ether, hydroquinone monopentyl ether, hydroquinone monooctyl ether, hydroquinone monooctyl ether, hydroquinone monoheptyl ether, etc. A phenol-based polymerization inhibitor having a substituent such as a polymerization inhibitor, 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, or the like can be used. However, hydroquinone-based polymerization inhibitors such as hydroquinone and benzoquinone-based polymerization inhibitors such as benzoquinone are not preferable because they may turn yellow upon UV irradiation.

  As the polymerization inhibitor, those described above as the polymerization inhibitor at the time of reaction or storage can be used, but k is not limited thereto. The addition amount is preferably in the range of 0.01% by mass to 1.00% by mass with respect to the composition for optics. Further, only one polymerization inhibitor may be used, or two or more polymerization inhibitors may be used in combination. Specifically, in consideration of the low coloring, it is preferable to use a combination of hydroquinone polymerization inhibitors.

  Photosensitizers include benzophenone, 4,4-diethylaminobenzophenone, 1-hydroxycyclohexyl phenyl ketone, isoamyl p-dimethylaminobenzoate, methyl 4-dimethylaminobenzoate, benzoin, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl Ether, 2,2-diethoxyacetophenone, methyl o-benzoylbenzoate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, acyl phosphine oxide and the like can be used. The addition amount is preferably in the range of 0.01% by mass to 10.00% by mass with respect to the composition for optics.

  The light stabilizer is not particularly limited as long as it does not significantly affect the optical properties of the cured product, and 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazole) 2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butyl) ) Phenol, 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3) -Tetramethylbutyl) phenol, 2,2'-Methylenebis [6- (2H-benzotriazol-2-yl)]-4- (1,1,3,3-tetramethylbutyl) phenol, 2- ( Benzotriazole compounds such as H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol, ethyl 2-cyano-3,3-diphenylacrylate, 2-cyano-3,3-diphenylacrylic acid It is possible to use cyanoacrylate compounds such as 2-ethylhexyl, triazine compounds, and benzophenone compounds such as octabenzone and 2,2'-4,4'-tetrahydrobenzophenone. In some cases, the above-mentioned light stabilizer plays a role of a photosensitizer, in which case the photosensitizer may not be added. The amount of addition is preferably in the range of 0.01% by mass or more and 10.00% by mass or less with respect to the optical composition.

  The heat-resistant stabilizer is not particularly limited as long as it does not greatly affect the optical properties of the cured product, and pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl)] propionate, Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,5-bis (1,1-dimethylethyl) -4-hydroxybenzenepropanoic acid having 7 carbon atoms having a side chain -9 alkyl esters, 4,6-bis (octylthiomethyl) -o-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylene bis (oxyethylene) bis [3- (5-tert) -Butyl-4-hydroxy-m-tolyl)] propionate, hexamethylene bis [3- (3,5-di-tert-butyl) Hindered phenol compounds such as -4-hydroxyphenyl)] propionate, phosphorus compounds such as tris (2,4-di-tert-butylphenyl) phosphite, dioctadecyl-3,3'-thiodipropio A sulfur-based compound such as a nitrate can be used. The amount of addition is preferably in the range of 0.01% by mass or more and 10.00% by mass or less with respect to the optical composition.

  The antioxidant is not particularly limited as long as it does not significantly affect the optical properties of the cured product, and bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,7) Use of hindered amine compounds such as 2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate etc. it can. The amount of addition is preferably in the range of 0.01% by mass or more and 10.00% by mass or less with respect to the optical composition.

  When the cured product of the present embodiment is the aspect (B), the cured product is produced by polymerizing an optical composition comprising a polymerizable material copolymerizable with the compound represented by the general formula (1). Be done. The content of the compound represented by the general formula (1) in the optical composition is preferably 1.0% by mass or more and 99.9% by mass or less. The compound represented by the general formula (1) is preferably contained in an amount of 50.0% by mass or more and 99.9% by mass or less in order to set the dispersion property and the secondary dispersion property of the cured product in a range useful for optical design . The composition for optics may further contain, if necessary, a polymerization inhibitor, a photosensitizer, a light stabilizer, a heat stabilizer, an antioxidant, a mold release agent, a fungicide and the like. .

