JP7086588B2 - Cured products, optical elements, optical instruments and methods for manufacturing optical elements - Google Patents

Description

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

In general, 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. Examples of the index showing the wavelength dispersibility of the refractive index include Abbe number (dispersion characteristic) (ν _d ) and secondary dispersion characteristic (θg, F). The Abbe number, θg, and F value are values peculiar to each optical material, but in many cases, they are within a certain range. FIG. 2 is a diagram showing the relationship between the secondary dispersion characteristics of conventional optical materials (glass material and organic material) and the Abbe number.

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

Further, when manufacturing an optical element having an excellent chromatic aberration correction function and having an aspherical shape or the like, a method such as molding an organic material on a glass material such as spherical glass is known rather than using only a glass material as a material. Has been done. Using this method has the advantages of being able to manufacture an optical element having excellent mass productivity, formability, degree of freedom in shape, and light weight. However, as shown in FIG. 2, the optical characteristics of the conventional organic material are within a limited range (secondary dispersion characteristics [θg, F] are 0.700 or less), and have peculiar dispersion characteristics. Very few organic materials are shown.

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

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

Japanese Unexamined Patent Publication No. 2012-1670119 Japanese Unexamined Patent Publication No. 2011-136961

However, although the organic material shown in Patent Document 1 has a higher θg and F value than the conventional general-purpose organic material, the adhesion between the glass substrate and the organic material is low, so that cracks occur during molding. Further, the organic material shown in Patent Document 2 has a very high θg and F value, but on the other hand, has a very low transmittance.

The present invention has been made in view of the background techniques described above, and has high refractive index dispersion characteristics (Abbe number (ν _d )) and secondary dispersion characteristics (θg, F), and high internal transmittance. It provides a cured product and an optical element or the like using the cured product.

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 the polymer material. It is characterized by.

(In the general formula (1), R ₁ and R ₂ are one selected from the following general formulas (2) to (5), and may be the same or different from each other.

＊は結合手を表す。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。）

* Represents a bond. In the general formulas (2) to (5), Z ₁ to Z ₄ are substituents having a molecular weight of 1 or more and less than 200 having hydrogen, carbon, oxygen, sulfur, nitrogen or halogen as a bonding atom, and are the same. 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 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 molded.

The optical device of the present invention is characterized by having the above-mentioned optical device.

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

The method for manufacturing an optical element of the present invention is characterized by including a step of providing the above-mentioned cured product on a base material or between two base materials, and a step of molding the cured product.

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

It is a schematic diagram 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 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. As used herein, the optical composition refers to a composition containing 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 of the substituents selected from the following general formulas (2) to (5), even if they are the same. It may be different. If a substituent other than hydrogen is present at the ortho position of the aromatic substituent, the refractive index property is deteriorated, the compatibility with other materials is high in the state of the optical composition, and the adhesion is improved in the state of the cured product. Therefore, these substituents are preferable.

* Represents a bond. In the general formulas (2) to (5), Z ₁ to Z ₄ are substituents having a molecular weight of 1 or more and less than 200 having hydrogen, carbon, oxygen, sulfur, nitrogen or halogen as a bonding atom, and are the same. 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 any integer selected from 1 to 3, and when b is 2 or 3, Z ₂ may be the same or different. )

When the molecular weight of Z ₁ to Z ₄ becomes large, the optical performance deteriorates, and it becomes impossible to crystallize in the purification process at the time of manufacturing, and it becomes difficult to improve the purity as an optical material. Therefore, 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 large molecular weight is selected from a substituent having a molecular weight of 1 or more and less than 200, it is preferable to highly control the purity and the residual solvent of the general formula (1) in order to maintain the optical performance of the cured product. .. Considering the difficulty in manufacturing, Z ₁ to Z ₄ have 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, and a trifluoro. 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 group, dimethylamino group, diethylamino group, dipropylamino 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- (Meta) acryloyloxyethoxy) ethyl group, 1- (3- (meth) acryloyloxypropoxy) ethyl group, 1- (3- (meth) acryloyloxy-2-methylpropoxy) ethyl group, 1-( It is more preferably a 4- (meth) acryloyloxybutoxy) ethyl group or the like.

