WO2021095326A1 - Precursor resin composition, and optical element - Google Patents

Precursor resin composition, and optical element Download PDF

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Publication number
WO2021095326A1
WO2021095326A1 PCT/JP2020/032813 JP2020032813W WO2021095326A1 WO 2021095326 A1 WO2021095326 A1 WO 2021095326A1 JP 2020032813 W JP2020032813 W JP 2020032813W WO 2021095326 A1 WO2021095326 A1 WO 2021095326A1
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component
resin composition
precursor resin
optical element
fluorine
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PCT/JP2020/032813
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French (fr)
Japanese (ja)
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一範 小森
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株式会社タムロン
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

Definitions

  • the present invention relates to a precursor resin composition and an optical element, and a precursor resin composition for obtaining a UV curable resin used for producing an optical element having anomalous partial dispersion characteristics, and such a UV curable resin.
  • the present invention relates to an optical element obtained by using a precursor resin composition used for production.
  • the optical glass forming the glass lenses There are many types, having various refractive index n d and the Abbe number [nu d and secondary dispersion characteristic theta gF have been developed. Distribution of the optical properties of these optical glasses, when the Abbe number [nu d is low has a high second-order dispersion characteristic theta gF, the second-order dispersion characteristic theta gF as the Abbe number [nu d is higher tended to be lower There is.
  • synthetic resins that may be used as a resin composition for forming the resin lens, on the small type, the range of the refractive index n d and the Abbe number [nu d and secondary dispersion characteristic theta gF is limited.
  • Patent Document 1 contains a sulfur-containing compound and a polymerization initiator, and the Abbe number ⁇ d after curing is determined.
  • a resin composition for forming an optical element which has a range of more than 18 and less than 23, and a secondary dispersion characteristic ⁇ gF of more than 0.68 and less than 0.69, is disclosed.
  • Patent Document 2 contains a fluorine-containing organic compound and a polymerization initiator, and the Abbe number ⁇ d after curing is in the range of more than 30 and less than 85, and the secondary dispersion characteristic ⁇ gF is 0.
  • Japanese Patent Publication Japanese Patent Laid-Open No. 2010-97195
  • Japanese Publication Application Gazette Japanese Patent Laid-Open No. 2019-151809
  • the resin composition for forming an optical element described in Patent Document 1 has poor compatibility with other solvents and tends to be easily discolored after curing. Moreover, since the crystallization temperature is higher than room temperature, it is difficult to handle as a resin composition used for an optical element.
  • the resin composition for forming an optical element described in Patent Document 2 has a low refractive index.
  • the shape of the optical element becomes a biconvex shape close to a sphere.
  • the resin composition has a larger linear expansion and dn / dT (temperature coefficient of refractive index) than glass, and a biconvex shape close to a sphere is not preferable as a lens because these effects are remarkably exhibited.
  • precursors can have a higher degree of freedom in optical design It is an object of the present invention to provide a resin composition and an optical element using such a precursor resin composition.
  • the precursor resin composition for obtaining the UV curable resin according to the present invention is a UV curable resin used for manufacturing an optical element having anomalous partial dispersion characteristics. It is a precursor resin composition for obtaining, and the above-mentioned precursor resin composition is characterized by containing the following A component, B component, and C component.
  • Component A Bifunctional fluorine-containing acrylate and / or bifunctional fluorine-containing methacrylate.
  • Component B Bifunctional acrylate having a benzene ring and / or bifunctional methacrylate having a benzene ring.
  • Component C Photopolymerization initiator.
  • optical element having anomalous partial dispersion characteristics The optical element having anomalous partial dispersion performance according to the present invention is characterized by being obtained by using a precursor resin composition for obtaining the above UV curable resin.
  • Precursor resin composition according to the present invention by containing a fluorine-containing organic compounds described above, the characteristics of the refractive index n d and second-order dispersion characteristic theta gF against Abbe number [nu d after curing and conventional glass lenses Different properties can be obtained. As a result, the precursor resin composition according to the present invention can have a higher degree of freedom in optical design.
  • the precursor resin composition for obtaining the UV curable resin according to the present invention is a UV used for producing an optical element having anomalous partial dispersion characteristics. It is a precursor resin composition for obtaining a curable resin, and the above-mentioned precursor resin composition is characterized by containing a component A, a component B, and a component C shown below.
  • Component A Bifunctional fluorine-containing acrylate and / or bifunctional fluorine-containing methacrylate.
  • Component B Bifunctional acrylate having a benzene ring and / or bifunctional methacrylate having a benzene ring.
  • Component C Photopolymerization initiator.
  • the precursor resin composition for obtaining the UV curable resin according to the present invention contains the above-mentioned fluorine-containing organic compound, so that the Abbe number ⁇ d after curing. characteristics of the refractive index n d and secondary dispersion characteristics theta gF against is different from the conventional glass lens or a plastic lens (e.g., a resin lens obtained by the optical element-forming resin composition described in Patent Document 2). Thereby, the chromatic aberration can be corrected more effectively in combination with the glass lens, and a higher degree of freedom can be given in the optical design. Specifically, compared to the optical element forming resin composition described in Patent Document 2, the extent Abbe number [nu d is 20 to 50.
  • the refractive index n d is high, a higher second-order dispersion characteristic theta gF Optical characteristics can be realized. Therefore, the a precursor resin composition resin lens formed using, when "the Abbe number [nu d is low has a high second-order dispersion characteristic theta gF, second-order dispersion characteristic as the Abbe number [nu d is increased theta gF By combining with a "glass lens that exhibits low optical characteristics", it is possible to have a higher degree of freedom in optical design, and it is possible to sufficiently correct chromatic aberration.
  • the precursor resin composition for obtaining the UV curable resin according to the present invention contains at least one of a fluorine-containing organic compound, a bifunctional fluorine-containing acrylate and a bifunctional fluorine-containing methacrylate, as the component A. It is something to do.
  • the fluorine content of the fluorine-containing organic compound is preferably 20% by mass or more and 50% by mass or less. When the fluorine content is less than 20% by mass, after curing, when compared with the resin composition for forming an optical element described in Patent Document 2, "the refractive index is in the range where the Abbe number ⁇ d is 20 or more and 50 or less.
  • n d is high, second-order dispersion characteristic theta gF is unfavorably fail to achieve high precursor resin composition ". It is difficult to obtain a fluorine-containing organic compound having a fluorine content of more than 50% by mass.
  • the content of the component A in the precursor resin composition for obtaining the UV curable resin according to the present invention is preferably 20% by mass or more and 80% by mass or less. If the content of the component A is less than 20% by mass, the secondary dispersion characteristic ⁇ gF is too low, which is not preferable. If the content of the component A exceeds 80% by mass, the refractive index nd is too low, which is not preferable.
  • the component A according to the present invention has the structural formula shown in Chemical formula 1 below. It is known that an organic compound having a benzene ring is effective for increasing the refractive index in a resin composition. By containing at least one bifunctional fluorine acrylate and bifunctional fluorine methacrylate as the A component, the A component and the B component containing at least one of the bifunctional acrylate and the bifunctional methacrylate containing a large amount of benzene rings. This is because the compatibility with is improved.
  • R 21 and R 22 are independent hydrogen atoms or methyl groups, x is an integer of 1 to 2, and Y is a perfluoroalkyl group having 2 to 12 carbon atoms or-(CF 2- O). -CF 2 ) Z- , and z is an integer of 1 to 4. ]
  • fluorine-containing organic compound used as the component A examples include 2,2,3,3,4,5,5-Octafluorohexan-1,6-diyl dialclylate (CAS: 2264-01-9), 2. , 2,3,3,4,5,5-Octofluorohexan-1,6-diyl compound (CAS: 66818-54-0), 2,2,3,3,4,4-Hexafluoropen-1,5 -Diyl dimethacrylate (CAS: 918-36-5) and the like can be mentioned.
  • the precursor resin composition for obtaining the UV curable resin according to the present invention contains at least one of a bifunctional acrylate having a benzene ring and a bifunctional methacrylate having a benzene ring as the component B. is there.
  • the content of the B component in the precursor resin composition for obtaining the UV curable resin according to the present invention is preferably 20% by mass or more and 80% by mass or less. If the content of the B component is less than 20% by mass, the refractive index nd is too low, which is not preferable. If the content of the B component exceeds 80% by mass, the secondary dispersion characteristic ⁇ gF is too low, which is not preferable.
  • organic compound used as the B component examples include 2.2 Bis [4- (Acryloxy Polyethoxy) Phenyl] Propane ethoxylated bisphenol A diacrylate (CAS: 64401-02-1), 9,9-Bis [4. -(2-acryloyloxy) phenyl] fluorene 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (CAS: 1234827-45-2), Bis (4-methacryloylthiophenyl) Sulfide (CAS: 129283-) 82-5), bis [4- (2-hydroxyethoxy) phenyl] sulfone (CAS: 27205-03-4) and the like can be mentioned.
  • the precursor resin composition for obtaining the UV curable resin according to the present invention contains a photopolymerization initiator as the component C.
  • the photopolymerization initiator is used to polymerize a fluorine-containing organic compound.
  • the photopolymerization initiator only one type may be used or two or more types may be used in combination depending on the reactivity of the fluorine-containing organic compound and the wavelength of light irradiation.
  • the amount of the C component added to the precursor resin composition for obtaining the UV curable resin according to the present invention is preferably 0.001% by mass or more and 5% by mass or less. If the content of the C component is less than 0.001% by mass, it does not cure, which is not preferable. If the content of the C component exceeds 5% by mass, it will be cured during storage, which is not preferable.
  • photopolymerization initiator used as the C component examples include 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, 1- [4- (4).
  • the precursor resin composition for obtaining the UV curable resin according to the present invention also contains at least one of a fluorine-containing organic compound, a monofunctional fluorine-containing acrylate and a monofunctional fluorine-containing methacrylate, as the D component. Is preferably included.
  • the fluorine content in the D component which is a fluorine-containing organic compound, is preferably 20% by mass or more and 70% by mass or less. When the fluorine content is less than 20% by mass, the refractive index n after curing is in the range where the Abbe number ⁇ d is 20 or more and 50 or less as compared with the resin composition for forming an optical element described in Patent Document 2.
  • the content of the D component in the precursor resin composition for obtaining the UV curable resin according to the present invention is preferably 1% by mass or more and 30% by mass or less. If the content of the D component is less than 1% by mass, the secondary dispersion characteristic ⁇ gF cannot be improved, which is not preferable. If the content of the D component exceeds 30% by mass, compatibility is lost and transparency is lost, which is not preferable.
  • fluorine-containing organic compound used as the D component examples include 2,2,3,3,4,5,5,6,6,7,7-Dodecafluoroheptyl Acrylate (CAS: 2993-85-3). , 1H, 1H, 2H, 2H-Heptadecafluorodecil Acrylate (CAS: 27905-45-9), 2,2,3,4,5,4-Hexafluorobutyl Acrylate (CAS: 54052-90-3), 1,1,1 , 3,3,3-Hexafluoroisopropyl Acrylate (CAS: 2160-89-6), 1H, 1H, 2H, 2H-Nonafluorohexyl Acrylate (CAS: 52591-27-2), 1H, 1H, 5H-Octal 376-84-1), 1H, 1H-Pentadecafluoro-n-octyl Acrylate (CAS: 307-98-2), Pentafluorophenyl Acrylate (CAS: 71195-85-2), 2,
  • Component E The precursor resin composition for obtaining the UV curable resin according to the present invention also contains at least one of a monofunctional acrylate having a benzene ring and a monofunctional methacrylate having a benzene ring as the E component. Is preferable.
  • the amount of the E component added to the precursor resin composition for obtaining the UV curable resin according to the present invention is preferably 1% by mass or more and 40% by mass or less. When the content of component E is less than 1 mass% is not preferable because the refractive index n d is not high. If the content of the E component exceeds 40% by mass, compatibility is lost and transparency is lost, which is not preferable.
  • organic compound used as the E component examples include Benzyl Acrylate (CAS: 2495-35-4), Benzyl Cinnamate (CAS: 103-41-3), Pentafluorobenzolylate (CAS: 114859-23-3), and Pentabro.
  • the precursor resin composition for obtaining the UV curable resin according to the present invention contains the above-mentioned components, and after curing, the optical element described in Patent Document 2.