  As the copolymerizable polymerizable material, for example, (meth) acrylic monomers can be used. For example, 1,3-adamantane diol dimethacrylate, 1,3-adamantane dimethanol dimethacrylate, tricyclodecane dimethanol diacrylate, pentaerythritol tetraacrylate, propoxylated neopentyl glycol diacrylate, dipropylene glycol diacrylate, ethoxylated Bisphenol A dimethacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, 2- (2-ethoxyethoxy) ethyl acrylate, stearyl acrylate, tetrahydrofurfuryl acrylate, 2-phenoxyethyl acrylate, isodecyl acrylate, isobonyl acrylate, Isobonyl methacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol di Crylates, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, tripropylene glycol dimethacrylate, dipropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, 9,9-bis [4- (2 -Acrylyloxyethoxy) phenyl] fluorene, 9,9-bis [4- (2-) Tacryloyloxyethoxy) phenyl] fluorene, 9,9-bis [4- (2-acryloyloxy) phenyl] fluorene, 9,9-bis [4- (2-methacryloyloxy) phenyl] fluorene, benzyl acrylate, benzyl methacrylate , Butoxyethyl acrylate, butoxymethyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenyl methacrylate, ethylene glycol diacrylate, ethylene Glycol dimethacrylate, diethylene glycol diacrylate, diethylene Glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate Ethylene glycol bisglycidyl acrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, 2,2-bis (4-acryloxyethoxyphenyl) propane, 2,2-bis (4-methacryloxyethoxyphenyl) ) Propane, 2,2-bis (4-acryloxydiethoxy group) Nyl) propane, 2,2-bis (4-methacryloxydiethoxyphenyl) propane, bisphenol F diacrylate, bisphenol F dimethacrylate, 1,1-bis (4-acryloxyethoxyphenyl) methane, 1,1-bis (4-methacryloxyethoxyphenyl) methane, 1,1-bis (4-acryloxydiethoxyphenyl) methane, 1,1-bis (4-methacryloxydiethoxyphenyl) methane, 1,1-bis (4-) Acryloxyethoxyphenyl) sulfone, 1,1-bis (4-methacryloxyethoxyphenyl) sulfone, 1,1-bis (4-acryloxydiethoxyphenyl) sulfone, 1,1-bis (4-methacryloxydiethoxy) Phenyl) sulfone, dimethylol tricyclodecane diacrylate, tri Tyrolpropane triacrylate, trimethylolpropane trimethacrylate, glycerol diacrylate, glycerol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, methylthioacrylate, methylthiomethacrylate, phenylthioacrylate, benzylthiomethacrylate, xylylene (Meth) acrylate compounds such as thiol diacrylate, xylylene dithiol dimethacrylate, mercaptoethyl sulfide diacrylate, mercaptoethyl sulfide dimethacrylate, allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, diaryl carbonate Use allyl compounds such as ethylene glycol bisallyl carbonate, vinyl compounds such as styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene, 3,9-divinyl spirobi (m-dioxane), diisopropenyl benzene and the like But not limited thereto.

  The addition amount of the copolymerizable polymerizable material is preferably in the range of 0.10% by mass to 80.00% by mass with respect to the mass of the composition for optics. It is preferably 0.10% by mass or more and 30.00% by mass or less, considering that the dispersion property and the secondary dispersion property of the cured product fall within a useful range in optical design.

  The polymerization initiator contained in the optical composition for producing the cured product of the embodiment of (B) uses the polymerization initiator shown in the embodiment of (A) at the addition ratio shown by the embodiment of (A) I can do it. Moreover, when using the polymerization inhibitor, the photosensitizer, the light-resistant stabilizer, the heat resistant stabilizer, and antioxidant which are contained in the composition for optics for manufacturing the hardened | cured material of the aspect of (B), Those shown in the embodiment of A) can be used at the addition ratio shown by the embodiment of (A).

  When the cured product of the present invention is a cured product of the aspect of (C), the cured product is an optical composition in which the compound represented by the general formula (1) is dispersed in a copolymerizable material. It is manufactured by polymerizing. The content of the copolymerizable polymerizable material contained in the optical composition is preferably 1.0% by mass or more and 99.0% by mass or less. The content of the compound represented by the general formula (1) is 50, taking into consideration the dispersion characteristics and secondary dispersion characteristics of the obtained cured product, and the compatibility between the compound represented by the general formula (1) and the polymerizable material. The content is preferably from 0% by weight to 99.9% by weight.

