WO2019216008A1 - Optical resin composition and optical lens - Google Patents

Abstract

Disclosed is an optical resin composition containing (A) a first radical polymerizable component comprising at least one compound represented by formula (a1), etc., and (B) a second radical polymerizable component comprising a compound different from the first radical polymerizable component. When the first and second radical polymerizable components are radically polymerized, a resin material containing their polymers is formed, wherein the resin material has an Abbe number νd and a relative partial dispersion θg,F that satisfy the formulas 18 ≤ νd ≤ 25 and θg,F ≥ 0.700. [In formula (a1), at least one of X¹, X⁴, or X⁵ is a group having a (meth)acryloyl group.]

Description

Optical resin composition and optical lens

The present invention relates to an optical resin composition and an optical lens obtained from the composition.

Many optical materials that constitute an imaging optical system such as a camera are known. In particular, organic optical materials such as plastic lenses are lighter and harder to break than inorganic materials, can be processed into various shapes, and have a high degree of freedom in designing materials with desired characteristics. Recently, it is rapidly spreading in various applications.

Generally, an imaging optical system such as a camera is configured by combining a plurality of types of optical lenses having different optical properties. In particular, a technique for correcting chromatic aberration of an optical system by combining optical lenses having different refractive index wavelength dispersion characteristics is employed. Conventionally, the Abbe number νd is mainly used as an index indicating wavelength dispersion characteristics, and it has been attempted to correct chromatic aberration by combining a material having a high Abbe number and a material having a low Abbe number.

Furthermore, as a method of correcting chromatic aberration at a higher level with respect to organic optical materials, it has been proposed to use an optical material that exhibits a low Abbe number and a specific partial dispersion ratio θg, F (Patent Document 1). ).

On the other hand, Patent Document 2 describes that an organic-inorganic composite material in which inorganic fine particles are dispersed in a thermoplastic resin having a specific benzotriazole skeleton has a high refractive index and a low Abbe number. Patent Document 3 describes that a high refractive index polymer having a benzotriazole skeleton as an ultraviolet absorbing group is excellent in light resistance and does not cause bleed-out with respect to materials used for paints and the like.

JP 2010-097195 A JP 2010-189562 A JP 2014-201735 A

Generally, although the partial dispersion ratio tends to be relatively high when the Abbe number is low, a material having a low Abbe number does not always exhibit a sufficiently high partial dispersion ratio. Furthermore, conventionally, materials exhibiting a low Abbe number and a high partial dispersion ratio often lack characteristics required for optical lenses such as light transmittance, heat resistance, and light resistance. For example, an optical material including a compound having a diphenyl sulfide skeleton disclosed in Patent Document 1 has low light resistance and heat resistance, and there is room for improvement in terms of long-term reliability.

An object of the present invention is to provide an optical resin composition that can form a resin material for an optical member that exhibits a low Abbe number and a high partial dispersion ratio, and has excellent light resistance, high light transmittance, and high heat resistance. Is to provide.

One aspect of the present invention is: (A) a first radical polymerizable component comprising at least one radical polymerizable compound represented by the following formula (a1), (a2) or (a3); The present invention relates to an optical resin composition containing a second radical polymerizable component comprising a radical polymerizable compound different from the first radical polymerizable component. When the first radical polymerizable component and the second radical polymerizable component are radically polymerized, a resin material containing these polymers is formed. The Abbe number νd and the partial dispersion ratio θg, F of the resin material are expressed by the following formula:
18 ≦ νd ≦ 25; and θg, F ≧ 0.700
Meet.

In formula (a1),
X ¹ represents a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, an optionally substituted alkoxycarbonylalkyl group having 1 to 18 carbon atoms, or , A group having a (meth) acryloyl group,
X ² and X ³ each independently represent a hydrogen atom, a halogen atom, or an optionally substituted hydrocarbon group having 1 to 18 carbon atoms,
X ⁴ represents a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, or a group having a (meth) acryloyl group,
X ⁵ represents a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, or a group having a (meth) acryloyl group,
At least one of X ¹ , X ⁴ or X ⁵ is a group having a (meth) acryloyl group.