  • the resin composition for forming an Abbe number [nu d is in the range of 20 to 50 or less it is possible to realize a high refractive index n d, and a high second-order dispersion characteristic theta gF. Therefore, the resin lens formed by using the precursor resin composition tends to have a high secondary dispersion characteristic ⁇ gF when the Abbe number ⁇ d is low, and a low secondary dispersion characteristic ⁇ gF when the Abbe number ⁇ d is high.
  • the precursor resin composition for obtaining the UV curable resin according to the present invention has an Abbe number in the range of 20 or more and 50 or less as compared with the resin composition for forming an optical element described in Patent Document 1. Almost the same optical characteristics can be realized, and it can be used for correction of chromatic aberration as described above. Further, unlike the resin composition for forming an optical element described in Patent Document 1, the precursor resin composition has a structure in which oxygen is not attached to sulfur in the chemical formula, so that the precursor resin compositions are compatible with each other. It is easy to handle as a resin composition used for forming an optical element because of its good quality and low crystallization temperature.
  • Embodiment of an Optical Element with Anomalous Partial Dispersion Characteristics is characterized by being obtained by curing the above-mentioned precursor resin composition by irradiating it with ultraviolet rays.
  • the internal transmittance with respect to light having a wavelength of 430 nm is preferably 90% or more. If the internal transmittance is less than 90%, the use as an optical element is limited, which is not preferable.
  • abnormal partial dispersion characteristic means a characteristic in which the refractive index difference (partial dispersion) changes peculiarly depending on the wavelength
  • having an abnormal partial dispersion characteristic means that the abnormal partial dispersion characteristic is. It means high.
  • the optical element having anomalous partial dispersion characteristics according to the present invention in order to increase the degree of freedom in optical design to correct chromatic aberration by combining a glass lens, a refractive index n d of 1.50 or more 1.65 or less Yes, the Abbe number ⁇ d is 20 or more and 50 or less, the secondary dispersion characteristic ⁇ gF is 0.62 or more and 0.70 or less, and the bias ⁇ gF of the secondary dispersion characteristic is 0.02 or more and 0.08 or less. It is preferable to have.
  • the optical element having the abnormal partial dispersion characteristic according to the present invention has an Abbe number ⁇ d in the range of 20 or more and 50 or less as compared with the resin composition for forming an optical element described in Patent Document 2 after curing.
  • the refractive index nd is high. Therefore, when the chromatic aberration is corrected by combining the resin lens and the glass lens, which are the optical elements, the resin lens can be composed of thin convex, concave, and meniscus-shaped resin layers, and linear expansion and dn /. It is possible to obtain an optical element that is less affected by dT (temperature coefficient of refractive index).
  • the following components A and B are weighted at a weight ratio of 50:50. Mixed in. Further, 0.1 parts by weight of the C component shown below was mixed to obtain a precursor resin composition in which all of them were uniformly compatible.
  • Component A Bifunctional fluorine-containing acrylate with a fluorine content of 41.1% by mass B5278 "2,2,3,3,4,5,5-octafluorohexane-1,6-” manufactured by Tokyo Kasei Co., Ltd. Dimethacrylic acid “(structural formula is shown in Chemical formula 2).
  • Component B A-BPEF-2 "9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene” manufactured by Shin-Nakamura Chemical Industry Co., Ltd., a bifunctional acrylate having a benzene ring (the structural formula is shown in Chemical formula 3).
  • Component C Irgacare® 184, manufactured by Ciba Specialty Chemicals, a photopolymerization initiator.
  • the precursor resin composition obtained by mixing the above was sandwiched between two glass substrates provided with a spacer having a thickness of 1.0 mm at the peripheral portion and spread out. Subsequently, by irradiating ultraviolet rays (UV) from the glass substrate side (30 mW / cm 2 x 3 min), the precursor resin composition sandwiched between the glass substrates is cured, and a flat plate having a thickness of 1.0 mm is cured. An optical element was obtained. Then, the obtained optical element was annealed at 80 ° C. for 2 hours. And using refractometer Abbemat MW a (Anton Paar), the refractive index n d of the formed optical element was measured Abbe number [nu d and second-order dispersion characteristic theta gF.
  • UV ultraviolet rays
  • the components A and B shown below are weight-ratio 50: It was mixed at 50. Further, 0.1 parts by weight of the C component shown below was mixed to obtain a precursor resin composition in which all of them were uniformly compatible.
  • a flat plate-shaped optical element was obtained by the method described in Example 1. And using refractometer Abbemat MW a (Anton Paar), the refractive index n d of the formed optical element was measured Abbe number [nu d and second-order dispersion characteristic theta gF.
  • Component A Bifunctional fluorine-containing acrylate with a fluorine content of 41.1% by mass B5278 "2,2,3,3,4,5,5-octafluorohexane-1,6-” manufactured by Tokyo Kasei Co., Ltd. Dimethacrylic acid "(structural formula is shown in Chemical formula 2).
  • Component B Osaka Organic Chemical Industry Biscort # 700HV "bisphenol AEO 3.8 molar adduct diacrylate” (structural formula is shown in Chemical formula 4), which is a bifunctional acrylate having a benzene ring.
  • Component C Irgacare® 184, manufactured by Ciba Specialty Chemicals, a photopolymerization initiator.
  • the components A, B and E shown below are weighted.
  • the mixture was mixed at a ratio of 40:40:20. Further, 0.1 parts by weight of the C component shown below was mixed to obtain a precursor resin composition in which all of them were uniformly compatible.
  • a flat plate-shaped optical element was obtained by the method described in Example 1. And using refractometer Abbemat MW a (Anton Paar), the refractive index n d of the formed optical element was measured Abbe number [nu d and second-order dispersion characteristic theta gF.
  • Component A Bifunctional fluorine-containing acrylate with a fluorine content of 41.1% by mass B5278 "2,2,3,3,4,5,5-octafluorohexane-1,6-” manufactured by Tokyo Kasei Co., Ltd. Dimethacrylic acid “(structural formula is shown in Chemical formula 2).
  • Component B A-BPEF-2 "9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene” manufactured by Shin-Nakamura Chemical Industry Co., Ltd., a bifunctional acrylate having a benzene ring (the structural formula is shown in Chemical formula 3). ).
  • Component E Kyoeisha Chemical Light Acrylate (registered trademark) POB-A "3-phenoxybenzyl acrylate” (structural formula is shown in Chemical formula 5), which is a monofunctional acrylate having a benzene ring.
  • Component C Irgacare® 184, manufactured by Ciba Specialty Chemicals, a photopolymerization initiator.
  • the components A, B and D shown below are weighted.
  • the mixture was mixed at a ratio of 45:45:10. Further, 0.1 parts by weight of the C component shown below was mixed to obtain a precursor resin composition in which all of them were uniformly compatible.
  • a flat plate-shaped optical element was obtained by the method described in Example 1. And using refractometer Abbemat MW a (Anton Paar), the refractive index n d of the formed optical element was measured Abbe number [nu d and second-order dispersion characteristic theta gF.
  • Component A Bifunctional fluorine-containing acrylate with a fluorine content of 41.1% by mass B5278 "2,2,3,3,4,5,5-octafluorohexane-1,6-” manufactured by Tokyo Kasei Co., Ltd. Dimethacrylic acid “(structural formula is shown in Chemical formula 2).
  • Component B A-BPEF-2 "9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene” manufactured by Shin-Nakamura Chemical Industry Co., Ltd., a bifunctional acrylate having a benzene ring (the structural formula is shown in Chemical formula 3). ).
  • Component D CHEMINOX® FAAC-6 "2- (perfluorohexyl) ethyl methacrylate" manufactured by Unimatec, a monofunctional fluorine-containing acrylate having a fluorine content of 59.1% by mass (structural formula is shown in Chemical formula 6). ).
  • Component C Irgacare® 184, manufactured by Ciba Specialty Chemicals, a photopolymerization initiator.
  • the components A to E of the precursor resin composition for obtaining the UV curable resin described in the embodiment for carrying out the invention were mixed at a weight ratio of 40:40:10:10. Further, 0.1 parts by weight of the C component shown below was mixed to obtain a precursor resin composition in which all of them were uniformly compatible.
  • a flat plate-shaped optical element was obtained by the method described in Example 1. And using refractometer Abbemat MW a (Anton Paar), the refractive index n d of the formed optical element was measured Abbe number [nu d and second-order dispersion characteristic theta gF.
  • Component A Bifunctional fluorine-containing acrylate with a fluorine content of 41.1% by mass B5278 "2,2,3,3,4,5,5-octafluorohexane-1,6-” manufactured by Tokyo Kasei Co., Ltd. Dimethacrylic acid “(structural formula is shown in Chemical formula 2).
  • Component B A-BPEF-2 "9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene” manufactured by Shin-Nakamura Chemical Industry Co., Ltd., a bifunctional acrylate having a benzene ring (the structural formula is shown in Chemical formula 3).
  • Component D CHEMINOX® FAAC-6 "2- (perfluorohexyl) ethyl methacrylate” manufactured by Unimatec, a monofunctional fluorine-containing acrylate having a fluorine content of 59.1% by mass (structural formula is shown in Chemical formula 6). ).
  • Component E Kyoeisha Chemical Light Acrylate (registered trademark) POB-A "3-phenoxybenzyl acrylate” (structural formula is shown in Chemical formula 5), which is a monofunctional acrylate having a benzene ring.
  • Component C Irgacare® 184, manufactured by Ciba Specialty Chemicals, a photopolymerization initiator.
  • Example 1 The evaluation results of Examples 1 to 5 are shown in Table 1.
  • Table 1 the numerical values described in the column of each component indicate the weight ratio.
  • the precursor resin composition for obtaining a UV-curable resin according to the present invention of Examples 1 to 5 are both refractive index n d be 1.50 or more 1.65 or less
  • the Abbe number ⁇ d is 20 or more and 50 or less
  • the secondary dispersion characteristic ⁇ gF is 0.62 or more and 0.70 or less
  • the bias ⁇ gF of the secondary dispersion characteristic is in the range of 0.02 or more and 0.08 or less.
  • FIG graph showing the relationship between distribution of an Abbe number [nu d and the refractive index n d of the commercially available optical glasses of Example 1 to Example 5 of the precursor molded body of the resin composition obtained by curing No. 2 is a graph showing the relationship distribution between the Abbe number ⁇ d and the secondary dispersion characteristic ⁇ gF in a commercially available optical glass and a molded product obtained by curing the precursor resin compositions of Examples 1 to 5. Is shown in FIG. As shown in FIG.
  • the precursor resin composition for obtaining a UV-curable resin according to the present invention of Examples 1 to 5 in relation to the refractive index n d and the Abbe number [nu d after curing, compared with an optical element forming resin composition described in Patent Document 2, it was confirmed that the Abbe number [nu d is higher refractive index n d in the range of 20 to 50..
  • the precursor resin composition for obtaining the UV curable resin according to the present invention of Examples 1 to 5 has an Abbe number ⁇ d after curing and a secondary dispersion characteristic ⁇ g F.
  • the secondary dispersion characteristic ⁇ gF is higher in the range where the Abbe number ⁇ d is 20 or more and 50 or less as compared with the commercially available glass and the resin composition for forming an optical element described in Patent Document 2. It was confirmed that The straight lines in FIG. 1 are Abbe numbers ⁇ d (60.49, 36.3) and 2 in HOYA's C7 (code 511-605) and F2 (code 620-363), which are the standards for normally dispersed glass. It is a standard line passing through the next dispersion characteristic ⁇ gF (0.5393, 0.5829).
  • the precursor resin composition for obtaining the UV curable resin according to the present invention has an Abbe number ⁇ d of 20 or more and 50 or less as compared with the resin composition for forming an optical element described in Patent Document 2 after curing. in the range, the refractive index n d is high, because the second-order dispersion characteristic theta gF having optical properties of high, and a resin lens formed by using the precursor resin composition was formed using a commercially available optical glass By combining with a glass lens, it is possible to have a higher degree of freedom in optical design, and chromatic aberration can be satisfactorily corrected.

Abstract

This precursor resin composition is for obtaining a UV curable resin used for producing an optical element having anomalous partial dispersion characteristics. The precursor resin composition includes: a component A including a bifunctional fluorine-containing acrylate and/or a bifunctional fluorine-containing methacrylate; a component B including a bifunctional acrylate having a benzene ring and/or a bifunctional methacrylate having a benzene ring; and a component C of a photopolymerization initiator.