Considering the difficulty in manufacturing, 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, and a 2- (meth) acryloyloxyethoxymethyl group. , 3- (meth) acryloyloxypropoxymethyl group, 3- (meth) acryloyloxy-2-methylpropoxymethyl group, 3- (meth) acryloyloxy-2, 2-dimethylpropoxymethyl group, 4- (meth) acryloyl Oxybutoxymethyl group, 1- (meth) acryloyloxyethyl group, 1- (2- (meth) acryloyloxyethoxy) ethyl group, 1- (3- (meth) acryloyloxypropoxy) ethyl group, 1- (3- (3-) It is more preferably a (meth) acryloyloxy-2-methylpropoxy) ethyl group or a 1- (4- (meth) acryloyloxybutoxy) ethyl group.

[Cursed product]
Next, the cured product of this embodiment will be described.

In the cured product of the present 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 is a feature.

The cured product of the present invention is roughly classified into the following aspects (A) to (D).
(A) A cured product in which the compound represented by the general formula (1) is polymerized.
(B) A cured product obtained by copolymerizing a compound represented by the general formula (1) with another copolymerizable polymerizable material.
(C) A cured product in which a 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.

[Manufacturing method of cured product]
Further, the method for producing a cured product of the present invention comprises a step of preparing an optical composition containing at least the compound represented by the general formula (1) and a step of polymerizing and curing the optical composition. It is a method for producing a cured product, which is characterized by having.

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

As the polymerization initiator, one that generates an active species such as a radical species or a cation species by light irradiation, or one that generates an active species such as a radical species by heat can be used.

Examples of the polymerization initiator that generates radical species by light irradiation include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 1-hydroxycyclohexylphenylketone, and 2-hydroxy-2-. Methyl-1-phenyl-Propane-1-one, Bis (2,4,6-trimethylbenzoyl) -Phenylphosphinoxide, 4-Phenylbenzophenone, 4-Phenyloxybenzophenone, 4,4'-Diphenylbenzophenone, 4,4' -Diphenoxybenzophenone and the like can be used.

Further, as the polymerization initiator that generates a cationic species by light irradiation, it is preferable to use iodonium (4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate.

Examples of the polymerization initiator that generates radical species by heat include azo compounds such as azobisisobutynitrile (AIBN), benzoyl peroxide, tert-butylperoxypivalate, tert-butylperoxyneohexanoate, and tert-hexyl. Use peroxides such as peroxyneohexanoate, tert-butyl peroxyneodecanoate, tert-hexyl peroxyneodecanoate, cumylperoxyneohexanoate, and cumylperoxyneodecanoate. Can be done.

The amount of the polymerization initiator added to the optical composition for producing the cured product of the present embodiment is 0.01% by mass or more with respect to the total mass of the compound represented by the general formula (1). The range of 00% by mass or less is preferable. The polymerization initiator may be used alone or in combination of two or more. The ratio of the polymerization initiator added to the compound represented by the general formula (1) may be appropriately selected depending on the amount of light irradiation and the additional heating temperature. Further, it may be adjusted according to the target average molecular weight of the obtained polymer.

The polymerization inhibitor is a hydroquinone-based agent such as hydroquinone, hydroquinone monomethyl ether, hydroquinone monoethyl ether, hydroquinone monopropyl ether, hydroquinone monobutyl ether, hydroquinone monopentyl ether, hydroquinone monohexyl ether, hydroquinone monooctyl ether, and hydroquinone monoheptyl ether. 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 suitable because they may turn yellow due to UV irradiation.