  The composition for optics may further contain, if necessary, a polymerization inhibitor, a photosensitizer, a light stabilizer, a heat stabilizer, an antioxidant, a mold release agent, a fungicide and the like. .

  The polymerizable material is not particularly limited as long as the dispersion property and the secondary dispersion property of the cured product fall within a useful range in optical design. Specifically, (meth) acrylic monomers, allyl compounds, vinyl compounds, diisopropenyl benzene compounds, epoxy compounds, thiirane compounds, etc. shown in the embodiment of (B) can be used.

  The polymerization initiator contained in the optical composition for producing the cured product of the aspect of (C) uses the polymerization initiator shown in the aspect of (A) at the addition ratio shown by the aspect of (A) I can do it. In the case of using a polymerization inhibitor, a photosensitizer, a light resistance stabilizer, a heat resistance stabilizer, and an antioxidant contained in the optical composition for producing the cured product of the aspect of (C), Those shown in the embodiment of A) can be used at the addition ratio shown by the embodiment of (A).

  When the cured product of the present invention is the cured product of the embodiment (D), the cured product can be dispersed with the compound represented by the general formula (1) and the compound represented by the compound represented by the general formula (1) Manufactured by polymerizing or molding an optical composition comprising the above matrix polymer. The content of the matrix polymer compound contained in the optical composition is preferably 1.0% by mass or more and 99.0% by mass or less. Considering the dispersion characteristics and secondary dispersion characteristics of the resulting cured product, and the compatibility between the compound represented by the general formula (1) and the matrix polymer, the content of the matrix polymer is 1.0% by mass or more and 50.0 or more % Or less is preferred. The composition for optics may further contain, if necessary, a polymerization inhibitor, a photosensitizer, a light stabilizer, a heat stabilizer, an antioxidant, a mold release agent, a fungicide and the like. .

  Examples of matrix polymers include (meth) acrylic polymers; allyl polymers; ethylene homopolymers, ethylene and propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, etc. Random or block copolymer with a kind or more of α-olefin, ethylene and vinyl acetate, acrylic acid, methacrylic acid, methyl acrylate, methyl acrylate, methyl methacrylate, methyl methacrylate, methyl methacrylate or random copolymer of one or more kinds, propylene Homopolymers, random or block copolymers of propylene and one or more α-olefins such as 1-butene other than propylene, 1-pentene, 1-hexene, 4-methyl-1-pentene, etc. -Polyolefins such as butene homopolymers, ionomer resins, and mixtures of these polymers Resins; hydrocarbon resins such as petroleum resins and terpene resins; polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 6/66 Polyamide resins such as nylon 66/610 and nylon MXD; acrylic resins such as polymethyl methacrylate; polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, styrene such as polyacrylonitrile, acrylonitrile resin; Polyvinyl alcohol resins such as polyvinyl alcohol and ethylene-vinyl alcohol copolymer; polycarbonate resin; polyketone resin; polymethylene oxide resin; polysulfone resin Polyimide resins; but polyamideimide resins are not limited thereto. These resins may be used alone or in combination of two or more. Further, these matrix polymers are appropriately selected in consideration of the compatibility with the compound represented by the general formula (1), the dispersion characteristics of the cured product and the secondary dispersion characteristics.

  The polymerization initiator contained in the optical composition for producing the cured product of the embodiment of (D) uses the polymerization initiator shown in the embodiment of (A) at the addition ratio shown by the embodiment of (A) I can do it. In the case of using a polymerization inhibitor, a photosensitizer, a light resistance stabilizer, a heat resistance stabilizer, and an antioxidant contained in the optical composition for producing the cured product of the embodiment of (D), Those shown in the embodiment of A) can be used at the addition ratio shown by the embodiment of (A).

  The mixing method with various additives, general purpose monomers and matrix polymer is not particularly limited as long as they can be uniformly mixed. For example, after mixing all the materials in a solvent etc., the method of removing a solvent, the method of heating and melting material, and mixing as it can be used. In preparing the optical composition for obtaining the cured product of the embodiments of (A), (B) and (C), the method of mixing in a solvent is preferable because the method is uniform. When preparing the optical composition for obtaining the cured product of the embodiment of (D), a method of heating and mixing the materials as it is is preferable in consideration of the low solubility of the matrix monomer in the solvent.