In formula (a2),
Y ¹ and Y ² each independently represent a hydrogen atom, a hydroxyl group, an optionally substituted alkoxy group having 1 to 8 carbon atoms, or a group having a (meth) acryloyl group,
Y ³ and Y ⁴ each independently represent a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, or a group having a (meth) acryloyl group,
At least one of Y ¹ , Y ² , Y ³ or Y ⁴ is a group having a (meth) acryloyl group.

In formula (a3),
Z ¹ has an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, an optionally substituted alkylcarbonyloxyalkyl group having 1 to 18 carbon atoms, and a substituent. An optionally substituted alkoxycarbonylalkyl group having 1 to 18 carbon atoms, or an optionally substituted alkoxyalkyl group having 1 to 18 carbon atoms;
Z ² , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁸ and Z ⁹ are each independently a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, or a substituent. An alkoxy group having 1 to 8 carbon atoms which may be present;
Z ³ represents a hydrogen atom or a group having a (meth) acryloyl group,
Z ⁷ represents a hydrogen atom, a hydroxyl group, an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, an optionally substituted alkoxy group having 1 to 8 carbon atoms, or (meth) A group having an acryloyl group;
At least one of Z ^{3 and} Z ⁷ is a group having a (meth) acryloyl group.

As described above, the optical resin composition containing the first radical polymerizable component and the second radical polymerizable component exhibits a low Abbe number and a high partial dispersion ratio, and has excellent light resistance, high light transmittance, and A resin material for an optical member having high heat resistance can be formed.

Another aspect of the present invention relates to an optical lens made of a resin material including a polymer formed by radical polymerization of a first radical polymerizable component and a second radical polymerizable component in the optical resin composition. The optical lens can exhibit a low Abbe number and a high partial dispersion ratio, and can have excellent light resistance, high light transmittance, and high heat resistance.

The optical resin composition according to the present invention can form a resin material for an optical member that exhibits a low Abbe number and a high partial dispersion ratio, and has excellent light resistance, high light transmittance, and high heat resistance. By using this molded body of resin material as an optical lens, chromatic aberration of the optical system can be efficiently removed.

It is sectional drawing which shows one Embodiment of an optical lens.

Hereinafter, some embodiments of the present invention will be described in detail.

In this specification, “(meth) acryl” means “acryl” and “metaacryl”.

An optical resin composition according to an embodiment includes a first radical polymerizable component composed of at least one radical polymerizable compound represented by formula (a1), (a2), or (a3), and (B) And a second radical polymerizable component made of a radical polymerizable compound different from the first radical polymerizable component. When the first radical polymerizable component and the second radical polymerizable component undergo radical polymerization, a solid resin material containing a polymer of these radical polymerizable components is formed. For example, when at least one of the first radical polymerizable component or the second radical polymerizable component contains a polyfunctional radical polymerizable compound having two or more radical polymerizable groups, a crosslinked polymer is used. A resin material (cured product) is formed.

The Abbe number νd and the partial dispersion ratio θg, F of the resin material formed from the optical resin composition according to this embodiment satisfy the following expressions. Satisfaction of these equations means that the resin material exhibits a significantly high partial dispersion ratio while exhibiting a relatively low Abbe number.
18 ≦ νd ≦ 25
θg, F ≧ 0.700

(A) The first radical polymerizable component is a radical polymerizable compound represented by formula (a1), a radical polymerizable compound represented by formula (a2), or a radical polymerizable compound represented by formula (a3). Or a combination of two or more selected from these. Each of the radically polymerizable compounds represented by the formula (a1), (a2) or (a3) constituting the first radically polymerizable component has one or more (meth) acryloyl groups. The radically polymerizable compound represented by the formula (a1), (a2) or (a3) may be a monofunctional radically polymerizable compound having one (meth) acryloyl group.