Description

前駆体樹脂組成物及び光学素子Precursor resin composition and optical element
　本件発明は、前駆体樹脂組成物及び光学素子に関し、異常部分分散特性を備えた光学素子の製造に用いるＵＶ硬化型樹脂を得るための前駆体樹脂組成物、及び、そのようなＵＶ硬化型樹脂製造に用いる前駆体樹脂組成物を用いて得られた光学素子に関する。 The present invention relates to a precursor resin composition and an optical element, and a precursor resin composition for obtaining a UV curable resin used for producing an optical element having anomalous partial dispersion characteristics, and such a UV curable resin. The present invention relates to an optical element obtained by using a precursor resin composition used for production.
　従来、屈折系光学素子のみによって構成した光学系では、屈折率ｎｄ及びアッベ数νｄや２次分散特性θｇＦが異なるガラスレンズを組み合わせることにより、色収差を補正する技術が知られている。さらに、ガラスレンズ同士を組み合わせる以外に、ガラスレンズと樹脂レンズとを組み合わせることで補正する技術も知られている。 Conventionally, in the optical system constituted only by refraction system optical element, by combining the refractive index n d and the Abbe number [nu d and secondary dispersion characteristic theta gF is different glass lens, a technique for correcting chromatic aberration are known. Further, in addition to combining glass lenses, a technique for correcting by combining a glass lens and a resin lens is also known.
　ガラスレンズを形成する光学ガラスには多くの種類があり、種々の屈折率ｎｄ及びアッベ数νｄや２次分散特性θｇＦを有するものが開発されている。これらの光学ガラスの光学特性の分布は、アッベ数νｄが低いときは２次分散特性θｇＦが高く、アッベ数νｄが高くになるにつれて２次分散特性θｇＦが低くなる傾向を示している。 The optical glass forming the glass lenses There are many types, having various refractive index n d and the Abbe number [nu d and secondary dispersion characteristic theta gF have been developed. Distribution of the optical properties of these optical glasses, when the Abbe number [nu d is low has a high second-order dispersion characteristic theta gF, the second-order dispersion characteristic theta gF as the Abbe number [nu d is higher tended to be lower There is.
　一方、樹脂レンズを形成する樹脂組成物として用いることができる合成樹脂は、種類が少ない上に、屈折率ｎｄ及びアッベ数νｄや２次分散特性θｇＦの範囲が限られている。 On the other hand, synthetic resins that may be used as a resin composition for forming the resin lens, on the small type, the range of the refractive index n d and the Abbe number [nu d and secondary dispersion characteristic theta gF is limited.
　このように、使用できるガラスレンズ及び樹脂レンズの光学特性の範囲が限られるため、光学設計における自由度が低く、色収差を十分に補正することができなかった。 As described above, since the range of optical characteristics of the glass lens and the resin lens that can be used is limited, the degree of freedom in the optical design is low, and the chromatic aberration cannot be sufficiently corrected.
　そこで、ガラスレンズと組合せて色収差を補正するのに用いる樹脂レンズの樹脂組成物として、例えば、特許文献１には、硫黄含有化合物と重合開始剤とを含有し、硬化後のアッベ数νｄが１８より大、２３より小の範囲であり、２次分散特性θｇＦが０．６８より大、０．６９より小の範囲である光学素子形成用樹脂組成物が開示されている。 Therefore, as a resin composition of a resin lens used for correcting chromatic aberration in combination with a glass lens, for example, Patent Document 1 contains a sulfur-containing compound and a polymerization initiator, and the Abbe number ν d after curing is determined. A resin composition for forming an optical element, which has a range of more than 18 and less than 23, and a secondary dispersion characteristic θ gF of more than 0.68 and less than 0.69, is disclosed.
　また、特許文献２には、フッ素含有有機化合物と重合開始剤とを含有し、硬化後のアッベ数νｄが３０より大、８５より小の範囲であり、２次分散特性θｇＦが０．５３より大、０．６５より小の範囲である光学素子形成用樹脂組成物が開示されている。 Further, Patent Document 2 contains a fluorine-containing organic compound and a polymerization initiator, and the Abbe number ν d after curing is in the range of more than 30 and less than 85, and the secondary dispersion characteristic θ gF is 0. A resin composition for forming an optical element, which is larger than 53 and smaller than 0.65, is disclosed.
日本国公開特許公報「特開２０１０－９７１９５号公報」Japanese Patent Publication "Japanese Patent Laid-Open No. 2010-97195" 日本国公開出願公報「特開２０１９－１５１８０９号公報」Japanese Publication Application Gazette "Japanese Patent Laid-Open No. 2019-151809"
　しかしながら、特許文献１に記載の光学素子形成用樹脂組成物は、他の溶剤との相溶性が悪く、硬化後の変色もおこりやすい傾向にある。また、結晶化温度が常温より高いので、光学素子に用いる樹脂組成物として取り扱い性が悪い。 However, the resin composition for forming an optical element described in Patent Document 1 has poor compatibility with other solvents and tends to be easily discolored after curing. Moreover, since the crystallization temperature is higher than room temperature, it is difficult to handle as a resin composition used for an optical element.
　また、特許文献２に記載の光学素子形成用樹脂組成物は、屈折率が低い。この樹脂組成物と高屈折率高分散の硝材と組み合わせて色収差を補正しようとすると、光学素子の形状が球に近い両凸形状になる。樹脂組成物はガラスに比べ線膨張、及びｄｎ／ｄＴ（屈折率の温度係数）が大きく、球に近い両凸形状はこれらの影響が顕著に現れるためレンズとして好ましくない。 Further, the resin composition for forming an optical element described in Patent Document 2 has a low refractive index. When an attempt is made to correct chromatic aberration by combining this resin composition with a glass material having a high refractive index and high dispersion, the shape of the optical element becomes a biconvex shape close to a sphere. The resin composition has a larger linear expansion and dn / dT (temperature coefficient of refractive index) than glass, and a biconvex shape close to a sphere is not preferable as a lens because these effects are remarkably exhibited.
　本件発明は、硬化後のアッベ数νｄに対する屈折率ｎｄ及び２次分散特性θｇＦの特性が従来のガラスレンズと異なることにより、光学設計においてより高い自由度を持たせることができる前駆体樹脂組成物、及びそのような前駆体樹脂組成物を用いた光学素子を提供することを目的とする。 Present invention, by the characteristics of the refractive index n d and second-order dispersion characteristic theta gF against Abbe number [nu d after curing is different from the conventional glass lenses, precursors can have a higher degree of freedom in optical design It is an object of the present invention to provide a resin composition and an optical element using such a precursor resin composition.
　上述した課題を解決するために、鋭意研究の結果、以下の発明に想到した。 In order to solve the above-mentioned problems, as a result of diligent research, we came up with the following inventions.
１．ＵＶ硬化型樹脂を得るための前駆体樹脂組成物
　本件発明に係るＵＶ硬化型樹脂を得るための前駆体樹脂組成物は、異常部分分散特性を備えた光学素子の製造に用いるＵＶ硬化型樹脂を得るための前駆体樹脂組成物であって、上述の前駆体樹脂組成物には、以下に示すＡ成分と、Ｂ成分と、Ｃ成分とを含むことを特徴としている。
　Ａ成分：２官能含フッ素アクリレート及び／又は２官能含フッ素メタクリレート。
　Ｂ成分：ベンゼン環を有する２官能アクリレート及び／又はベンゼン環を有する２官能メタクリレート。
　Ｃ成分：光重合開始剤。 1. 1. Precursor Resin Composition for Obtaining UV Curable Resin The precursor resin composition for obtaining the UV curable resin according to the present invention is a UV curable resin used for manufacturing an optical element having anomalous partial dispersion characteristics. It is a precursor resin composition for obtaining, and the above-mentioned precursor resin composition is characterized by containing the following A component, B component, and C component.
Component A: Bifunctional fluorine-containing acrylate and / or bifunctional fluorine-containing methacrylate.
Component B: Bifunctional acrylate having a benzene ring and / or bifunctional methacrylate having a benzene ring.
Component C: Photopolymerization initiator.
２．異常部分分散特性を備える光学素子
　本件発明に係る異常部分分散性能を備える光学素子は、上記ＵＶ硬化型樹脂を得るための前駆体樹脂組成物を用いて得られることを特徴としている。 2. Optical element having anomalous partial dispersion characteristics The optical element having anomalous partial dispersion performance according to the present invention is characterized by being obtained by using a precursor resin composition for obtaining the above UV curable resin.
　本件発明に係る前駆体樹脂組成物は、上述したフッ素含有有機化合物を含有することにより、硬化後のアッベ数νｄに対する屈折率ｎｄ及び２次分散特性θｇＦの特性が従来のガラスレンズと異なる特性を得ることができる。これにより、本件発明に係る前駆体樹脂組成物は、光学設計においてより高い自由度を持たせることができる。 Precursor resin composition according to the present invention, by containing a fluorine-containing organic compounds described above, the characteristics of the refractive index n d and second-order dispersion characteristic theta gF against Abbe number [nu d after curing and conventional glass lenses Different properties can be obtained. As a result, the precursor resin composition according to the present invention can have a higher degree of freedom in optical design.
市販の光学ガラスと実施例１～５の前駆体樹脂組成物を硬化して得られた成形体とのアッベ数νｄと２次分散特性θｇＦとの関係分布を示すグラフである。It is a graph which shows the relationship distribution of the Abbe number ν d and the secondary dispersion characteristic θ g F of the molded article obtained by curing the precursor resin composition of Examples 1 to 5 with the commercially available optical glass. 市販の光学ガラスと実施例１～５の前駆体樹脂組成物を硬化して得られた成形体とのアッベ数νｄと屈折率ｎｄとの関係分布を示すグラフである。Is a graph showing the relationship between distribution of an Abbe number [nu d and the refractive index n d of the commercially available optical glasses of Examples 1 to 5 precursor resin composition molded article obtained by curing the.
　以下、本件発明に係るＵＶ硬化型樹脂を得るための前駆体樹脂組成物の実施の形態を説明する。 Hereinafter, embodiments of the precursor resin composition for obtaining the UV curable resin according to the present invention will be described.
１．ＵＶ硬化型樹脂を得るための前駆体樹脂組成物の実施の形態
　本件発明に係るＵＶ硬化型樹脂を得るための前駆体樹脂組成物は、異常部分分散特性を備えた光学素子の製造に用いるＵＶ硬化型樹脂を得るための前駆体樹脂組成物であって、上述の前駆体樹脂組成物は以下に示すＡ成分と、Ｂ成分と、Ｃ成分とを含むことを特徴としている。
　Ａ成分：２官能含フッ素アクリレート及び／又は２官能含フッ素メタクリレート。
　Ｂ成分：ベンゼン環を有する２官能アクリレート及び／又はベンゼン環を有する２官能メタクリレート。
　Ｃ成分：光重合開始剤。 1. 1. Embodiment of Precursor Resin Composition for Obtaining UV Curable Resin The precursor resin composition for obtaining the UV curable resin according to the present invention is a UV used for producing an optical element having anomalous partial dispersion characteristics. It is a precursor resin composition for obtaining a curable resin, and the above-mentioned precursor resin composition is characterized by containing a component A, a component B, and a component C shown below.
Component A: Bifunctional fluorine-containing acrylate and / or bifunctional fluorine-containing methacrylate.
Component B: Bifunctional acrylate having a benzene ring and / or bifunctional methacrylate having a benzene ring.
Component C: Photopolymerization initiator.