The polymerization inhibitor may be k, which uses the above-mentioned polymerization inhibitor as a polymerization inhibitor during reaction or storage, but is not limited thereto. The addition amount is preferably in the range of 0.01% by mass or more and 1.00% by mass or less with respect to the optical composition. Further, only one polymerization inhibitor may be used, or two or more kinds of polymerization inhibitors may be used in combination. Considering the amount of coloring, it is preferable to use a hydroquinone-based polymerization inhibitor in combination.

Photosensitizers include benzophenone, 4,4-diethylaminobenzophenone, 1-hydroxycyclohexylphenylketone, 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, acylphosphine oxide and the like can be used. The addition amount 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 light-resistant stabilizer is not particularly limited as long as it does not significantly affect the optical properties of the cured product, and is 2- (2H-benzotriazole-2-yl) -p-cresol, 2- (2H-benzotriazole-). 2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- [5-chloro (2H) -benzotriazole-2-yl] -4-methyl-6- (tert-butyl) ) Phenol, 2- (2H-benzotriazole-2-yl) -4,6-di-tert-pentylphenol, 2- (2H-benzotriazole-2-yl) -4- (1,1,3,3) -Tetramethylbutyl) phenol, 2,2'-methyllenbis [6- (2H-benzotriazole-2-yl)]-4- (1,1,3,3-tetramethylbutyl) phenol, 2- (2H-) Benzotriazole-2-yl) -6-dodecyl-4-methylphenol and other benzotriazole compounds, 2-cyano-3,3-diphenylacrylic acid ethyl, 2-cyano-3,3-diphenylacrylic acid 2- A cyanoacrylate-based compound such as ethylhexyl, a triazine-based compound, an octabenzone, a benzophenone-based compound such as 2,2'-4,4'-tetrahydrobenzophenone, and the like can be used. The light-resistant stabilizer may serve as a photosensitizer, in which case the photosensitizer may not be added. The addition amount 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 significantly 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 with side chains and 7 carbon atoms Alkyl esters of ~ 9, 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, hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl)] propionate and other hindered phenolic compounds, tris (2) , 4-Di-tert-butylphenyl) Phosphite and other phosphorus-based compounds, dioctadecyl-3,3'-thiodipropionate and other sulfur-based compounds can be used. The addition amount 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 is bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2, 2,6,6-Pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] A hindered amine compound such as butyl malonate can be used. can. The addition amount 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 embodiment (B), the cured product is produced by polymerizing an optical composition composed of a copolymerizable material and a compound represented by the general formula (1). Will 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 keep the dispersion characteristics and the secondary dispersion characteristics of the cured product in a range useful in optical design. .. The optical composition may further contain a polymerization inhibitor, a photosensitizer, a light-resistant stabilizer, a heat-resistant stabilizer, an antioxidant, a mold release agent, an antifungal agent and the like, if necessary. ..

As the copolymerizable polymerizable material, for example, a (meth) acrylic monomer can be used. For example, 1,3-adamantandiol dimethacrylate, 1,3-adamantandimethanol dimethacrylate, tricyclodecanedimethanol 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 diacrylate, 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 Glycoldimethacrylate, Trimethylol Propanetrimethacrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [4- (2-methacryloyloxyethoxy) 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, dietile Ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 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-acryloxydiethoxyphenyl) 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-methacrylate) Loxydiethoxyphenyl) methane, 1,1-bis (4-acryloxyethoxyphenyl) sulfone, 1,1-bis (4-methacryloxyethoxyphenyl) sulfone, 1,1-bis (4-acryloxydiethoxyphenyl) ) Sulfon, 1,1-bis (4-methacryloxydiethoxyphenyl) sulfone, dimethyloltricyclodecanediacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, glycerol diacrylate, glycerol dimethacrylate, pentaerythritol tri Aacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, methylthioacrylate, methylthiomethacrylate, phenylthioacrylate, benzylthiomethacrylate, xylylene dithioldiacrylate, xylylene dithioldimethacrylate, mercaptoethylsulfide diacrylate, mercaptoethylsulfide dimethacrylate, etc. (Meta) acrylate compound, allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, di Use allyl compounds such as ethylene glycol bisallyl carbonate, vinyl compounds such as styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene, 3,9-divinylspirobi (m-dioxane), diisopropenylbenzene and the like. However, it is not limited to these.