  The method for removing the solvent is not particularly limited as long as the amount of residual solvent in the optical composition decreases, and a vacuum distillation method, a distillation method, or the like can be used. In the reduced pressure distillation method, since the polymerization reaction may be promoted under reduced pressure, it is preferable to carry out the reduced pressure distillation while flowing a gas containing oxygen. Further, in the distillation method, since the polymerization reaction may be promoted by heating, it is preferable to appropriately adjust the addition of the polymerization inhibitor and the heating temperature.

  When the optical composition of this embodiment is polymerized to produce the cured products of the aspects (A) to (D), the polymerization reaction is initiated by the polymerization initiator in the optical composition. When the polymerization initiator is a photopolymerization initiator that generates active species by light irradiation, the cured product of the present invention is produced by irradiating light of a suitable wavelength at which the photopolymerization initiator generates active species. Do. The light of suitable wavelength includes, for example, ultraviolet light or visible light. When the polymerization initiator is a thermal polymerization initiator that generates active species by heating, the cured product of the present invention is produced by heating the thermal polymerization initiator to a suitable temperature that generates the active species. . A suitable temperature is, for example, 80 ° C. or more and 180 ° or less.

(Optical element, manufacturing method of optical element)
Next, the optical element of the present embodiment and the method of manufacturing the same will be described with reference to the drawings.

  The optical element of the present embodiment is characterized in that the cured product of the above aspects (A) to (D) is formed. FIG. 2 is a schematic view showing an optical lens as an example of the optical element of the present invention. In the optical element shown in FIG. 2A, a thin film (optical member 10) obtained by molding and processing the cured product of the present invention is provided on one surface of a substrate 20 which is a substrate. In the optical element of FIG. 2B, a thin film (optical member 10) formed by molding the cured product of the present invention is provided between two substrates, that is, between the substrate 30 and the substrate 40.

  As the substrates 20, 30, 40, plastic substrates, glass substrates or resin substrates can be used. Among these, in consideration of environmental resistance performance, it is preferable to use a glass substrate. The use of a glass substrate is also not limited in its shape, and may be flat, curved, concave, convex, or film-like.

  Since the optical element of the present embodiment has a cured product containing the compound of the general formula (1), it has both high secondary dispersion and high transmittance. Conventionally, materials with high secondary dispersion properties have electron donating substituents or large conjugated structures, but compounds of general formula (1) have electron donating substituents or an aromatic donating substituent by introducing an aromatic heterocycle. It exhibits high second-order dispersion characteristics without having a large conjugated structure. In addition, the optical element of the present embodiment suppresses the extreme decrease of the transmittance, and the adhesion between the base and the cured product is high, so that cracking does not easily occur.

  As a method of manufacturing the optical element of FIG. 1 (a), the method of forming the hardened | cured material of this invention of a layer structure with a thin film thickness is mentioned, for example on the base material which consists of light transmissive materials. Specifically, a mold made of a metal material or the like is provided at a certain distance from the glass substrate, and the space between this mold and the glass substrate 20 is filled with the composition for optical of the present invention having fluidity. Thereafter, molding is performed by holding the mold lightly. Then, while the mold is held down, the optical composition is polymerized. The polymerization reaction is carried out by light irradiation or heating.

  In the case of polymerizing an optical composition by photopolymerization, for example, as a raw material such as a light transmitting material used as the substrate, specifically, a monomer of the optical composition being molded via the glass substrate 20 On the other hand, light irradiation is carried out uniformly. The amount of light to be irradiated is appropriately selected according to the reaction mechanism using the photopolymerization initiator and according to the content ratio of the photopolymerization initiator to be contained.

  As described above, in the production of the cured product of the optical composition by the photopolymerization reaction, it is more preferable that the irradiated light be uniformly irradiated on the whole of the raw material such as the monomer being molded. Therefore, it is more preferable to select the light of the wavelength which can be uniformly performed via the light transmissive material used for a board | substrate, for example, a glass substrate, for the light irradiation utilized. Under the present circumstances, if the thickness of the composition for optics formed on the substrate of light transmission material is made thin, the amount of light irradiation at the time of manufacture will become small and lightweight, and also optical deformation which can reduce the deformation by thermal expansion and moisture absorption of hardened material It is preferable because it becomes an element.