　本件発明によれば、後述するように、本件発明に係るＵＶ硬化型樹脂を得るための前駆体樹脂組成物は、上述したフッ素含有有機化合物を含有することにより、硬化後において、アッベ数νｄに対する屈折率ｎｄ及び二次分散特性θｇＦの特性が、従来のガラスレンズや樹脂レンズ（例えば、特許文献２に記載の光学素子形成用樹脂組成物により得られる樹脂レンズなど）と異なる。これにより、ガラスレンズと組合せてより効果的に色収差を補正することができ、光学設計においてより高い自由度を持たせることができる。具体的には、特許文献２に記載の光学素子形成用樹脂組成物と比べて、アッベ数νｄが２０以上５０以下の範囲において、屈折率ｎｄが高く、２次分散特性θｇＦが高い光学特性を実現することができる。そのため、当該前駆体樹脂組成物を用いて形成した樹脂レンズと、「アッベ数νｄが低いときは２次分散特性θｇＦが高く、アッベ数νｄが高くになるにつれて２次分散特性θｇＦが低くなる光学特性を示すガラスレンズ」とを組み合わせることで、光学設計においてより高い自由度を持たせることができ、色収差を十分に補正することができる。 According to the present invention, as will be described later, the precursor resin composition for obtaining the UV curable resin according to the present invention contains the above-mentioned fluorine-containing organic compound, so that the Abbe number ν d after curing. characteristics of the refractive index n d and secondary dispersion characteristics theta gF against is different from the conventional glass lens or a plastic lens (e.g., a resin lens obtained by the optical element-forming resin composition described in Patent Document 2). Thereby, the chromatic aberration can be corrected more effectively in combination with the glass lens, and a higher degree of freedom can be given in the optical design. Specifically, compared to the optical element forming resin composition described in Patent Document 2, the extent Abbe number [nu d is 20 to 50. The refractive index n d is high, a higher second-order dispersion characteristic theta gF Optical characteristics can be realized. Therefore, the a precursor resin composition resin lens formed using, when "the Abbe number [nu d is low has a high second-order dispersion characteristic theta gF, second-order dispersion characteristic as the Abbe number [nu d is increased theta gF By combining with a "glass lens that exhibits low optical characteristics", it is possible to have a higher degree of freedom in optical design, and it is possible to sufficiently correct chromatic aberration.
１－１．Ａ成分
　本件発明に係るＵＶ硬化型樹脂を得るための前駆体樹脂組成物は、Ａ成分として、フッ素含有有機化合物である、２官能含フッ素アクリレートと２官能含フッ素メタクリレートとの少なくとも１つを含有するものである。フッ素含有有機化合物におけるフッ素含有量は、２０質量％以上５０質量％以下が好ましい。フッ素含有量が２０質量％未満であると、硬化後において、特許文献２に記載の光学素子形成用樹脂組成物と比べた場合、「アッベ数νｄが２０以上５０以下の範囲において、屈折率ｎｄが高く、２次分散特性θｇＦが高い前駆体樹脂組成物」を実現できないため好ましくない。フッ素含有量が５０質量％を越えるフッ素含有有機化合物は入手が困難である。また、本件発明に係るＵＶ硬化型樹脂を得るための前駆体樹脂組成物におけるＡ成分の含有量は、２０質量％以上８０質量％以下であることが好ましい。Ａ成分の含有量が２０質量％未満であると、２次分散特性θｇＦが低すぎるため好ましくない。Ａ成分の含有量が８０質量％を越えると、屈折率ｎｄが低すぎるため好ましくない。 1-1. Component A The precursor resin composition for obtaining the UV curable resin according to the present invention contains at least one of a fluorine-containing organic compound, a bifunctional fluorine-containing acrylate and a bifunctional fluorine-containing methacrylate, as the component A. It is something to do. The fluorine content of the fluorine-containing organic compound is preferably 20% by mass or more and 50% by mass or less. When the fluorine content is less than 20% by mass, after curing, when compared with the resin composition for forming an optical element described in Patent Document 2, "the refractive index is in the range where the Abbe number ν d is 20 or more and 50 or less. n d is high, second-order dispersion characteristic theta gF is unfavorably fail to achieve high precursor resin composition ". It is difficult to obtain a fluorine-containing organic compound having a fluorine content of more than 50% by mass. Further, the content of the component A in the precursor resin composition for obtaining the UV curable resin according to the present invention is preferably 20% by mass or more and 80% by mass or less. If the content of the component A is less than 20% by mass, the secondary dispersion characteristic θ gF is too low, which is not preferable. If the content of the component A exceeds 80% by mass, the refractive index nd is too low, which is not preferable.
　また、本件発明に係るＡ成分は、以下の化１に示す構造式を備えることが好ましい。樹脂組成物において屈折率を高めるには、ベンゼン環を有する有機化合物が有効であることが知られている。Ａ成分として２官能フッ素アクリレートと２官能フッ素メタクリレートとの少なくとも１つを含有することで、Ａ成分と、ベンゼン環を多く含有する２官能アクリレートと２官能メタクリレートとの少なくとも１つを含有するＢ成分との相溶性が良好になるからである。 Further, it is preferable that the component A according to the present invention has the structural formula shown in Chemical formula 1 below. It is known that an organic compound having a benzene ring is effective for increasing the refractive index in a resin composition. By containing at least one bifunctional fluorine acrylate and bifunctional fluorine methacrylate as the A component, the A component and the B component containing at least one of the bifunctional acrylate and the bifunctional methacrylate containing a large amount of benzene rings. This is because the compatibility with is improved.
Figure JPOXMLDOC01-appb-C000002
 ［式中、Ｒ２１及びＲ２２はそれぞれ独立に水素原子又はメチル基であり、ｘは１～２の整数であり、Ｙは炭素数２～１２のパーフルオロアルキル基又は－（ＣＦ２－Ｏ－ＣＦ２）Ｚ－であり、前記ｚは１～４の整数である。］
Figure JPOXMLDOC01-appb-C000002
 [In the formula, R 21 and R 22 are independent hydrogen atoms or methyl groups, x is an integer of 1 to 2, and Y is a perfluoroalkyl group having 2 to 12 carbon atoms or-(CF 2- O). -CF 2 ) Z- , and z is an integer of 1 to 4. ]
　Ａ成分として用いられるフッ素含有有機化合物の具体例としては、２，２，３，３，４，４，５，５－Ｏｃｔａｆｌｕｏｒｏｈｅｘａｎ－１，６－ｄｉｙｌ　ｄｉａｃｒｙｌａｔｅ（ＣＡＳ：２２６４－０１－９）、２，２，３，３，４，４，５，５－Ｏｃｔａｆｌｕｏｒｏｈｅｘａｎ－１，６－ｄｉｙｌ　ｄｉｍｅｔｈａｃｒｙｌａｔｅ（ＣＡＳ：６６８１８－５４－０）、２，２，３，３，４，４－Ｈｅｘａｆｌｕｏｒｏｐｅｎｔ－１，５－ｄｉｙｌ　ｄｉｍｅｔｈａｃｒｙｌａｔｅ（ＣＡＳ：９１８－３６－５）等が挙げられる。 Specific examples of the fluorine-containing organic compound used as the component A include 2,2,3,3,4,5,5-Octafluorohexan-1,6-diyl dialclylate (CAS: 2264-01-9), 2. , 2,3,3,4,5,5-Octofluorohexan-1,6-diyl compound (CAS: 66818-54-0), 2,2,3,3,4,4-Hexafluoropen-1,5 -Diyl dimethacrylate (CAS: 918-36-5) and the like can be mentioned.
１－２．Ｂ成分
　本件発明に係るＵＶ硬化型樹脂を得るための前駆体樹脂組成物は、Ｂ成分として、ベンゼン環を有する２官能アクリレートとベンゼン環を有する２官能メタクリレートとの少なくとも１つを含有するものである。本件発明に係るＵＶ硬化型樹脂を得るための前駆体樹脂組成物におけるＢ成分の含有量は、２０質量％以上８０質量％以下であることが好ましい。Ｂ成分の含有量が２０質量％未満であると、屈折率ｎｄが低すぎるため好ましくない。Ｂ成分の含有量が８０質量％を越えると、２次分散特性θｇＦが低すぎるため好ましくない。 1-2. Component B The precursor resin composition for obtaining the UV curable resin according to the present invention contains at least one of a bifunctional acrylate having a benzene ring and a bifunctional methacrylate having a benzene ring as the component B. is there. The content of the B component in the precursor resin composition for obtaining the UV curable resin according to the present invention is preferably 20% by mass or more and 80% by mass or less. If the content of the B component is less than 20% by mass, the refractive index nd is too low, which is not preferable. If the content of the B component exceeds 80% by mass, the secondary dispersion characteristic θ gF is too low, which is not preferable.
　Ｂ成分として用いられる有機化合物の具体例としては、２．２　Ｂｉｓ〔４－（Ａｃｒｙｌｏｘｙ　Ｐｏｌｙｅｔｈｏｘｙ）Ｐｈｅｎｙｌ〕Ｐｒｏｐａｎｅ　エトキシ化ビスフェノールＡジアクリレート（ＣＡＳ：６４４０１－０２－１）、９，９－Ｂｉｓ［４－（２－ａｃｒｙｌｏｙｌｏｘｙ　ｅｔｈｏｘｙ）ｐｈｅｎｙ］ｆｌｕｏｒｅｎｅ　９，９－ビス［４－（２－アクリロイルオキシエトキシ）フェニル］フルオレン（ＣＡＳ：１２３４８２７－４５－２）、Ｂｉｓ（４－ｍｅｔｈａｃｒｙｌｏｙｌｔｈｉｏｐｈｅｎｙｌ）Ｓｕｌｆｉｄｅ（ＣＡＳ：１２９２８３－８２－５）、ビス［４－（２－ヒドロキシエトキシ）フェニル］スルホン（ＣＡＳ：２７２０５－０３－４）等が挙げられる。 Specific examples of the organic compound used as the B component include 2.2 Bis [4- (Acryloxy Polyethoxy) Phenyl] Propane ethoxylated bisphenol A diacrylate (CAS: 64401-02-1), 9,9-Bis [4. -(2-acryloyloxy) phenyl] fluorene 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (CAS: 1234827-45-2), Bis (4-methacryloylthiophenyl) Sulfide (CAS: 129283-) 82-5), bis [4- (2-hydroxyethoxy) phenyl] sulfone (CAS: 27205-03-4) and the like can be mentioned.
１－３．Ｃ成分
　本件発明に係るＵＶ硬化型樹脂を得るための前駆体樹脂組成物は、Ｃ成分として、光重合開始剤を含有するものである。光重合開始剤は、フッ素含有有機化合物を重合するために用いる。光重合開始剤は、フッ素含有有機化合物の反応性や光照射の波長に応じて、１種類のみを使用してもよく、２種類以上を併用して使用してもよい。本件発明に係るＵＶ硬化型樹脂を得るための前駆体樹脂組成物におけるＣ成分の添加量は、０．００１質量％以上５質量％以下であることが好ましい。Ｃ成分の含有量が０．００１質量％未満であると、硬化しないので好ましくない。Ｃ成分の含有量が５質量％を越えると、保存時に硬化してしまうため好ましくない。 1-3. Component C The precursor resin composition for obtaining the UV curable resin according to the present invention contains a photopolymerization initiator as the component C. The photopolymerization initiator is used to polymerize a fluorine-containing organic compound. As the photopolymerization initiator, only one type may be used or two or more types may be used in combination depending on the reactivity of the fluorine-containing organic compound and the wavelength of light irradiation. The amount of the C component added to the precursor resin composition for obtaining the UV curable resin according to the present invention is preferably 0.001% by mass or more and 5% by mass or less. If the content of the C component is less than 0.001% by mass, it does not cure, which is not preferable. If the content of the C component exceeds 5% by mass, it will be cured during storage, which is not preferable.
　Ｃ成分として用いられる光重合開始剤の具体例としては、２，２－ｄｉｍｅｔｈｏｘｙ－２－ｐｈｅｎｙｌａｃｅｔｏｐｈｅｎｏｎｅ、１－ｈｙｄｒｏｘｙｃｙｃｌｏｈｅｘｙｌ－ｐｈｅｎｙｌ　ｋｅｔｏｎｅ、２－ｈｙｄｒｏｘｙ－２－ｍｅｔｈｙｌ－１－ｐｈｅｎｙｌｐｒｏｐａｎｏｎｅ、１－［４－（２－ｈｙｄｒｏｘｙｅｔｈｏｘｙｌ）－ｐｈｅｎｙｌ］－２－ｈｙｄｒｏｘｙ－ｍｅｔｈｙｌｐｒｏｐａｎｏｎｅ、２－ｈｙｄｒｏｘｙ－１－（４－（４－（２－ｈｙｄｒｏｘｙ－２－ｍｅｔｈｙｌｐｒｏｐｉｏｎｙｌ）ｂｅｎｚｙｌ）ｐｈｅｎｙｌ）－２－ｍｅｔｈｙｌｐｒｏｐａｎ－１－ｏｎｅ、２－ｍｅｔｈｙｌ－１－［４－（ｍｅｔｈｙｌｔｈｉｏ）ｐｈｅｎｙｌ］－２－ｍｏｒｐｈｏｌｉｎｏｐｒｏｐａｎ－１－ｏｎｅ、２－ｂｅｎｚｙｌ－２－（ｄｉｍｅｔｈｙｌａｍｉｎｏ）－４’－ｍｏｒｐｈｏｌｉｎｏｂｕｔｙｒｏｐｈｅｎｏｎｅ、２－ｄｉｍｅｔｈｙｌａｍｉｎｏ－２－（４－ｍｅｔｈｙｌ－ｂｅｎｚｙｌ）－１－（４－ｍｏｒｐｈｏｌｉｎ－４－ｙｌ－ｐｈｅｎｙｌ）－ｂｕｔａｎ－１－ｏｎｅ等が挙げられる。 Specific examples of the photopolymerization initiator used as the C component include 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, 1- [4- (4). 2-hydroxyethoxyl) -phenyl] -2-hydroxy-methylpropanone, 2-hydroxy-1- (4- (4- (2-hydroxy-2-methylpropionyl) benzyl) phenyl) -2-methylpropan-1 methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2- (dimerylamino) -4'-morpholino phenylphenone, 2-dimerylamino-2- (4-methyl-ben) 1- (4-morpholin-4-yl-phenyl) -butan-1-one and the like can be mentioned.