The radically polymerizable compound represented by the formula (a1) has a benzotriazole skeleton, and has a (meth) acryloyl group in at least one of X ¹ , X ^{4 and} X ⁵ .

Examples of the halogen atom represented by X ¹ in the formula (a1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. X ¹ may be a chlorine atom.

When the formula (a1) is a hydrocarbon group having 1 to 18 carbon atoms having a substituent, the substituent may be, for example, a halogeno group, an alkoxy group or a hydroxy group. The same applies to specific examples of substituents in other compounds described below. Examples of the optionally substituted hydrocarbon group having 1 to 18 carbon atoms represented by X ¹ in the formula (a1) include a methyl group, an ethyl group, a 2-methoxyethyl group, and n-propyl. Group, isopropyl group, 3-chloro-n-propyl group, n-butyl group, sec-butyl group, tert-butyl group, 4-hydroxy-n-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert -Pentyl group, n-hexyl group, isohexyl group, cyclohexyl group, 6-phenyl-n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, 1,1,3,3-tetramethylbutyl group, n-dodecyl group, n-octadecyl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3-chlorophenyl group, 4-bromophenyl Group, 3,4-dichlorophenyl group, naphthyl group, benzyl group, phenethyl group, 1-methyl-1-phenethyl group and the like. X ¹ may be a hydrocarbon group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, isopentyl group, neopentyl group, It may be an n-pentyl group, a tert-pentyl group, an n-hexyl group, or an n-octyl group.

Examples of the alkoxycarbonylalkyl group having 1 to 18 carbon atoms which may have a substituent represented by X ¹ in the formula (a1) include a methoxycarbonylethyl group, an ethoxycarbonylethyl group, n-octoxy Carbonylethyl group, isooctyloxycarbonylethyl group, n-dodecyloxycarbonylethyl group, methoxycarbonylpropyl group, ethoxycarbonylpropyl group, n-octoxycarbonylpropyl group, isooctyloxycarbonylpropyl group, and n-dodecyloxycarbonyl A propyl group etc. are mentioned. X ¹ may be a methoxycarbonylethyl group, an ethoxycarbonylethyl group, an n-octoxycarbonylethyl group, or an isooctyloxycarbonylethyl group. The number of carbon atoms of the alkoxycarbonylalkyl group means the total number of carbon atoms contained in the alkoxy moiety, the carbonyl moiety, and the alkyl moiety contained in the alkoxycarbonylalkyl group.

Examples of the group having a (meth) acryloyl group represented by X ¹ in the formula (a1) include an acryloyl group, an acryloyloxy group, an acryloyloxyethyl group, a methacryloyl group, a methacryloyloxy group, and a methacryloyloxyethyl group. Is mentioned. X ¹ may be an acryloyloxyethyl group or a methacryloyloxyethyl group.

The hydrocarbon group having 1 to 18 carbon atoms which may have a halogen atom and a substituent represented by X ² or X ³ in the formula (a1) is a halogen atom and a substituent represented by X ^1. It is synonymous with the C1-C18 hydrocarbon group which may have.

Represented by X ⁴ in the formula (a1), a hydrocarbon group which has carbon atoms 1 be ~ 18 have a substituent, represented by X ^1, carbon atoms which may have a substituent 1 Synonymous with ˜18 hydrocarbon groups.

Examples of the group having a (meth) acryloyl group represented by X ⁴ in the formula (a1) include an acryloyl group, 2- (acryloyloxy) ethylcarbamoyl group, methacryloyl group, and 2- (methacryloyloxy) ethylcarbamoyl. Groups and the like.

The hydrocarbon group having 1 to 18 carbon atoms which may have a halogen atom and a substituent represented by X ⁵ in the formula (a1) has a halogen atom and a substituent represented by X ^1. It is synonymous with a hydrocarbon group having 1 to 18 carbon atoms.

Examples of the group having a (meth) acryloyl group represented by X ⁵ in the formula (a1) include an acryloyl group, an acryloyloxy group, an acryloyloxyethyl group, an acryloyloxyethoxy group, a methacryloyl group, a methacryloyloxy group, and a methacryloyl group. Examples thereof include an oxyethyl group and a methacryloyloxyethoxy group. X ⁵ may be an acryloyloxyethoxy group or a methacryloyloxyethoxy group.