The amount of the copolymerizable polymerizable material added is preferably in the range of 0.10% by mass or more and 80.00% by mass or less with respect to the mass of the optical composition. Considering that the dispersion characteristics and the secondary dispersion characteristics of the cured product are in a range useful for optical design, it is preferably 0.10% by mass or more and 30.00% by mass or less.

As the polymerization initiator contained in the optical composition for producing the cured product of the aspect (B), the polymerization initiator shown in the aspect of (A) is used in the addition ratio shown in the aspect of (A). Can be done. Further, when a polymerization inhibitor, a photosensitizer, a light-resistant stabilizer, a heat-resistant stabilizer, or an antioxidant contained in the optical composition for producing the cured product of the aspect (B) is used, ( What is shown in the aspect of A) can be used in the addition ratio shown in the aspect of (A).

When the cured product of the present invention is the cured product of the aspect (C), the cured product is an optical composition in which the compound represented by the general formula (1) is dispersed in a copolymerizable polymerizable material. Manufactured by polymerization. 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. Considering 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 of the compound represented by the general formula (1) is 50. It is preferably 9.0% by mass or more and 99.9% by mass or less.

The optical composition may further contain a polymerization inhibitor, a photosensitizer, a light-resistant stabilizer, a heat-resistant stabilizer, an antioxidant, a mold release agent, an antifungal agent and the like, if necessary. ..

The polymerizable material is not particularly limited as long as the dispersion characteristics and the secondary dispersion characteristics of the cured product are within the useful range in optical design. Specifically, the (meth) acrylic monomer, allyl compound, vinyl compound, diisopropenylbenzene compound, epoxy compound, thylane compound and the like shown in the embodiment (B) can be used.

As the polymerization initiator contained in the optical composition for producing the cured product according to the aspect (C), the polymerization initiator shown in the aspect (A) is used in the addition ratio shown in the aspect (A). Can be done. Further, when a polymerization inhibitor, a photosensitizer, a light-resistant stabilizer, a heat-resistant stabilizer, or an antioxidant contained in the optical composition for producing the cured product of the aspect (C) is used, ( What is shown in the aspect of A) can be used in the addition ratio shown in the aspect 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 a compound represented by the general formula (1) and a compound represented by the compound represented by the general formula (1). It is produced by polymerizing or molding an optical composition composed of a 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 obtained 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. It is preferably mass% or less. The optical composition may further contain a polymerization inhibitor, a photosensitizer, a light-resistant stabilizer, a heat-resistant stabilizer, an antioxidant, a mold release agent, an antifungal agent and the like, if necessary. ..

The matrix polymer may be one or two (meth) acrylic polymer; allyl polymer; ethylene homopolymer, ethylene and propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and the like. Random or block copolymers with one or more α-olefins, one or more random or block copolymers with ethylene and vinyl acetate, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, propylene Homopolymer, random or block copolymer with one or more α-olefins such as propylene and 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, etc., 1 -Conduit-based resins such as butene homopolymers, ionomer resins, and mixtures of these polymers; hydrocarbon-based resins such as petroleum resins and terpene resins; polyester-based resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; nylon. 6, Nylon 66, Nylon 11, Nylon 12, Nylon 610, Nylon 6/66, Nylon 66/610, Nylon MXD and other polyamide-based resins; Acrylic resins such as polymethylmethacrylate; Polystyrene, styrene-acrylonitrile copolymers, styrene -Acrylonitrile-butadiene copolymer, styrene such as polyacrylonitrile, acrylonitrile resin; polyvinyl alcohol, polyvinyl alcohol resin such as ethylene-vinyl alcohol copolymer; polycarbonate resin; polyketone resin; polymethylene oxide resin; polysulfone resin; polyimide Resin; Polymerimide resin and the like can be mentioned, but the present invention is not limited thereto. One type of these resins may be used alone, or two or more types may be mixed and used. Further, these matrix polymers are appropriately selected in consideration of compatibility with the compound represented by the general formula (1), dispersion characteristics of the cured product, and secondary dispersion characteristics.