１－４．Ｄ成分
　本件発明に係るＵＶ硬化型樹脂を得るための前駆体樹脂組成物は、また、Ｄ成分として、フッ素含有有機化合物である、単官能含フッ素アクリレートと単官能含フッ素メタクリレートとの少なくとも１つを含むことが好ましい。フッ素含有有機化合物であるＤ成分におけるフッ素含有量は、２０質量％以上７０質量％以下が好ましい。フッ素含有量が２０質量％未満であると、硬化後において、特許文献２に記載の光学素子形成用樹脂組成物と比べた場合、アッベ数νｄが２０以上５０以下の範囲において、屈折率ｎｄが高く、２次分散特性θｇＦが高い前駆体樹脂組成物を実現できないため好ましくない。フッ素含有量が７０質量％を越えるフッ素含有有機化合物は入手が困難である。また、本件発明に係るＵＶ硬化型樹脂を得るための前駆体樹脂組成物におけるＤ成分の含有量は、１質量％以上３０質量％以下であることが好ましい。Ｄ成分の含有量が１質量％未満であると、２次分散特性θｇＦを向上できないので好ましくない。Ｄ成分の含有量が３０質量％を越えると、相溶性が無くなり透明性を失うので好ましくない。 1-4. Component D The precursor resin composition for obtaining the UV curable resin according to the present invention also contains at least one of a fluorine-containing organic compound, a monofunctional fluorine-containing acrylate and a monofunctional fluorine-containing methacrylate, as the D component. Is preferably included. The fluorine content in the D component, which is a fluorine-containing organic compound, is preferably 20% by mass or more and 70% by mass or less. When the fluorine content is less than 20% by mass, the refractive index n after curing is in the range where the Abbe number ν d is 20 or more and 50 or less as compared with the resin composition for forming an optical element described in Patent Document 2. It is not preferable because a precursor resin composition having a high d and a high secondary dispersion characteristic θ gF cannot be realized. It is difficult to obtain a fluorine-containing organic compound having a fluorine content of more than 70% by mass. Further, the content of the D component in the precursor resin composition for obtaining the UV curable resin according to the present invention is preferably 1% by mass or more and 30% by mass or less. If the content of the D component is less than 1% by mass, the secondary dispersion characteristic θ gF cannot be improved, which is not preferable. If the content of the D component exceeds 30% by mass, compatibility is lost and transparency is lost, which is not preferable.
　Ｄ成分として用いられるフッ素含有有機化合物の具体例としては、２，２，３，３，４，４，５，５，６，６，７，７－Ｄｏｄｅｃａｆｌｕｏｒｏｈｅｐｔｙｌ　Ａｃｒｙｌａｔｅ（ＣＡＳ：２９９３－８５－３）、１Ｈ，１Ｈ，２Ｈ，２Ｈ－Ｈｅｐｔａｄｅｃａｆｌｕｏｒｏｄｅｃｙｌ　Ａｃｒｙｌａｔｅ（ＣＡＳ：２７９０５－４５－９）、２，２，３，４，４，４－Ｈｅｘａｆｌｕｏｒｏｂｕｔｙｌ　Ａｃｒｙｌａｔｅ（ＣＡＳ：５４０５２－９０－３）、１，１，１，３，３，３－Ｈｅｘａｆｌｕｏｒｏｉｓｏｐｒｏｐｙｌ　Ａｃｒｙｌａｔｅ（ＣＡＳ：２１６０－８９－６）、１Ｈ，１Ｈ，２Ｈ，２Ｈ－Ｎｏｎａｆｌｕｏｒｏｈｅｘｙｌ　Ａｃｒｙｌａｔｅ（ＣＡＳ：５２５９１－２７－２）、１Ｈ，１Ｈ，５Ｈ－Ｏｃｔａｆｌｕｏｒｏｐｅｎｔｙｌ　Ａｃｒｙｌａｔｅ（ＣＡＳ：３７６－８４－１）、１Ｈ，１Ｈ－Ｐｅｎｔａｄｅｃａｆｌｕｏｒｏ－ｎ－ｏｃｔｙｌ　Ａｃｒｙｌａｔｅ（ＣＡＳ：３０７－９８－２）、Ｐｅｎｔａｆｌｕｏｒｏｐｈｅｎｙｌ　Ａｃｒｙｌａｔｅ（ＣＡＳ：７１１９５－８５－２）、２，２，３，３－Ｔｅｔｒａｆｌｕｏｒｏｐｒｏｐｙｌ　Ａｃｒｙｌａｔｅ（ＣＡＳ：７３８３－７１－３）、１Ｈ，１Ｈ，２Ｈ，２Ｈ－Ｔｒｉｄｅｃａｆｌｕｏｒｏ－ｎ－ｏｃｔｙｌ　Ａｃｒｙｌａｔｅ（ＣＡＳ：１７５２７－２９－６）、２，２，２－Ｔｒｉｆｌｕｏｒｏｅｔｈｙｌ　Ａｃｒｙｌａｔｅ（ＣＡＳ：４０７－４７－６）、２，２，３，３，４，４，５，５，６，６，７，７－Ｄｏｄｅｃａｆｌｕｏｒｏｈｅｐｔｙｌ　Ｍｅｔｈａｃｒｙｌａｔｅ（ＣＡＳ：２２６１－９９－６）、２，２，３，３，４，４，４－Ｈｅｐｔａｆｌｕｏｒｏｂｕｔｙｌ　Ｍｅｔｈａｃｒｙｌａｔｅ（ＣＡＳ：１３６９５－３１－３）、２，２，３，４，４，４－Ｈｅｘａｆｌｕｏｒｏｂｕｔｙｌ　Ｍｅｔｈａｃｒｙｌａｔｅ（ＣＡＳ：３６４０５－４７－７）、１，１，１，３，３，３－Ｈｅｘａｆｌｕｏｒｏｉｓｏｐｒｏｐｙｌ　Ｍｅｔｈａｃｒｙｌａｔｅ（ＣＡＳ：３０６３－９４－３）、１Ｈ，１Ｈ，２Ｈ，２Ｈ－Ｎｏｎａｆｌｕｏｒｏｈｅｘｙｌ　Ｍｅｔｈａｃｒｙｌａｔｅ（ＣＡＳ：１７９９－８４－４）、１Ｈ，１Ｈ，５Ｈ－Ｏｃｔａｆｌｕｏｒｏｐｅｎｔｙｌ　Ｍｅｔｈａｃｒｙｌａｔｅ（ＣＡＳ：３５５－９３－１）、Ｐｅｎｔａｆｌｕｏｒｏｂｅｎｚｙｌ　Ｍｅｔｈａｃｒｙｌａｔｅ（ＣＡＳ：１１４８５９－２３－３）、Ｐｅｎｔａｆｌｕｏｒｏｐｈｅｎｙｌ　Ｍｅｔｈａｃｒｙｌａｔｅ（ＣＡＳ：１３６４２－９７－２）、２，２，３，３，３－Ｐｅｎｔａｆｌｕｏｒｏｐｒｏｐｙｌ　Ｍｅｔｈａｃｒｙｌａｔｅ（ＣＡＳ：４５１１５－５３－５）、２，２，３，３－Ｔｅｔｒａｆｌｕｏｒｏｐｒｏｐｙｌ　Ｍｅｔｈａｃｒｙｌａｔｅ（ＣＡＳ：４５１０２－５２－１）、１Ｈ，１Ｈ，２Ｈ，２Ｈ－Ｔｒｉｄｅｃａｆｌｕｏｒｏ－ｎ－ｏｃｔｙｌ　Ｍｅｔｈａｃｒｙｌａｔｅ（ＣＡＳ：２１４４－５３－８）、２，２，２－Ｔｒｉｆｌｕｏｒｏｅｔｈｙｌ　Ｍｅｔｈａｃｒｙｌａｔｅ（ＣＡＳ：３５２－８７－４）等が挙げられる。 Specific examples of the fluorine-containing organic compound used as the D component include 2,2,3,3,4,5,5,6,6,7,7-Dodecafluoroheptyl Acrylate (CAS: 2993-85-3). , 1H, 1H, 2H, 2H-Heptadecafluorodecil Acrylate (CAS: 27905-45-9), 2,2,3,4,5,4-Hexafluorobutyl Acrylate (CAS: 54052-90-3), 1,1,1 , 3,3,3-Hexafluoroisopropyl Acrylate (CAS: 2160-89-6), 1H, 1H, 2H, 2H-Nonafluorohexyl Acrylate (CAS: 52591-27-2), 1H, 1H, 5H-Octal 376-84-1), 1H, 1H-Pentadecafluoro-n-octyl Acrylate (CAS: 307-98-2), Pentafluorophenyl Acrylate (CAS: 71195-85-2), 2,2,3,3-Tetrafluoropoly CAS: 7383-71-3), 1H, 1H, 2H, 2H-Tridecafluoro-n-octyl Acrylate (CAS: 17527-29-6), 2,2,2-Trifluoroethyl Acrylate (CAS: 407-47-6) , 2,2,3,3,4,5,5,6,6,7,7-Dodecafluoroheptyl Methacrylate (CAS: 2261-99-6), 2,2,3,3,4,4,4 -Heptafluorobutyl Methacrylate (CAS: 13695-31-3), 2,2,3,4,5,4-Hexafluorobutyl Methacrylate (CAS: 36405-47-7), 1,1,1,3,3,3-Hexafluoroisopropyl Acrylate (CAS: 3063-94-3), 1H, 1H, 2H, 2H-Nonafluorohexyl Methacrylate (CAS: 1799-84-4), 1H, 1H, 5H-Octafluoropentyl Methacrylate (CAS: 355-) Methacryl ate (CAS: 114859-23-3), Pentafluoropheneyl Metacrylate (CAS: 13642-97-2), 2,2,3,3,3-Pentaffulotropyl Metasian (CAS: 45115-53-5), 2,2,3 , 3-Tetrafluoropropyl Metasis (CAS: 45102-52-1), 1H, 1H, 2H, 2H-Tridecafluoro-n-octyl Metration (CAS: 2144-53-8), 2,2,2-Trifoil 352-87-4) and the like.
１－５．Ｅ成分
　本件発明に係るＵＶ硬化型樹脂を得るための前駆体樹脂組成物は、また、Ｅ成分として、ベンゼン環を有する単官能アクリレートとベンゼン環を有する単官能メタクリレートとの少なくとも１つを含むことが好ましい。本件発明に係るＵＶ硬化型樹脂を得るための前駆体樹脂組成物におけるＥ成分の添加量は、１質量％以上４０質量％以下であることが好ましい。Ｅ成分の含有量が１質量％未満であると、屈折率ｎｄが高くならないので好ましくない。Ｅ成分の含有量が４０質量％を越えると、相溶性が無くなり透明性を失うので好ましくない。 1-5. Component E The precursor resin composition for obtaining the UV curable resin according to the present invention also contains at least one of a monofunctional acrylate having a benzene ring and a monofunctional methacrylate having a benzene ring as the E component. Is preferable. The amount of the E component added to the precursor resin composition for obtaining the UV curable resin according to the present invention is preferably 1% by mass or more and 40% by mass or less. When the content of component E is less than 1 mass% is not preferable because the refractive index n d is not high. If the content of the E component exceeds 40% by mass, compatibility is lost and transparency is lost, which is not preferable.