  When the optical composition is polymerized by thermal polymerization, the optical composition may be polymerized by heating the mold, and the molded optical composition is heated in a heating apparatus such as an oven. The optical composition may be polymerized by heating. The heating temperature is appropriately selected according to the reaction mechanism using the thermal polymerization initiator and according to the content ratio of the photopolymerization initiator to be contained.

  Similar to the production of a cured product of the optical composition by the photopolymerization reaction, it is more preferable that heat be uniformly applied to the entire raw material of the optical composition being molded. Therefore, as a heating method to be used, it is more preferable that the molded optical composition be uniformly heated in a heating apparatus. Further, by thinning the thickness of the cured product formed on the mold, the optical composition can be uniformly heated even by a manufacturing method in which the optical composition is polymerized by heating the mold.

  As a method of manufacturing the optical element of FIG. 2B, for example, an uncured composition for optics of the present invention or the like is poured between the substrate 30 and the substrate 40, and molding is performed by lightly suppressing. And it is set as hardened | cured material by photopolymerizing an unhardened resin composition, keeping it in this state. As a result, an optical element in which the cured product of the present invention is sandwiched between the substrate 30 and the substrate 40 can be obtained.

  It is also possible to form a cured product by a thermal polymerization method. In this case, it is desirable to make the overall temperature more uniform, and it is more preferable for the optical element of the present invention to reduce the film thickness of the cured product of the polymerizable composition formed on the light transmitting material substrate. It becomes a thing.

  When the thickness of the cured product to be formed is increased, the film thickness, the irradiation amount of light in consideration of the light absorption of the resin component, the irradiation intensity of light, the light source, etc., and the heating temperature, heating time, etc. are appropriately selected. It is possible to thicken the cured product.

  On the other hand, when using the hardened | cured material of this invention in the aspect of said (C), a melt molding method can be used as a shaping | molding method of this hardened | cured material. By using the melt molding method, it is possible to obtain a molded product excellent in properties such as low birefringence, mechanical strength and dimensional accuracy. Examples of the melt molding method include press molding, extrusion molding, injection molding and the like, but injection molding is preferable from the viewpoint of moldability and productivity.

  The molding conditions in the molding step are appropriately selected depending on the purpose of use or the molding method. The temperature of the cured product in injection molding is preferably in the range of 150 ° C. to 400 ° C., more preferably in the range of 200 ° C. to 350 ° C., and particularly preferably in the range of 200 ° C. to 330 ° C. By molding the cured product within the above temperature range, it is possible to impart appropriate fluidity to the resin at the time of molding, and to prevent the occurrence of sink marks and distortion of the optical element of the present invention which is a molded product. Further, by molding the cured product in the above temperature range, it is possible to prevent the generation of silver streaks due to the thermal decomposition of the cured product, and to effectively prevent the yellowing of the optical element.

(Optical equipment)
The optical apparatus of this embodiment can be used, for example, for a camera having an optical lens, binoculars, a telescope, and the like.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the examples described below as long as the gist of the present invention is not exceeded.

(Compounds A to E)
The following compounds A to E were synthesized with reference to JP-A-2014-43565 and JP-A-2012-167019.

  As an example, Compound D was prepared by the following synthesis method.