As the polymerization initiator contained in the optical composition for producing the cured product according to the aspect (D), the polymerization initiator shown in the aspect (A) is used in the addition ratio shown in the aspect (A). Can be done. Further, when a polymerization inhibitor, a photosensitizer, a light-resistant stabilizer, a heat-resistant stabilizer, or an antioxidant contained in the optical composition for producing the cured product of the aspect (D) is used, ( What is shown in the aspect of A) can be used in the addition ratio shown in the aspect of (A).

The mixing method with various additives, general-purpose monomers and matrix polymers is not particularly limited as long as they can be mixed uniformly. For example, a method of mixing all the materials with a solvent or the like and then removing the solvent, a method of heating the materials to melt them and mixing them as they are can be used. When preparing the optical composition for obtaining the cured product according to the embodiments (A), (B) and (C), the method of mixing in a solvent is preferable because it becomes uniform. When preparing the optical composition for obtaining the cured product according to the aspect (D), a method of heating the material and mixing it 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 the residual solvent in the optical composition is small, and a vacuum distillation method, a distillation method, or the like can be used. In the vacuum distillation method, since the polymerization reaction may be promoted under reduced pressure, it is preferable to distill under reduced pressure while circulating a gas containing oxygen. Further, in the distillation method, since the polymerization reaction may be promoted by heating, it is preferable to add a polymerization inhibitor and adjust the heating temperature as appropriate.

When the optical composition of the present embodiment is polymerized to produce the cured product according to the embodiments (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 an active species by light irradiation, the cured product of the present invention can be produced by irradiating the photopolymerization initiator with light having a suitable wavelength for generating an active species. conduct. Examples of light having a suitable wavelength include ultraviolet light or visible light. When the polymerization initiator is a thermal polymerization initiator that generates an active species by heating, the cured product of the present invention is produced by heating the thermal polymerization initiator to a suitable temperature for generating an active species. .. The suitable temperature is, for example, 80 ° C. or higher and 180 ° C. or lower.

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

The optical element of the present embodiment is characterized in that it is formed by molding a cured product according to the above embodiments (A) to (D). 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 of FIG. 2A, a thin film (optical member 10) formed by molding a cured product of the present invention is provided on one surface of a base material 20 as a base material. In the optical element of FIG. 2B, a thin film (optical member 10) formed by molding a cured product of the present invention is provided between two base materials, that is, between a substrate 30 and a substrate 40.

As the base materials 20, 30, 40, a plastic base material, a glass base material, or a resin base material can be used. Among these, it is preferable to use a glass base material in consideration of environmental resistance. The shape of the glass substrate is not limited, and it may be a flat surface, a curved surface, a concave surface, a convex surface, or a film.

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 dispersibility and high transmittance. Conventionally, a material having a high secondary dispersion property has an electron-donating substituent or a large conjugated structure, but the compound of the general formula (1) has an electron-donating substituent by introducing an aromatic heterocycle. It exhibits high secondary dispersion characteristics without having a large conjugated structure. In addition, the optical element of the present embodiment suppresses an extreme decrease in transmittance, has high adhesion between the base material and the cured product, and is less likely to crack.

Examples of the method for manufacturing the optical element of FIG. 1A include a method of forming a cured product of the present invention having a thin layer structure on a substrate made of a light-transmitting material. Specifically, a mold made of a metal material or the like is provided at a certain distance from the glass substrate, and the void between the mold and the glass substrate 20 is filled with the fluid optical composition of the present invention. After that, the mold is lightly pressed to perform mold molding. Then, the optical composition is polymerized while the mold is held down. The polymerization reaction is carried out by light irradiation or heating.