　Ｅ成分として用いられる有機化合物の具体例としては、Ｂｅｎｚｙｌ　Ａｃｒｙｌａｔｅ（ＣＡＳ：２４９５－３５－４）、Ｂｅｎｚｙｌ　Ｃｉｎｎａｍａｔｅ（ＣＡＳ：１０３－４１－３）、Ｐｅｎｔａｆｌｕｏｒｏｂｅｎｚｙｌ　Ｍｅｔｈａｃｒｙｌａｔｅ（ＣＡＳ：１１４８５９－２３－３）、Ｐｅｎｔａｂｒｏｍｏｂｅｎｚｙｌ　Ａｃｒｙｌａｔｅ（ＣＡＳ：５９４４７－５５－１）、Ｅｔｈｙｌ　４－［（４－Ｍｅｔｈｏｘｙｂｅｎｚｙｌｉｄｅｎｅ）ａｍｉｎｏ］ｃｉｎｎａｍａｔｅ（ＣＡＳ：６４２１－３０－３）、Ｅｔｈｙｌ　ｔｒａｎｓ－３－Ｂｅｎｚｏｙｌａｃｒｙｌａｔｅ（ＣＡＳ：１５１２１－８９－８）、Ｂｕｔｙｌ　４－［（４－Ｍｅｔｈｏｘｙｂｅｎｚｙｌｉｄｅｎｅ）ａｍｉｎｏ］ｃｉｎｎａｍａｔｅ（ＣＡＳ：１６８３３－１７－３）、４－Ｂｅｎｚｏｙｌｐｈｅｎｙｌ　Ｍｅｔｈａｃｒｙｌａｔｅ（ＣＡＳ：５６４６７－４３－７）、２－Ｐｈｅｎｏｘｙ　ｅｔｈｙｌ　ｍｅｔｈａｃｒｙｌａｔｅ（ＣＡＳ：１０５９５－０６－９）、Ｐｈｅｎｏｘｙ　ｅｔｈｙｌ　ａｃｒｙｌａｔｅ（ＣＡＳ：４８１４５－０４－６）、Ｍｅｔｈｙｌ　Ｐｈｅｎｏｘｙ　ｅｔｈｙｌ　ａｃｒｙｌａｔｅ（ＣＡＳ：１０５８４９－３１－８）、Ｐｈｅｎｏｘｙ　ｄｉｅｔｈｙｌｅｎｅｇｌｙｃｏｌ　ａｃｒｙｌａｔｅ（ＣＡＳ：６１６３０－２５－９）、Ｐｈｅｎｏｘｙ　ｐｏｌｙｅｔｈｙｌｅｎｅｇｌｙｃｏｌｌ　ａｃｒｙｌａｔｅ（ＣＡＳ：５６６４１－０５－５）、ｍ－Ｐｈｅｎｏｘｙｂｅｎｚｙｌ　ａｃｒｙｌａｔｅ（ＣＡＳ：４０９３２５－０６－０）、２－Ｈｙｄｒｏｘｙ　３－ｐｈｅｎｏｘｙ　ｐｒｏｐｙｌ　ａｃｒｙｌａｔｅ（ＣＡＳ：１６９６９－１０－１）、Ｎｅｏｐｅｎｔｈｙｌｇｌｙｃｏｌ－ｂｅｎｚｏａｔｅ－ａｃｒｙｌａｔｅ（ＣＡＳ：６６６７１－２２－５）等が挙げられる。 Specific examples of the organic compound used as the E component include Benzyl Acrylate (CAS: 2495-35-4), Benzyl Cinnamate (CAS: 103-41-3), Pentafluorobenzolylate (CAS: 114859-23-3), and Pentabro. Acrylate (CAS: 59447-55-1), Ethyl 4-[(4-Methoxybenzylidene) amino] cinnamate (CAS: 6421-30-3), Ethyl trans-3-Benzoyllate (CAS: 15121-89-8), 4-[(4-Methoxybenzylidene) amino] cinamate (CAS: 16833-17-3), 4-Benzoylphenyl Methacrylate (CAS: 56467-43-7), 2-Phenoxyethyl methacrylate (CAS: 16833-17-3), 2-Phenoxyethyl methacrylate (CAS) Phenoxy ester acrylicate (CAS: 48145-04-6), Methyl Phenoxy ester acryliclate (CAS: 105849-31-8), Phenoxy diestyleneglycolor (CAS: 48145-04-6), Phenoxy diesyleneglycol acrylicyllate (CAS: 105849-31-8) 5), m-Phenoxybenzyl acrylicate (CAS: 409325-06-0), 2-Hydroxy 3-phenyloxypropyl acrylicate (CAS: 16696-10-1), Neopenthylglycol-Benzoate-cer Can be mentioned.
１－６．前駆体樹脂組成物の硬化後の光学特性
　本件発明に係るＵＶ硬化型樹脂を得るための前駆体樹脂組成物は、上述の成分を含むことにより、硬化後において、特許文献２に記載の光学素子形成用樹脂組成物と比べて、アッベ数νｄが２０以上５０以下の範囲において、高い屈折率ｎｄと、高い２次分散特性θｇＦとを実現することができる。そのため、当該前駆体樹脂組成物を用いて形成した樹脂レンズと、「アッベ数νｄが低いと２次分散特性θｇＦが高く、アッベ数νｄが高いと２次分散特性θｇＦが低い傾向にある市販の光学ガラスを用いて形成されたガラスレンズ」とを組み合わせることによって、光学設計においてより高い自由度を持たせることができ、色収差を十分に補正した光学素子を得ることができる。 1-6. Optical Properties of Precursor Resin Composition After Curing The precursor resin composition for obtaining the UV curable resin according to the present invention contains the above-mentioned components, and after curing, the optical element described in Patent Document 2. compared with the resin composition for forming an Abbe number [nu d is in the range of 20 to 50 or less, it is possible to realize a high refractive index n d, and a high second-order dispersion characteristic theta gF. Therefore, the resin lens formed by using the precursor resin composition tends to have a high secondary dispersion characteristic θ gF when the Abbe number ν d is low, and a low secondary dispersion characteristic θ gF when the Abbe number ν d is high. By combining with a "glass lens formed by using commercially available optical glass" in the above, it is possible to have a higher degree of freedom in optical design, and it is possible to obtain an optical element in which chromatic aberration is sufficiently corrected.
　さらに、本件発明に係るＵＶ硬化型樹脂を得るための前駆体樹脂組成物は、特許文献１に記載の光学素子形成用樹脂組成物と比べた場合、アッベ数が２０以上５０以下の範囲において、ほぼ同等の光学特性を実現できており、上述の通り色収差の補正に使用することができる。また、当該前駆体樹脂組成物は、特許文献１に記載の光学素子形成用樹脂組成物と異なり、化学式において硫黄に酸素が付いていない構造であることから当該前駆体樹脂組成物同士の相溶性が良く、結晶化温度が低いので、光学素子を形成するに用いる樹脂組成物として取り扱い性が良い。 Further, the precursor resin composition for obtaining the UV curable resin according to the present invention has an Abbe number in the range of 20 or more and 50 or less as compared with the resin composition for forming an optical element described in Patent Document 1. Almost the same optical characteristics can be realized, and it can be used for correction of chromatic aberration as described above. Further, unlike the resin composition for forming an optical element described in Patent Document 1, the precursor resin composition has a structure in which oxygen is not attached to sulfur in the chemical formula, so that the precursor resin compositions are compatible with each other. It is easy to handle as a resin composition used for forming an optical element because of its good quality and low crystallization temperature.
２．異常部分分散特性を備える光学素子の実施の形態
　本件発明に係る異常部分分散特性を備える光学素子は、上述の前駆体樹脂組成物に紫外線を照射することによる硬化で得られることを特徴とする。そして膜厚が１．０ｍｍの時の波長４３０ｎｍの光に対する内部透過率が９０％以上であることが好ましい。内部透過率が９０％未満であると、光学素子としての用途が限定されるため好ましくない。なお、本明細書における「異常部分分散特性」とは、波長によって屈折率差（部分分散）が特異に変化する特性をいい、「異常部分分散特性を備える」とは、この異常部分分散特性が高いことを意味する。 2. Embodiment of an Optical Element with Anomalous Partial Dispersion Characteristics The optical element with anomalous partial dispersion characteristics according to the present invention is characterized by being obtained by curing the above-mentioned precursor resin composition by irradiating it with ultraviolet rays. When the film thickness is 1.0 mm, the internal transmittance with respect to light having a wavelength of 430 nm is preferably 90% or more. If the internal transmittance is less than 90%, the use as an optical element is limited, which is not preferable. In the present specification, the "abnormal partial dispersion characteristic" means a characteristic in which the refractive index difference (partial dispersion) changes peculiarly depending on the wavelength, and "having an abnormal partial dispersion characteristic" means that the abnormal partial dispersion characteristic is. It means high.
　また、本件発明に係る異常部分分散特性を備える光学素子は、ガラスレンズと組み合わせて色収差を補正する光学設計の自由度を高くするために、屈折率ｎｄが１．５０以上１．６５以下であり、アッベ数νｄが２０以上５０以下であり、２次分散特性θｇＦが０．６２以上０．７０以下であり、２次分散特性の偏りΔθｇＦが０．０２以上０．０８以下であることが好ましい。 The optical element having anomalous partial dispersion characteristics according to the present invention, in order to increase the degree of freedom in optical design to correct chromatic aberration by combining a glass lens, a refractive index n d of 1.50 or more 1.65 or less Yes, the Abbe number ν d is 20 or more and 50 or less, the secondary dispersion characteristic θ gF is 0.62 or more and 0.70 or less, and the bias Δθ gF of the secondary dispersion characteristic is 0.02 or more and 0.08 or less. It is preferable to have.
　さらに、本件発明に係る異常部分分散特性を備える光学素子は、硬化後において、特許文献２に記載の光学素子形成用樹脂組成物と比べて、アッベ数νｄが２０以上５０以下の範囲において、屈折率ｎｄが高い。そのため、当該光学素子である樹脂レンズとガラスレンズとを組み合わせて色収差を補正した場合、樹脂レンズは薄い凸形状、凹形状、メニスカス形状の樹脂層で構成することができ、線膨張、及びｄｎ／ｄＴ（屈折率の温度係数）の影響が少ない光学素子を得ることができる。 Further, the optical element having the abnormal partial dispersion characteristic according to the present invention has an Abbe number ν d in the range of 20 or more and 50 or less as compared with the resin composition for forming an optical element described in Patent Document 2 after curing. The refractive index nd is high. Therefore, when the chromatic aberration is corrected by combining the resin lens and the glass lens, which are the optical elements, the resin lens can be composed of thin convex, concave, and meniscus-shaped resin layers, and linear expansion and dn /. It is possible to obtain an optical element that is less affected by dT (temperature coefficient of refractive index).
　以上説明した本件発明に係る実施の形態は、本件発明の一態様であり、本件発明の趣旨を逸脱しない範囲で適宜変更可能である。また、以下実施例を挙げて本件発明をより具体的に説明するが、本件発明は、以下の実施例に限定されるものではない。 The embodiment of the present invention described above is one aspect of the present invention and can be appropriately changed without departing from the spirit of the present invention. Further, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples.
　はじめに、発明を実施するための形態において記載した、ＵＶ硬化型樹脂を得るための前駆体樹脂組成物のＡ成分～Ｅ成分のうち、以下に示すＡ成分とＢ成分とを重量比５０：５０で混合した。さらに以下に示すＣ成分を０．１重量部混合し、全てが均一に相溶している前駆体樹脂組成物を得た。 First, among the components A to E of the precursor resin composition for obtaining a UV curable resin described in the embodiment for carrying out the invention, the following components A and B are weighted at a weight ratio of 50:50. Mixed in. Further, 0.1 parts by weight of the C component shown below was mixed to obtain a precursor resin composition in which all of them were uniformly compatible.
　Ａ成分：フッ素含有量が４１．１質量％である２官能含フッ素アクリレートの東京化成社製Ｂ５２７８「２，２，３，３，４，４，５，５－オクタフルオロヘキサン－１，６－ジメタクリル酸」（構造式を化２に示す）。
　Ｂ成分：ベンゼン環を有する２官能アクリレートの新中村化学工業社製Ａ－ＢＰＥＦ－２「９，９－ビス［４－（２－アクリロイルオキシエトキシ）フェニル］フルオレン」（構造式を化３に示す）。
　Ｃ成分：光重合開始剤のＣｉｂａ　Ｓｐｅｃｉａｌｔｙ　Ｃｈｅｍｉｃａｌｓ社製Ｉｒｇａｃｕｒｅ（登録商標）１８４。 Component A: Bifunctional fluorine-containing acrylate with a fluorine content of 41.1% by mass B5278 "2,2,3,3,4,5,5-octafluorohexane-1,6-" manufactured by Tokyo Kasei Co., Ltd. Dimethacrylic acid "(structural formula is shown in Chemical formula 2).