44 g of diphenyl sulfone-4,4'-diylbis (trifluoromethanesulfonate), 30 g of 5-formyl-2-furanboronic acid, 45 g of sodium carbonate, 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl 1 After degassing a solution of 6 g, 1,4-dioxane 400 ml, and pure water 200 ml, 1.0 g of bis (dibenzylideneacetone) palladium is added, and the mixture is heated and stirred at 80 ° C. for 5 hours to perform a post treatment I got A mixed solution of 400 g of tetrahydrofuran and 400 ml of 14 g of the obtained coupling body was cooled to 0 ° C., 3.2 g of sodium borohydride was added little by little, and the temperature was raised to 24 ° C. over 5 hours. After confirming the end point of the reaction by liquid chromatography, water was added to stop the reaction and work up was carried out to obtain a reductant. After reacting the hydroxyl group of the obtained reductant with 2- (2-bromoethoxy) tetrahydro-2H-pyran and sodium hydride, the precursor of compound D was obtained by post-treatment with an acidic aqueous solution. Compound D was synthesized by cooling a solution of 5 g of a precursor of compound D in 50 ml of ethyl acetate and 10 ml of pyridine to 0 ° C. and slowly adding 5.6 g of methacrylic anhydride. The structure of the obtained compound D was confirmed by 1 H NMR.
¹ H-NMR (CDCl 3; TMS): δ 1.92 (s, 6 H), 3.21 (t, 4 H), 4.34 (t, 4 H), 4.58 (s, 4 H), 5.61 (S, 2H), 6.11 (s, 2H), 6.70 (d, 2H), 7.07 (d, 2H), 7.76-7.78 (m, 4H), 7.91 7.98 (m, 4H)

  Moreover, the composition for optics which consists of said General formula (1) was mixed in the solvent in which all the required materials melt | dissolve, and the solvent was depressurizingly distilled and manufactured. At that time, in order to suppress the polymerization of the optical composition, it was carried out while passing a gas containing 5% oxygen into the liquid.

(Preparation procedure of evaluation sample)
(1) Preparation of composition for optics Each material was weighed and mixed so that content of the compound represented by General formula (1) might become content shown by each Example or each comparative example. 0.1 mass% of 4-methoxyphenol as a polymerization inhibitor, 1.0 mass% of 1-hydroxy-cyclohexyl phenyl ketone as a polymerization initiator (IRGACURE 184 / BASF (formerly Ciba)) relative to the mixture Product was weighed. An optical composition was prepared by dissolving and mixing all the materials in a 3-fold amount of acetone of general formula (1) and mixing the above mixture and the weighed compounds. In order to reduce the amount of residual solvent, the final step of solvent evaporation was evaporation under reduced pressure at 80 ° C. for 15 minutes while passing a gas containing 5% oxygen through the solution.

(2) Preparation of Sample for Evaluation (2a) Sample for Refractive Index Measurement Two disc-shaped glass substrates each having a diameter of 30 mm are prepared, and the above optical composition containing a polymerization inhibitor to be measured, a polymerization initiator, etc. The object was sandwiched by a glass substrate provided with a spacer so as to be uniform at a thickness of 500 μm. The sample was irradiated with ultraviolet light to cure the optical composition sandwiched between the two glass substrates, and a sample for measuring the refractive index was manufactured.

(2b) Samples for transmittance measurement Prepare four disk-shaped glass substrates with a diameter of 30 mm, and use the above-mentioned optical composition containing a polymerization inhibitor to be measured, a polymerization initiator, etc. to a thickness of 500 μm and It was sandwiched by a glass substrate provided with a spacer so as to be uniform at 200 μm. Each sample was irradiated with ultraviolet light to cure the optical composition sandwiched between the two glass substrates, and a sample for transmittance measurement was manufactured.

(2c) Sample for measuring adhesion force Prepare a disc-shaped glass substrate of 30 mm in diameter and 1 mm in thickness, and a disc-shaped glass substrate of 15 mm in diameter and 5 mm in thickness, A spacer was installed so as to have a thickness of 50 μm, and the above-mentioned optical composition containing an agent etc. was sandwiched by the above-mentioned glass substrate. The composition for optics pinched between two glass substrates was hardened by irradiating ultraviolet light there, and the sample for adhesion measurement was manufactured.

(Evaluation method of preparation sample)
(2) Measurement and evaluation (2a) Refractive index, dispersion characteristic (Abbe number), second-order dispersion characteristic (θg, F)
The refractive index at a wavelength of 587.6 nm and the dispersion characteristics and secondary dispersion characteristics calculated from the following equation are shown in the table.
Abbe number (dispersion characteristic): [ν _d ] = (n _d −1) / (n _F −n _C )
Secondary dispersion _{characteristic: [θg, F] = (} n g -n F) / (n F -n C)

Second-order dispersion characteristics (θg, F) were evaluated according to the following criteria.
A: 0.75 or more (The effect of correcting the chromatic aberration is very high, and even if it is a thin film, the effect can be exhibited, which is also very useful in terms of durability.)
B: 0.68 or more and less than 0.75 (The chromatic aberration correction effect is high, but in order to exert the effect sufficiently, it is necessary to increase the film thickness of the lens, so it is necessary to pay attention to the durability)
C: less than 0.68 (the chromatic aberration correction effect is low even if the film thickness is increased)