Specific examples of the radical polymerizable compound represented by the formula (a1) include 2- [2-hydroxy-5- [2- (methacryloyloxy) ethyl] phenyl] -2H-benzotriazole (for example, trade name “RUVA” -93 "(manufactured by Otsuka Chemical Co., Ltd.) or Tokyo Chemical Industry Co., Ltd.), 2- [2-hydroxy-3-tert-butyl-5- [2- (methacryloyloxy) ethyl] phenyl] -2H- Benzotriazole, 2- (2-hydroxy-5-methylphenyl) -5- [2- (methacryloyloxy) ethyl] -2H-benzotriazole, 2- [2- (2-hydroxy-4-octyloxyphenyl)- 2H-1,2,3-benzotriazol-5-yloxy] ethyl methacrylate, 2- [2- (2- (methacryloyloxy) ethylcarbamo Ruoxy) -5- [2- (methacryloyloxy) ethyl] phenyl] -2H-benzotriazole, 2- [2-methacryloyloxy-5- [2- (methacryloyloxy) ethyl] phenyl] -2H-benzotriazole, etc. Is mentioned.

The radically polymerizable compound represented by the formula (a2) has a benzophenone skeleton, and has a (meth) acryloyl group in at least one of Y ¹ , Y ² , Y ³ or Y ⁴ .

Examples of the optionally substituted alkoxy group represented by Y ¹ or Y ² in the formula (a2) having 1 to 8 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group Group, n-butoxy group, sec-butoxy group, tert-butoxy group, 4-hydroxy-n-butoxy group, n-pentoxy group, isopentoxy group, neopentoxy group, tert-pentoxy group, n-hexyloxy group, isohexyl Examples thereof include an oxy group, a cyclohexyloxy group, an n-heptyloxy group, an n-octyloxy group, an isooctyloxy group, and a 1,1,3,3-tetramethylbutoxy group. Y ¹ and Y ² are each independently methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-hexyloxy group, isohexyloxy group Or a n-octyloxy group.

Examples of the group having a (meth) acryloyl group represented by Y ¹ or Y ² in the formula (a2) include acryloyl group, acryloyloxy group, acryloyloxyethyl group, acryloyloxyethoxy group, 2- (acryloyloxy) ) An ethylcarbamoyloxy group, a methacryloyl group, a methacryloyloxy group, a methacryloyloxyethyl group, a methacryloyloxyethoxy group, and a 2- (methacryloyloxy) ethylcarbamoyloxy group. Y ¹ and Y ² may each independently be an acryloyloxy group, a 2- (acryloyloxy) ethylcarbamoyloxy group, a methacryloyloxy group, or a 2- (methacryloyloxy) ethylcarbamoyloxy group.

Examples of the optionally substituted hydrocarbon group having 1 to 18 carbon atoms represented by Y ³ or Y ⁴ in the formula (a2) include a methyl group, an ethyl group, a 2-methoxyethyl group, n-propyl, isopropyl, 3-chloro-n-propyl, n-butyl, sec-butyl, tert-butyl, 4-hydroxy-n-butyl, n-pentyl, isopentyl, neopentyl Group, tert-pentyl group, n-hexyl group, isohexyl group, cyclohexyl group, 6-phenyl-n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, 1,1,3,3-tetramethyl Butyl, n-dodecyl, n-octadecyl, phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 3-chlorophenyl, 4-butyl Mofeniru group, 3,4-dichlorophenyl group, a naphthyl group, a benzyl group, phenethyl group, and 1-methyl-1-phenethyl. Y ³ and Y ⁴ may each independently be a hydrocarbon group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group It may be a group, isopentyl group, neopentyl group, n-pentyl group, tert-pentyl group, n-hexyl group, or n-octyl group.