Component B: A-BPEF-2 "9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., a bifunctional acrylate having a benzene ring (the structural formula is shown in Chemical formula 3). ).
Component C: Irgacare® 184, manufactured by Ciba Specialty Chemicals, a photopolymerization initiator.
　次に、上述の混合して得られた前駆体樹脂組成物を、周縁部に厚さ１．０ｍｍのスペーサーを備えたガラス基板２枚で挟んで押し広げた。続いて、ガラス基板側から紫外線（ＵＶ）を照射（３０ｍＷ／ｃｍ２×３ｍｉｎ）することにより、ガラス基板に挟まれている前駆体樹脂組成物を硬化させ、厚さ１．０ｍｍの平板状の光学素子を得た。その後、得られた光学素子を８０℃で２時間アニール処理した。そして屈折計Ａｂｂｅｍａｔ　ＭＷ（アントンパール社）を用いて、形成した光学素子の屈折率ｎｄ、アッベ数νｄ及び２次分散特性θｇＦを測定した。 Next, the precursor resin composition obtained by mixing the above was sandwiched between two glass substrates provided with a spacer having a thickness of 1.0 mm at the peripheral portion and spread out. Subsequently, by irradiating ultraviolet rays (UV) from the glass substrate side (30 mW / cm 2 x 3 min), the precursor resin composition sandwiched between the glass substrates is cured, and a flat plate having a thickness of 1.0 mm is cured. An optical element was obtained. Then, the obtained optical element was annealed at 80 ° C. for 2 hours. And using refractometer Abbemat MW a (Anton Paar), the refractive index n d of the formed optical element was measured Abbe number [nu d and second-order dispersion characteristic theta gF.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　次に、発明を実施するための形態において記載した、ＵＶ硬化型樹脂を得るための前駆体樹脂組成物のＡ成分～Ｅ成分のうち、以下に示すＡ成分とＢ成分とを重量比５０：５０で混合した。さらに以下に示すＣ成分を０．１重量部混合し、全てが均一に相溶している前駆体樹脂組成物を得た。次に、上述の混合して得られた前駆体樹脂組成物を用いて、実施例１に記載の方法によって、平板状の光学素子を得た。そして屈折計Ａｂｂｅｍａｔ　ＭＷ（アントンパール社）を用いて、形成した光学素子の屈折率ｎｄ、アッベ数νｄ及び２次分散特性θｇＦを測定した。 Next, among the components A to E of the precursor resin composition for obtaining the UV curable resin described in the embodiment for carrying out the invention, the components A and B shown below are weight-ratio 50: It was mixed at 50. Further, 0.1 parts by weight of the C component shown below was mixed to obtain a precursor resin composition in which all of them were uniformly compatible. Next, using the precursor resin composition obtained by mixing as described above, a flat plate-shaped optical element was obtained by the method described in Example 1. And using refractometer Abbemat MW a (Anton Paar), the refractive index n d of the formed optical element was measured Abbe number [nu d and second-order dispersion characteristic theta gF.
　Ａ成分：フッ素含有量が４１．１質量％である２官能含フッ素アクリレートの東京化成社製Ｂ５２７８「２，２，３，３，４，４，５，５－オクタフルオロヘキサン－１，６－ジメタクリル酸」（構造式を化２に示す）。
　Ｂ成分：ベンゼン環を有する２官能アクリレートの大阪有機化学工業ビスコート＃７００ＨＶ「ビスフェノールＡＥＯ３．８モル付加物ジアクリレート」（構造式を化４に示す）。
　Ｃ成分：光重合開始剤のＣｉｂａ　Ｓｐｅｃｉａｌｔｙ　Ｃｈｅｍｉｃａｌｓ社製Ｉｒｇａｃｕｒｅ（登録商標）１８４。 Component A: Bifunctional fluorine-containing acrylate with a fluorine content of 41.1% by mass B5278 "2,2,3,3,4,5,5-octafluorohexane-1,6-" manufactured by Tokyo Kasei Co., Ltd. Dimethacrylic acid "(structural formula is shown in Chemical formula 2).
Component B: Osaka Organic Chemical Industry Biscort # 700HV "bisphenol AEO 3.8 molar adduct diacrylate" (structural formula is shown in Chemical formula 4), which is a bifunctional acrylate having a benzene ring.
Component C: Irgacare® 184, manufactured by Ciba Specialty Chemicals, a photopolymerization initiator.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　次に、発明を実施するための形態において記載した、ＵＶ硬化型樹脂を得るための前駆体樹脂組成物のＡ成分～Ｅ成分のうち、以下に示すＡ成分とＢ成分とＥ成分とを重量比４０：４０：２０で混合した。さらに以下に示すＣ成分を０．１重量部混合し、全てが均一に相溶している前駆体樹脂組成物を得た。次に、上述の混合して得られた前駆体樹脂組成物を用いて、実施例１に記載の方法によって、平板状の光学素子を得た。そして屈折計Ａｂｂｅｍａｔ　ＭＷ（アントンパール社）を用いて、形成した光学素子の屈折率ｎｄ、アッベ数νｄ及び２次分散特性θｇＦを測定した。 Next, among the components A to E of the precursor resin composition for obtaining the UV curable resin described in the embodiment for carrying out the invention, the components A, B and E shown below are weighted. The mixture was mixed at a ratio of 40:40:20. Further, 0.1 parts by weight of the C component shown below was mixed to obtain a precursor resin composition in which all of them were uniformly compatible. Next, using the precursor resin composition obtained by mixing as described above, a flat plate-shaped optical element was obtained by the method described in Example 1. And using refractometer Abbemat MW a (Anton Paar), the refractive index n d of the formed optical element was measured Abbe number [nu d and second-order dispersion characteristic theta gF.
　Ａ成分：フッ素含有量が４１．１質量％である２官能含フッ素アクリレートの東京化成社製Ｂ５２７８「２，２，３，３，４，４，５，５－オクタフルオロヘキサン－１，６－ジメタクリル酸」（構造式を化２に示す）。
　Ｂ成分：ベンゼン環を有する２官能アクリレートの新中村化学工業社製Ａ－ＢＰＥＦ－２「９，９－ビス［４－（２－アクリロイルオキシエトキシ）フェニル］フルオレン」（構造式を化３に示す）。
　Ｅ成分：ベンゼン環を有する単官能アクリレートの共栄社化学ライトアクリレート（登録商標）ＰＯＢ－Ａ「３－フェノキシベンジルアクリレート」（構造式を化５に示す）。
　Ｃ成分：光重合開始剤のＣｉｂａ　Ｓｐｅｃｉａｌｔｙ　Ｃｈｅｍｉｃａｌｓ社製Ｉｒｇａｃｕｒｅ（登録商標）１８４。 Component A: Bifunctional fluorine-containing acrylate with a fluorine content of 41.1% by mass B5278 "2,2,3,3,4,5,5-octafluorohexane-1,6-" manufactured by Tokyo Kasei Co., Ltd. Dimethacrylic acid "(structural formula is shown in Chemical formula 2).
Component B: A-BPEF-2 "9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., a bifunctional acrylate having a benzene ring (the structural formula is shown in Chemical formula 3). ).
Component E: Kyoeisha Chemical Light Acrylate (registered trademark) POB-A "3-phenoxybenzyl acrylate" (structural formula is shown in Chemical formula 5), which is a monofunctional acrylate having a benzene ring.
Component C: Irgacare® 184, manufactured by Ciba Specialty Chemicals, a photopolymerization initiator.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　次に、発明を実施するための形態において記載した、ＵＶ硬化型樹脂を得るための前駆体樹脂組成物のＡ成分～Ｅ成分のうち、以下に示すＡ成分とＢ成分とＤ成分とを重量比４５：４５：１０で混合した。さらに以下に示すＣ成分を０．１重量部混合し、全てが均一に相溶している前駆体樹脂組成物を得た。次に、上述の混合して得られた前駆体樹脂組成物を用いて、実施例１に記載の方法によって、平板状の光学素子を得た。そして屈折計Ａｂｂｅｍａｔ　ＭＷ（アントンパール社）を用いて、形成した光学素子の屈折率ｎｄ、アッベ数νｄ及び２次分散特性θｇＦを測定した。 Next, among the components A to E of the precursor resin composition for obtaining the UV curable resin described in the embodiment for carrying out the invention, the components A, B and D shown below are weighted. The mixture was mixed at a ratio of 45:45:10. Further, 0.1 parts by weight of the C component shown below was mixed to obtain a precursor resin composition in which all of them were uniformly compatible. Next, using the precursor resin composition obtained by mixing as described above, a flat plate-shaped optical element was obtained by the method described in Example 1. And using refractometer Abbemat MW a (Anton Paar), the refractive index n d of the formed optical element was measured Abbe number [nu d and second-order dispersion characteristic theta gF.
　Ａ成分：フッ素含有量が４１．１質量％である２官能含フッ素アクリレートの東京化成社製Ｂ５２７８「２，２，３，３，４，４，５，５－オクタフルオロヘキサン－１，６－ジメタクリル酸」（構造式を化２に示す）。
　Ｂ成分：ベンゼン環を有する２官能アクリレートの新中村化学工業社製Ａ－ＢＰＥＦ－２「９，９－ビス［４－（２－アクリロイルオキシエトキシ）フェニル］フルオレン」（構造式を化３に示す）。
　Ｄ成分：フッ素含有量が５９．１質量％である単官能含フッ素アクリレートのユニマテック社製ＣＨＥＭＩＮＯＸ（登録商標）ＦＡＡＣ－６「２－（パーフルオロヘキシル）エチルメタクリレート」（構造式を化６に示す）。
　Ｃ成分：光重合開始剤のＣｉｂａ　Ｓｐｅｃｉａｌｔｙ　Ｃｈｅｍｉｃａｌｓ社製Ｉｒｇａｃｕｒｅ（登録商標）１８４。 Component A: Bifunctional fluorine-containing acrylate with a fluorine content of 41.1% by mass B5278 "2,2,3,3,4,5,5-octafluorohexane-1,6-" manufactured by Tokyo Kasei Co., Ltd. Dimethacrylic acid "(structural formula is shown in Chemical formula 2).
Component B: A-BPEF-2 "9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., a bifunctional acrylate having a benzene ring (the structural formula is shown in Chemical formula 3). ).
Component D: CHEMINOX® FAAC-6 "2- (perfluorohexyl) ethyl methacrylate" manufactured by Unimatec, a monofunctional fluorine-containing acrylate having a fluorine content of 59.1% by mass (structural formula is shown in Chemical formula 6). ).
Component C: Irgacare® 184, manufactured by Ciba Specialty Chemicals, a photopolymerization initiator.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　次に、発明を実施するための形態において記載した、ＵＶ硬化型樹脂を得るための前駆体樹脂組成物のＡ成分～Ｅ成分のうち、以下に示すＡ成分とＢ成分とＤ成分とＥ成分とを重量比４０：４０：１０：１０で混合した。さらに以下に示すＣ成分を０．１重量部混合し、全てが均一に相溶している前駆体樹脂組成物を得た。次に、上述の混合して得られた前駆体樹脂組成物を用いて、実施例１に記載の方法によって、平板状の光学素子を得た。そして屈折計Ａｂｂｅｍａｔ　ＭＷ（アントンパール社）を用いて、形成した光学素子の屈折率ｎｄ、アッベ数νｄ及び２次分散特性θｇＦを測定した。 Next, among the components A to E of the precursor resin composition for obtaining the UV curable resin described in the embodiment for carrying out the invention, the components A, B, D and E shown below And were mixed at a weight ratio of 40:40:10:10. Further, 0.1 parts by weight of the C component shown below was mixed to obtain a precursor resin composition in which all of them were uniformly compatible. Next, using the precursor resin composition obtained by mixing as described above, a flat plate-shaped optical element was obtained by the method described in Example 1. And using refractometer Abbemat MW a (Anton Paar), the refractive index n d of the formed optical element was measured Abbe number [nu d and second-order dispersion characteristic theta gF.
