JP2021081464A - Precursor resin composition and optical element - Google Patents

Abstract

To provide a resin composition for forming an optical element for correcting chromatic aberration by combining a glass lens and a resin lens which has a high degree of freedom in optical design due to refraction index nd, Abbe number νd and secondary dispersion characteristics θgF after curing different from those of a conventional resin composition for forming an optical element, and an optical element using the resin composition for forming the optical element.SOLUTION: The precursor resin composition is a precursor resin composition for obtaining a UV curable resin used in production of an optical element having abnormal part dispersion characteristics. The precursor resin composition contains 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; and component C: photopolymerization initiator.SELECTED DRAWING: Figure 1

Description

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.

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.

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.

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.

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.

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.

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.

Japanese Unexamined Patent Publication No. 2010-97195 JP-A-2019-151809

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.

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.

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.

As a result of diligent research, we came up with the following inventions in order to solve the above-mentioned problems.
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. 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.

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 a commercially available optical glass and the precursor resin composition of Examples 1-5. It 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 glass and the precursor resin composition molded article obtained by curing the Examples 1-5.

Hereinafter, embodiments of a precursor resin composition for obtaining a UV curable resin according to the present invention will be described.

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.

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. 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.

Further, the component A according to the present invention preferably 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.

［式中、Ｒ^２１及びＲ^２２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−（ＣＦ_２−Ｏ−ＣＦ_２）_Ｚ−であり、前記ｚは１〜４の整数である。］

[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. ]

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 diacrylate (CAS: 2264-01-9), 2. , 2,3,3,4,5,5-Octofluorohexan-1,6-diyl dimethothericrate (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. 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.

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. 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.

Specific examples of the photopolymerization initiator used as the C component include 2,2-dimethoxy-2-phenylplasmenone, 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-methyltropionyl) benzyl) phenyl) -2-methylpropan-1-on Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2- (dimerylamino) -4'-morpholino phenylphenone, 2-dimerylamino-2- (4-methyl-benzyl) 1- (4-morpholin-4-yl-phenyl) -butan-1-one and the like can be mentioned.

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.

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 Acrylate (CAS: 2160-89-6) 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-Dodecafluoroheropeptide (CAS: 2261-99-6), 2,2,3,3,4,4 -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 Acrylate (CAS: 1799-84-4), 1H, 1H, 5H-Octofluoropendyl Acrylate (CAS: 355-) Benzyl Benzyllate (CAS: 114859-23-3), Pentafluoropheneyl Benzyllate (CAS: 13642-97-2), 2,2,3,3,3-Pentafluoropropyl Benzyllate (CAS: 45115-53-5), 2, 3,3-Tetrafluoropropyl Benzyl Rate (CAS: 45102-52-1), 1H, 1H, 2H, 2H-Tridecafluoro-n-octyl Benzyl Rate (CAS: 2144-53-8), 2,2,2-Trifuroethyl : 352-87-4) and the like.

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.

Specific examples of the organic compound used as the E component include Benzyl Acrylate (CAS: 2495-35-4), Benzyl Cinnamate (CAS: 103-41-3), Pentafluorobenzyl Methacrylate (CAS: 114859-23-3), and Pentaburo. 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] cinnamate (CAS: 16833-17-3), 4-Benzoylphenyl Metacrylate (CAS: 56467-43-7), 2-Phenoxy ethyl methacrylate (CAS: 16833-17-3), 2-Phenoxy ethyl methacrylate (CAS: 16833-17-3) Phenoxy ester acrylicate (CAS: 48145-04-6), Methyl Phenoxy ester acryliclate (CAS: 105489-31-8), Phenoxy dyeylenecrylate (CAS: 48145-04-6), Phenoxy dyeylyl acrylate (CAS: 48145-04-6), Phenoxy dyeylyl acrylate (CAS: 48145-04-6) 5), m-Phenoxybenzyl acrylicate (CAS: 409325-06-0), 2-Hydroxy 3-phenoxy acrylate (CAS: 16969-10-1), Neopenthylglycol-benzoate-cly Can be mentioned.

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.

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. 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.

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.

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).

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.

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.

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.

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 × 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.

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.

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.

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.

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.

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.

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.

Next, among the A component to the E component of the precursor resin composition for obtaining the UV curable resin described in the embodiment for carrying out the invention, the A component, the B component, the D component and the E component 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.

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.

〔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.

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 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..

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).}

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)

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. 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. 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. 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.

[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. ] 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. 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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