When the optical composition is polymerized by photopolymerization, for example, it is used as a raw material such as a monomer of the optical composition formed via a light transmissive material used as the substrate, specifically, a glass substrate 20. On the other hand, light irradiation is uniformly performed. 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 contained photopolymerization initiator.

As described above, in the production of a cured product of an optical composition by such a photopolymerization reaction, it is more preferable that the irradiated light uniformly irradiates the entire raw material such as a monomer to be molded. Therefore, it is more preferable to select light having a wavelength that can be uniformly irradiated through a light transmissive material used for the substrate, for example, a glass substrate. At this time, if the thickness of the optical composition formed on the substrate of the light-transmitting material is reduced, the amount of light irradiation during manufacturing is reduced and the weight is reduced, and the deformation due to thermal expansion and moisture absorption of the cured product can be reduced. 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 placed in a heating device 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 contained therein.

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

As a method for manufacturing the optical element of FIG. 2 (b), for example, an uncured optical composition of the present invention or the like is poured between the substrate 30 and the substrate 40 and lightly pressed to perform molding. Then, the uncured resin composition is photopolymerized while being maintained in this state to obtain a cured product. Thereby, 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 device of the present invention to reduce the film thickness of the cured product of the polymerizable composition formed on the substrate of the light-transmitting material. It will be something like that.

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

On the other hand, when the cured product of the present invention is used in the embodiment (C) above, a melt molding method can be used as the molding method for the cured product. By using the melt molding method, it is possible to obtain a molded product having excellent characteristics 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.

Further, 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 in the above temperature range, it is possible to impart appropriate fluidity to the resin during molding and prevent the occurrence of sink marks and strain 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 streak due to the thermal decomposition of the cured product, and further to effectively prevent the yellowing of the optical element.

(Optical equipment)
The optical device 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-2012-1670119.

As an example, compound D was produced by the following synthetic method.

Diphenylsulfone-4,4'-diylbis (trifluoromethanesulfonate) 44g, 5-formyl-2-franboronic acid 30g, sodium carbonate 45g, 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 (dibenzilidenacetone) palladium is added, and the mixture is heated and stirred at 80 ° C. for 5 hours for post-treatment. Got A mixed solution of 14 g of the obtained coupling body, 400 ml of tetrahydrofuran and 400 ml of methanol, 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 post-treatment was performed to obtain a reduced product. The hydroxyl group of the obtained reduced product was reacted with 2- (2-bromoethoxy) tetrahydro-2H-pyran with sodium hydride and then post-treated with an acidic aqueous solution to obtain a precursor of compound D. A solution of 5 g of the precursor of compound D in 50 ml of ethyl acetate and 10 ml of pyridine was cooled to 0 ° C., and 5.6 g of methacrylic anhydride was slowly added dropwise to synthesize compound D. The structure of the obtained compound D was confirmed by 1 HNMR.
^{1 1} H-NMR (CDCl3; TMS): δ 1.92 (s, 6H), 3.21 (t, 4H), 4.34 (t, 4H), 4.58 (s, 4H), 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)

The optical composition according to the general formula (1) was produced by mixing in a solvent in which all necessary materials were dissolved and distilling off the solvent under reduced pressure. At that time, in order to suppress the polymerization of the optical composition, a gas containing 5% oxygen was passed through the liquid.

(Procedure for preparing evaluation samples)
(1) Preparation of Optical Composition Each material was weighed and mixed so that the content of the compound represented by the general formula (1) was the content shown in each Example or each Comparative Example. For the mixture, 0.1% by mass of 4-methoxyphenol as a polymerization inhibitor and 1.0% by mass of 1-hydroxy-cyclohexylphenyl ketone as a polymerization initiator (IRGACURE 184 / BASF (formerly Ciba)). Made) was weighed. The above mixture and the weighed compound were mixed by dissolving all the materials in 3 times the amount of acetone of the general formula (1), and then the acetone was distilled off to prepare an optical composition. In the final step of distilling off the solvent in order to reduce the amount of residual solvent, a gas containing 5% oxygen was passed through the liquid and distilled off under reduced pressure at 80 ° C. for 15 minutes.