Examples of the group having a (meth) acryloyl group represented by Y ³ or Y ⁴ in the formula (a2) include an acryloyl group, a 2- (acryloyloxy) ethylcarbamoyl group, a methacryloyl group, and 2- (methacryloyloxy). ) Ethylcarbamoyl group and the like.

Specific examples of the radical polymerizable compound represented by the formula (a2) include 2-hydroxy-4-acryloyloxybenzophenone (for example, FINIPHARMA LIMITED), 2-hydroxy-4-methacryloyloxybenzophenone (for example, Alfa Aesar). 2,2 ′, 4,4′-tetramethacrylyloxybenzophenone, 2,2 ′, 4,4′-tetra [2- (methacrylyloxy) ethylcarbamoyloxy] benzophenone, and the like.

The radically polymerizable compound represented by the formula (a3) has a triazine skeleton, and has a (meth) acryloyl group in at least one of Z ^{3 and} Z ⁷ .

Examples of the optionally substituted hydrocarbon group having 1 to 18 carbon atoms represented by Z ¹ in the formula (a3) include a methyl group, an ethyl group, a 2-methoxyethyl group, and n-propyl. Group, isopropyl group, 3-chloro-n-propyl group, n-butyl group, sec-butyl group, tert-butyl group, 4-hydroxy-n-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert -Pentyl group, n-hexyl group, isohexyl group, cyclohexyl group, 6-phenyl-n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, 1,1,3,3-tetramethylbutyl group, n-dodecyl group, n-octadecyl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3-chlorophenyl group, 4-bromophenyl Group, 3,4-dichlorophenyl group, naphthyl group, benzyl group, phenethyl group, 1-methyl-1-phenethyl group and the like. Z ¹ may be a hydrocarbon group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, isopentyl group, neopentyl group N-pentyl group, tert-pentyl group, n-hexyl group, n-octyl group, or phenyl group.

Examples of the alkylcarbonyloxyalkyl group having 1 to 18 carbon atoms which may have a substituent represented by Z ¹ in the formula (a3) include a methylcarbonyloxyethyl group, an ethylcarbonyloxyethyl group, and And (2-ethylhexyl) carbonyloxyethyl group. Z ¹ may be a (2-ethylhexyl) carbonyloxyethyl group. The carbon number of the alkylcarbonyloxyalkyl group means the total number of carbon atoms contained in the two alkyl moieties contained in the alkylcarbonyloxyalkyl group and the carbonyl moiety.

Examples of the optionally substituted alkoxycarbonylalkyl group represented by Z ¹ in formula (a3) include a methoxycarbonylethyl group, an ethoxycarbonylethyl group, n-octoxy Carbonylethyl group, isooctyloxycarbonylethyl group, n-dodecyloxycarbonylethyl group, methoxycarbonylpropyl group, ethoxycarbonylpropyl group, n-octoxycarbonylpropyl group, isooctyloxycarbonylpropyl group, and n-dodecyloxycarbonyl A propyl group etc. are mentioned. Z ¹ may be a methoxycarbonylethyl group, an ethoxycarbonylethyl group, an n-octoxycarbonylethyl group, or an isooctyloxycarbonylethyl group. The number of carbon atoms of the alkoxycarbonylalkyl group means the total number of carbon atoms contained in the alkoxy moiety, carbonyl moiety and alkyl moiety contained in the alkoxycarbonylalkyl group.

Examples of the optionally substituted alkoxyalkyl group represented by Z ¹ in the formula (a3) include a methoxymethyl group, a methoxyethyl group, a 3-methoxypropyl group, an ethoxy group. Methyl group, ethoxyethyl group, 3-ethoxypropyl group, 3- (n-hexyloxy) propyl group, (2-ethylhexyloxy) -2-hydroxypropyl group, (dodecyloxy) -2-hydroxypropyl group, etc. Can be mentioned. Z ¹ may be a (2-ethylhexyloxy) -2-hydroxypropyl group. The carbon number of the alkoxyalkyl group means the total number of carbon atoms contained in the alkoxy moiety and the alkyl moiety contained in the alkoxyalkyl group.