(2b) Transmittance Samples of 500 μm and 200 μm were respectively measured using a spectrophotometer U-4000 (product name) manufactured by Hitachi High-Technologies Corporation. The internal transmittance of 500 μm was calculated from each data, and the transmittance at a wavelength of 430 nm was calculated. The transmittance was evaluated based on the following criteria.
A: Transmittance 98% or more (In an optical system used in combination with a glass material, it is possible to incorporate it into many types of optical systems.)
B: Transmittance 93% or more and less than 98% (It can be used only in a specific optical system using a glass material having a high transmittance)
C: Transmittance of less than 93% (It is possible to use only in a specific optical system by thinning)

(2c) Adhesive force A substrate with a diameter of 30 mm and a substrate with a diameter of 15 mm are fixed using a jig, and a tensile test is conducted at 0.1 mm / min using an Instron Japan tensile tester 5581 to obtain a resin layer. The adhesion of the sample was measured to determine the maximum load at break. The adhesion was evaluated based on the following criteria.
A: The maximum load is 140 N or more (It is possible to mold without peeling even when the mold release force is high, and it hardly peels even in the reliability test)
B: The maximum load is 100 N or more and less than 140 N (It may peel off rarely when the mold release force is high, but it hardly peels off in the reliability test)
C: Maximum load is less than 100 N (It is preferable to use a mold release agent because it is easy to peel off during mold release, and may peel off even in the reliability test)

(Examples 1 to 7)
Each material was weighed at the addition ratio described in Table 1, the polymerization initiator and the polymerization inhibitor were further weighed, and the preparation and evaluation were performed by the above-mentioned method. The evaluation results are shown in Table 1.

(Comparative Examples 1 to 3)
Each material was weighed at the addition ratio described in Table 1, the polymerization initiator and the polymerization inhibitor were further weighed, and the preparation and evaluation were performed by the method described above. The evaluation results are shown in Table 1.

  The optical element of the present invention can be used for lenses and prisms. Further, the optical apparatus of the present invention can be used for a telescope, binoculars, a camera or the like having the optical element of the present invention.

10 optical members 20, 30, 40 substrates

Claims (13)

A cured product characterized in that a compound represented by the following general formula (1) is polymerized or copolymerized, or a compound represented by the following general formula (1) is dispersed in a polymer material.

(In General Formula (1), R ₁ and R ₂ are one selected from the following General Formulas (2) to (5), and they may be the same or different from each other.

In the general formulas (2) to (5), Z _{1 to} Z _{4 each} represent a substituent having a molecular weight of 1 or more and less than 200, each of which has hydrogen, carbon, oxygen, sulfur, nitrogen or halogen as a bonding atom. Or even different. a is 1 or 2, and when a is 2, Z ₁ , Z ₃ and Z ₄ may be the same or different. b is any integer selected from 1 to 3, and when b is 2 or 3, Z ₂ may be the same or different. ) In the above general formulas (2) to (5), Z _{1 to} Z _{4 each} represents a hydrogen atom, methyl group, ethyl group, methoxy group, ethoxy group, ethoxy group, methylthio group, ethylthio group, dimethylamino group, diethylamino group, (meth) Acryloyloxymethyl group, 2- (meth) acryloyloxyethoxymethyl group, 3- (meth) acryloyloxypropoxymethyl group, 3- (meth) acryloyloxy-2-methylpropoxymethyl group, 3- (meth) acryloyloxy- 2,2-Dimethylpropoxymethyl group, 4- (meth) acryloyloxybutoxymethyl group, 1- (meth) acryloyloxyethyl group, 1- (2- (meth) acryloyloxyethoxy) ethyl group, 1- (3-) (Meth) acryloyloxypropoxy) ethyl group, 1- (3- (meth) acryloyloxy 2-methyl propoxy) ethyl group, 1- (4- (meth) acryloyloxy-butoxy) cured product according to claim 1, characterized in that one selected from an ethyl group. In the general formulas (2) to (5), Z _{1 to} Z _{4 each} represents a hydrogen atom, a methyl group, a methoxy group, a methylthio group, a dimethylamino group, a (meth) acryloyloxymethyl group, a 2- (meth) acryloyloxy Ethoxymethyl group, 3- (meth) acryloyloxypropoxymethyl group, 3- (meth) acryloyloxy-2-methylpropoxymethyl group, 3- (meth) acryloyloxy-2, 2-dimethylpropoxymethyl group, 4- (4-) 1) (meth) acryloyloxy butoxy methyl group, 1-(meth) acryloyl oxyethyl group, 1-(2- (meth) acryloyl oxy ethoxy) ethyl group, 1-(3- (meth) acryloyl oxy propoxy) ethyl group, 1- (3- (meth) acryloyloxy-2-methylpropoxy) ethyl group, 1- (4- (meth)) Acryloyloxy-butoxy) cured product according to claim 1 or 2, characterized in that one selected from an ethyl group.   The cured product according to any one of claims 1 to 3, wherein the compound represented by the general formula (1) is contained in an amount of 50.0% by mass to 99.9% by mass.   An optical element on which the cured product according to any one of claims 1 to 4 is formed.   The optical element according to claim 5, wherein the optical element is a lens.   The said optical element is a lens by which the said hardened | cured material was provided on the glass base material, The optical element of Claim 6 characterized by the above-mentioned.   The optical element according to claim 6, wherein the optical element is a lens in which the cured product is provided between two glass substrates.   An optical apparatus comprising the optical element according to any one of claims 5 to 8. The compound represented by following General formula (1).