(2) Preparation of evaluation sample (2a) Refractive index measurement sample The optical composition in which two disk-shaped glass substrates having a diameter of 30 mm are prepared and contains a polymerization inhibitor, a polymerization initiator, etc. to be measured. The object was sandwiched between glass substrates on which spacers were installed so that the thickness was uniform at 500 μm. By irradiating the sample with ultraviolet light, the optical composition sandwiched between the two glass substrates was cured to produce a sample for measuring the refractive index.

(2b) Sample for transmittance measurement Four disk-shaped glass substrates having a diameter of 30 mm are prepared, and the optical composition containing a polymerization inhibitor, a polymerization initiator, etc. to be measured has a thickness of 500 μm. It was sandwiched between glass substrates with spacers so that it would be uniform at 200 μm. By irradiating each sample with ultraviolet light, the optical composition sandwiched between the two glass substrates was cured to produce a sample for transmittance measurement.

(2c) Sample for adhesion force measurement A disk-shaped glass substrate with a diameter of 30 mm and a thickness of 1 mm and a disk-shaped glass substrate with a diameter of 15 mm and a thickness of 5 mm are prepared, and the polymerization inhibitor to be measured and the polymerization start. The optical composition containing the agent and the like was sandwiched between the glass substrates by installing spacers so as to have a thickness of 50 μm. By irradiating it with ultraviolet light, the optical composition sandwiched between two glass substrates was cured, and a sample for measuring adhesion was produced.

(Evaluation method of prepared sample)
(2) Measurement and evaluation (2a) Refractive index, dispersion characteristics (Abbe number), secondary dispersion characteristics (θg, F)
Measured using an Abbe refractometer (Carnew Optical Industry), the table shows the refractive index at a wavelength of 587.6 nm, and the dispersion characteristics and secondary dispersion characteristics calculated from the following formula.
Abbe number (dispersion characteristic): [ν _d ] = (n _d -1) / (n _F −n _C )
Secondary dispersion characteristics: [θg, _F ] = ( _ng -nF) / ( _nF - _nC )

The secondary dispersion characteristics (θg, F) were evaluated according to the following criteria.
A: 0.75 or more (It is very useful from the viewpoint of durability because it has a very high chromatic aberration correction effect and can exert its effect even with a thin film).
B: 0.68 or more and less than 0.75 (Although the chromatic aberration correction effect is high, it is necessary to pay attention to the durability because it is necessary to increase the film thickness of the lens in order to fully exert the effect).
C: Less than 0.68 (The chromatic aberration correction effect is low even if the film thickness is increased.)

(2b) Transmittance Using a spectrophotometer U-4000 (product name) manufactured by Hitachi High-Technology Co., Ltd., samples of 500 μm and 200 μm were measured, respectively. 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 according to the following criteria.
A: Transmittance is 98% or more (in an optical system used in combination with a glass material, it can be incorporated into many types of optical systems).
B: Transmittance is 93% or more and less than 98% (it can be used only in a specific optical system using a glass material having high transmittance).
C: Transmittance is less than 93% (it can be used only in a specific optical system by making it thinner).

(2c) Adhesion force A resin layer is formed by fixing a substrate with a diameter of 30 mm and a substrate with a diameter of 15 mm using a jig and performing a tensile test at 0.1 mm / min using a tensile tester 5581 manufactured by Instron Japan. The adhesion force was measured and the maximum load at the time of breakage was determined. Adhesion was evaluated according to 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 during the reliability test).
B: Maximum load is 100N or more and less than 140N (It may rarely peel off when the mold release force is high, but it hardly peels off during the reliability test).
C: Maximum load is less than 100N (It is easy to peel off at the time of mold release, it is preferable to use a mold release agent, and it may peel off even in the reliability test).