　Ａ成分：フッ素含有量が４１．１質量％である２官能含フッ素アクリレートの東京化成社製Ｂ５２７８「２，２，３，３，４，４，５，５－オクタフルオロヘキサン－１，６－ジメタクリル酸」（構造式を化２に示す）。
　Ｂ成分：ベンゼン環を有する２官能アクリレートの新中村化学工業社製Ａ－ＢＰＥＦ－２「９，９－ビス［４－（２－アクリロイルオキシエトキシ）フェニル］フルオレン」（構造式を化３に示す）
　Ｄ成分：フッ素含有量が５９．１質量％である単官能含フッ素アクリレートのユニマテック社製ＣＨＥＭＩＮＯＸ（登録商標）ＦＡＡＣ－６「２－（パーフルオロヘキシル）エチルメタクリレート」（構造式を化６に示す）。
　Ｅ成分：ベンゼン環を有する単官能アクリレートの共栄社化学ライトアクリレート（登録商標）ＰＯＢ－Ａ「３－フェノキシベンジルアクリレート」（構造式を化５に示す）。
　Ｃ成分：光重合開始剤のＣｉｂａ　Ｓｐｅｃｉａｌｔｙ　Ｃｈｅｍｉｃａｌｓ社製Ｉｒｇａｃｕｒｅ（登録商標）１８４。 Component A: Bifunctional fluorine-containing acrylate with a fluorine content of 41.1% by mass B5278 "2,2,3,3,4,5,5-octafluorohexane-1,6-" manufactured by Tokyo Kasei Co., Ltd. Dimethacrylic acid "(structural formula is shown in Chemical formula 2).
Component B: A-BPEF-2 "9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., a bifunctional acrylate having a benzene ring (the structural formula is shown in Chemical formula 3). )
Component D: CHEMINOX® FAAC-6 "2- (perfluorohexyl) ethyl methacrylate" manufactured by Unimatec, a monofunctional fluorine-containing acrylate having a fluorine content of 59.1% by mass (structural formula is shown in Chemical formula 6). ).
Component E: Kyoeisha Chemical Light Acrylate (registered trademark) POB-A "3-phenoxybenzyl acrylate" (structural formula is shown in Chemical formula 5), which is a monofunctional acrylate having a benzene ring.
Component C: Irgacare® 184, manufactured by Ciba Specialty Chemicals, a photopolymerization initiator.
〔評価結果〕
　実施例１～実施例５の評価結果を表１に示す。表１において各成分の欄に記載の数値は重量比を示している。表１に示すとおり、実施例１～実施例５の本件発明に係るＵＶ硬化型樹脂を得るための前駆体樹脂組成物は、いずれも屈折率ｎｄが１．５０以上１．６５以下であり、アッベ数νｄが２０以上５０以下であり、２次分散特性θｇＦが０．６２以上０．７０以下であり、２次分散特性の偏りΔθｇＦが０．０２以上０．０８以下の範囲であった。 〔Evaluation results〕
The evaluation results of Examples 1 to 5 are shown in Table 1. In Table 1, the numerical values described in the column of each component indicate the weight ratio. As shown in Table 1, the precursor resin composition for obtaining a UV-curable resin according to the present invention of Examples 1 to 5 are both refractive index n d be 1.50 or more 1.65 or less The Abbe number ν d is 20 or more and 50 or less, the secondary dispersion characteristic θ gF is 0.62 or more and 0.70 or less, and the bias Δθ gF of the secondary dispersion characteristic is in the range of 0.02 or more and 0.08 or less. Met.
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　次に、市販の光学ガラスと実施例１～実施例５の前駆体樹脂組成物を硬化して得られた成形体とにおけるアッベ数νｄと屈折率ｎｄとの関係分布を示すグラフを図２に、市販の光学ガラスと実施例１～実施例５の前駆体樹脂組成物を硬化して得られた成形体とにおけるアッベ数νｄと２次分散特性θｇＦとの関係分布を示すグラフを図１に示す。図２に示すとおり、実施例１～実施例５の本件発明に係るＵＶ硬化型樹脂を得るための前駆体樹脂組成物は、硬化後のアッベ数νｄと屈折率ｎｄとの関係において、特許文献２に記載の光学素子形成用樹脂組成物と比べて、アッベ数νｄが２０以上５０以下の範囲において高い屈折率ｎｄであることが確認できた。 Next, FIG graph showing the relationship between distribution of an Abbe number [nu d and the refractive index n d of the commercially available optical glasses of Example 1 to Example 5 of the precursor molded body of the resin composition obtained by curing No. 2 is a graph showing the relationship distribution between the Abbe number ν d and the secondary dispersion characteristic θ gF in a commercially available optical glass and a molded product obtained by curing the precursor resin compositions of Examples 1 to 5. Is shown in FIG. As shown in FIG. 2, the precursor resin composition for obtaining a UV-curable resin according to the present invention of Examples 1 to 5, in relation to the refractive index n d and the Abbe number [nu d after curing, compared with an optical element forming resin composition described in Patent Document 2, it was confirmed that the Abbe number [nu d is higher refractive index n d in the range of 20 to 50..
　また、図１に示すとおり、実施例１～実施例５の本件発明に係るＵＶ硬化型樹脂を得るための前駆体樹脂組成物は、硬化後のアッベ数νｄと２次分散特性θｇＦとの関係において、市販のガラス及び特許文献２に記載の光学素子形成用樹脂組成物と比較して、アッベ数νｄが２０以上５０以下の範囲において２次分散特性θｇＦが高い異常部分分散特性を示すことが確認できた。なお、図１中の直線は、正常分散ガラスの基準となるＨＯＹＡ社のＣ７（コード５１１－６０５）及びＦ２（コード６２０－３６３）におけるアッベ数νｄ（６０．４９、３６．３）と２次分散特性θｇＦ（０．５３９３、０．５８２９）とを通る標準線である。 Further, as shown in FIG. 1, the precursor resin composition for obtaining the UV curable resin according to the present invention of Examples 1 to 5 has an Abbe number ν d after curing and a secondary dispersion characteristic θ g F. In this relationship, the secondary dispersion characteristic θ gF is higher in the range where the Abbe number ν d is 20 or more and 50 or less as compared with the commercially available glass and the resin composition for forming an optical element described in Patent Document 2. It was confirmed that The straight lines in FIG. 1 are Abbe numbers ν d (60.49, 36.3) and 2 in HOYA's C7 (code 511-605) and F2 (code 620-363), which are the standards for normally dispersed glass. It is a standard line passing through the next dispersion characteristic θ gF (0.5393, 0.5829).
　本件発明に係るＵＶ硬化型樹脂を得るための前駆体樹脂組成物は、硬化後において、特許文献２に記載の光学素子形成用樹脂組成物と比べた場合、アッベ数νｄが２０以上５０以下の範囲において、屈折率ｎｄが高く、２次分散特性θｇＦが高いという光学特性を有するので、当該前駆体樹脂組成物を用いて形成した樹脂レンズと、市販の光学ガラスを用いて形成したガラスレンズとを組み合わせることで、光学設計においてより高い自由度を持たせることができ、色収差を良好に補正することができる。 The precursor resin composition for obtaining the UV curable resin according to the present invention has an Abbe number ν d of 20 or more and 50 or less as compared with the resin composition for forming an optical element described in Patent Document 2 after curing. in the range, the refractive index n d is high, because the second-order dispersion characteristic theta gF having optical properties of high, and a resin lens formed by using the precursor resin composition was formed using a commercially available optical glass By combining with a glass lens, it is possible to have a higher degree of freedom in optical design, and chromatic aberration can be satisfactorily corrected.

Claims (6)

  1. 　異常部分分散特性を備えた光学素子の製造に用いるＵＶ硬化型樹脂を得るための前駆体樹脂組成物であって、
    　前記前駆体樹脂組成物は、以下に示すＡ成分と、Ｂ成分と、Ｃ成分とを含むことを特徴とする前駆体樹脂組成物。
    　Ａ成分：２官能含フッ素アクリレート及び／又は２官能含フッ素メタクリレート。
    　Ｂ成分：ベンゼン環を有する２官能アクリレート及び／又はベンゼン環を有する２官能メタクリレート。
    　Ｃ成分：光重合開始剤。     A precursor resin composition for obtaining a UV curable resin used for manufacturing an optical element having anomalous partial dispersion characteristics.
    The precursor resin composition is a precursor resin composition containing the following A component, B component, and C component.
    Component A: Bifunctional fluorine-containing acrylate and / or bifunctional fluorine-containing methacrylate.
    Component B: Bifunctional acrylate having a benzene ring and / or bifunctional methacrylate having a benzene ring.
    Component C: Photopolymerization initiator.
  2. 　以下に示すＤ成分を含む、請求項１に記載の前駆体樹脂組成物。
    　Ｄ成分：単官能含フッ素アクリレート及び／又は単官能含フッ素メタクリレート。     The precursor resin composition according to claim 1, which comprises the D component shown below.
    Component D: monofunctional fluorine-containing acrylate and / or monofunctional fluorine-containing methacrylate.
  3. 　以下に示すＥ成分を含む、請求項１又は請求項２に記載の前駆体樹脂組成物。
    　Ｅ成分：ベンゼン環を有する単官能アクリレート及び／又はベンゼン環を有する単官能メタクリレート。     The precursor resin composition according to claim 1 or 2, which comprises the component E shown below.
    Component E: Monofunctional acrylate having a benzene ring and / or monofunctional methacrylate having a benzene ring.
  4. 　前記Ａ成分が、以下の化１に示す構造式を備える化合物である請求項１～請求項３のいずれか一項に記載の前駆体樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     ［式中、Ｒ２１及びＲ２２はそれぞれ独立に水素原子又はメチル基であり、ｘは１～２の整数であり、Ｙは炭素数２～１２のパーフルオロアルキル基又は－（ＣＦ２－Ｏ－ＣＦ２）Ｚ－であり、前記ｚは１～４の整数である。］     The precursor resin composition according to any one of claims 1 to 3, wherein the component A is a compound having the structural formula shown in Chemical formula 1 below.
    Figure JPOXMLDOC01-appb-C000001
     [In the formula, R 21 and R 22 are independent hydrogen atoms or methyl groups, x is an integer of 1 to 2, and Y is a perfluoroalkyl group having 2 to 12 carbon atoms or-(CF 2- O). -CF 2 ) Z- , and z is an integer of 1 to 4. ]
  5. 　請求項１～請求項４のいずれか一項に記載の前駆体樹脂組成物を用いて得られることを特徴とする異常部分分散特性を備える光学素子。 An optical element having anomalous partial dispersion characteristics, which is obtained by using the precursor resin composition according to any one of claims 1 to 4.
  6. 　屈折率ｎｄが１．５０以上１．６５以下であり、アッベ数νｄが２０以上５０以下であり、２次分散特性θｇＦが０．６２以上０．７０以下であり、２次分散特性の偏りΔθｇＦが０．０２以上０．０８以下である請求項５に記載の異常部分分散特性を備える光学素子。 The refractive index n d is 1.50 or more and 1.65 or less, the Abbe number ν d is 20 or more and 50 or less, the secondary dispersion characteristic θ gF is 0.62 or more and 0.70 or less, and the secondary dispersion characteristic. The optical element having the abnormal partial dispersion characteristic according to claim 5, wherein the bias Δθ gF is 0.02 or more and 0.08 or less.
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Citations (4)

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WO2006082845A1 (en) * 2005-02-04 2006-08-10 Daikin Industries, Ltd. Curable composition and optical member obtained by curing same
US7446159B1 (en) * 2007-09-20 2008-11-04 Sony Corporation Curable resin composition
WO2019069488A1 (en) * 2017-10-03 2019-04-11 株式会社ニコン Compound, resin precursor, cured product, optical element, optical system, interchangeable lens for camera, optical device, cemented lens, and production method for cemented lens
JP2019151809A (en) * 2018-03-06 2019-09-12 株式会社タムロン Resin composition for forming optical element and optical element

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006082845A1 (en) * 2005-02-04 2006-08-10 Daikin Industries, Ltd. Curable composition and optical member obtained by curing same
US7446159B1 (en) * 2007-09-20 2008-11-04 Sony Corporation Curable resin composition
WO2019069488A1 (en) * 2017-10-03 2019-04-11 株式会社ニコン Compound, resin precursor, cured product, optical element, optical system, interchangeable lens for camera, optical device, cemented lens, and production method for cemented lens
JP2019151809A (en) * 2018-03-06 2019-09-12 株式会社タムロン Resin composition for forming optical element and optical element

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