(In General Formula (1), R ₁ and R ₂ are any one selected from the following General Formulas (2) to (5), and they may be the same or different from each other.

In the general formulas (2) to (5), Z _{1 to} Z _{4 each} represents a substituent having a molecular weight of 1 or more and less than 200 starting with hydrogen, carbon, oxygen, sulfur, nitrogen or halogen It may be different. a is 1 or 2, and when a is 2, Z ₁ , Z ₃ and Z ₄ may be the same or different. b is one selected from 1 to 3, and when b is 2 or 3, Z ₂ may be the same or different. ) In the above general formulas (2) to (5), Z _{1 to} Z _{4 each} represents a hydrogen atom, methyl group, ethyl group, methoxy group, ethoxy group, ethoxy group, methylthio group, ethylthio group, dimethylamino group, diethylamino group, (meth) Acryloyloxymethyl group, 2- (meth) acryloyloxyethoxymethyl group, 3- (meth) acryloyloxypropoxymethyl group, 3- (meth) acryloyloxy-2-methylpropoxymethyl group, 3- (meth) acryloyloxy- 2,2-Dimethylpropoxymethyl group, 4- (meth) acryloyloxybutoxymethyl group, 1- (meth) acryloyloxyethyl group, 1- (2- (meth) acryloyloxyethoxy) ethyl group, 1- (3-) (Meth) acryloyloxypropoxy) ethyl group, 1- (3- (meth) acryloyloxy 2-methyl propoxy) ethyl group, 1- (4- (meth) acryloyloxy-butoxy) A compound according to claim 10, characterized in that any one selected from an ethyl group. In the general formulas (2) to (5), Z _{1 to} Z _{4 each} represents a hydrogen atom, a methyl group, a methoxy group, a methylthio group, a dimethylamino group, a (meth) acryloyloxymethyl group, a 2- (meth) acryloyloxy Ethoxymethyl group, 3- (meth) acryloyloxypropoxymethyl group, 3- (meth) acryloyloxy-2-methylpropoxymethyl group, 3- (meth) acryloyloxy-2, 2-dimethylpropoxymethyl group, 4- (4-) 1) (meth) acryloyloxy butoxy methyl group, 1-(meth) acryloyl oxyethyl group, 1-(2- (meth) acryloyl oxy ethoxy) ethyl group, 1-(3- (meth) acryloyl oxy propoxy) ethyl group, 1- (3- (meth) acryloyloxy-2-methylpropoxy) ethyl group, 1- (4- (meth)) A compound according to claim 10 or 11, wherein the acryloyloxy-butoxy) is one selected from an ethyl group. Providing the cured product according to any one of claims 1 to 3 on or between the substrates;
And b. Molding the cured product.

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