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

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

The optical element of the present invention can be used for a lens and a prism. Further, the optical device 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 Substrate

Claims (12)

A cured product characterized in that 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.

(In the general formula (1), R ₁ and R ₂ are one selected from the following general formulas (2) to (5), and may be the same or different from each other.

* Represents a bond. In the general formulas (2) to (5), Z ₁ to Z ₄ are substituents having a molecular weight of 1 or more and less than 200 having hydrogen, carbon, oxygen, sulfur, nitrogen or halogen as a bonding atom, and are the same. 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 any integer selected from 1 to 3, and when b is 2 or 3, Z ₂ may be the same or different. ) In the general formulas (2) to (5), Z ₁ to Z ₄ are a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a methylthio group, an ethylthio group, a dimethylamino group, a 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- (3-) It is one selected from (meth) acryloyloxypropoxy) ethyl group, 1- (3- (meth) acryloyloxy-2-methylpropoxy) ethyl group, and 1- (4- (meth) acryloyloxybutoxy) ethyl group. The cured product according to claim 1, wherein the cured product is characterized by the above. In the general formulas (2) to (5), 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, and a 2- (meth) acryloyloxy. Ethoxymethyl group, 3- (meth) acryloyloxypropoxymethyl group, 3- (meth) acryloyloxy-2-methylpropoxymethyl group, 3- (meth) acryloyloxy-2, 2-dimethylpropoxymethyl group, 4-( Meta) acryloyloxybutoxymethyl group, 1- (meth) acryloyloxyethyl group, 1- (2- (meth) acryloyloxyethoxy) ethyl group, 1- (3- (meth) acryloyloxypropoxy) ethyl group, 1- The invention according to claim 1 or 2, wherein the group is selected from (3- (meth) acryloyloxy-2-methylpropoxy) ethyl group and 1- (4- (meth) acryloyloxybutoxy) ethyl group. Hardened product. 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 or more and 99.9% by mass or less. An optical element according to any one of claims 1 to 4, wherein the cured product is molded. The optical element according to claim 5, wherein the optical element is a lens. The optical element according to claim 6, wherein the optical element is a lens in which the cured product is provided on a base material. The optical element according to claim 6, wherein the optical element is a lens in which the cured product is provided between two substrates. An optical device comprising the optical element according to any one of claims 5 to 8. A compound characterized by being represented by the following general formula (1).

(In the general formula (1), R ₁ and R ₂ are any one selected from the following general formulas (2) to (5), and may be the same or different from each other.

* Represents a bond. In the general formulas (2) to (5), Z ₁ to Z ₄ are a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a methylthio group, an ethylthio group, a dimethylamino group, a 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- (3-) Any one selected from (meth) acryloyloxypropoxy) ethyl group, 1- (3- (meth) acryloyloxy-2-methylpropoxy) ethyl group, 1- (4- (meth) acryloyloxybutoxy) ethyl group. However, they may be the same or different from each other. 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 general formulas (2) to (5), 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, and a 2- (meth) acryloyloxy. Ethoxymethyl group, 3- (meth) acryloyloxypropoxymethyl group, 3- (meth) acryloyloxy-2-methylpropoxymethyl group, 3- (meth) acryloyloxy-2, 2-dimethylpropoxymethyl group, 4-( Meta) acryloyloxybutoxymethyl group, 1- (meth) acryloyloxyethyl group, 1- (2- (meth) acryloyloxyethoxy) ethyl group, 1- (3- (meth) acryloyloxypropoxy) ethyl group, 1- The compound according to claim 10, wherein the compound is one selected from a (3- (meth) acryloyloxy-2-methylpropoxy) ethyl group and a 1- (4- (meth) acryloyloxybutoxy) ethyl group. .. The step of providing the cured product according to any one of claims 1 to 4 on the substrate or between two substrates.
A method for manufacturing an optical element, which comprises a step of molding the cured product.

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