The optionally substituted hydrocarbon group having 1 to 18 carbon atoms represented by Z ² , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁸ or Z ⁹ in the formula (a3) is Z ¹ It is synonymous with the C1-C18 hydrocarbon group which may have a substituent shown.

Examples of the optionally substituted alkoxy group having 1 to 8 carbon atoms represented by Z ² , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁸ or Z ⁹ in the formula (a3) include methoxy Group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, 4-hydroxy-n-butoxy group, n-pentoxy group, isopentoxy group, neopentoxy group, tert -Pentoxy group, n-hexyloxy group, isohexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, 1,1,3,3-tetramethylbutoxy group, etc. Is mentioned. Z ² , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁸ and Z ⁹ are each independently methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert It may be a -butoxy group, n-hexyloxy group, isohexyloxy group, or n-octyloxy group.

Examples of the group having a (meth) acryloyl group represented by Z ³ in the formula (a3) include an acryloyl group, 2- (acryloyloxy) ethylcarbamoyl group, methacryloyl group, and 2- (methacryloyloxy) ethylcarbamoyl. Groups and the like.

Represented by Z ⁷ in formula (a3), a hydrocarbon group which has carbon atoms 1 be ~ 18 have a substituent, represented by Z ^1, carbon atoms which may have a substituent 1 Synonymous with ˜18 hydrocarbon groups. The alkoxy group having 1 to 8 carbon atoms which may have a substituent represented by Z ⁷ in formula (a3) is an optionally substituted carbon group represented by Z ² or the like. Synonymous with the alkoxy group of ˜8.

Examples of the group having a (meth) acryloyl group represented by Z ⁷ in the formula (a3) include an acryloyl group, an acryloyloxy group, an acryloyloxyethyl group, an acryloyloxyethoxy group, and 2- (acryloyloxy) ethylcarbamoyl. Examples thereof include an oxy group, a methacryloyl group, a methacryloyloxy group, a methacryloyloxyethyl group, a methacryloyloxyethoxy group, and a 2- (methacryloyloxy) ethylcarbamoyloxy group. Z ⁷ may be an acryloyloxy group, a 2- (acryloyloxy) ethylcarbamoyloxy group, a methacryloyloxy group, or a 2- (methacryloyloxy) ethylcarbamoyloxy group.

As a specific example of the radically polymerizable compound represented by the formula (a3), in the formula (a3), Z ¹ is an isooctyloxycarbonylethyl group, and Z ² , Z ⁴ , Z ⁵ , Z ⁷ and Z ⁸ are hydrogen. A compound in which Z ³ is a 2- (acryloyloxy) ethylcarbamoyl group and Z ⁶ and Z ⁹ are phenyl groups, Z ¹ is an n-octyl group in formula (a3), Z ² , Z ⁵ and Z ^A compound in which ⁸ is a hydrogen atom, Z ⁴ , Z ⁶ , Z ⁷ and Z ⁹ are methyl groups and Z ³ is a 2- (methacryloyloxy) ethylcarbamoyl group, and in formula (a3), Z ¹ is n- Compounds such as a butyl group, Z ² , Z ⁵ and Z ⁸ are hydrogen atoms, Z ⁴ , Z ⁶ and Z ⁹ are n-butoxy groups, Z ³ is a methacryloyl group and Z ⁷ is a methacryloyloxy group. Can be mentioned.

The radical polymerizable compound represented by the formula (a1), (a2) or (a3) is, for example, a commercially available benzotriazole compound, benzophenone compound, triazine compound (hereinafter referred to as “raw material compound”) or a (meth) acryloyl group. Can be synthesized by introducing. The method for introducing the (meth) acryloyl group into the raw material compound is not particularly limited, and a usual method can be adopted. For example, a method in which (meth) acryloyl chloride is reacted in the presence of a base with a raw material compound having an active hydrogen group such as a hydroxyl group, an amino group, or a mercapto group, and 2-bromoethyl methacrylate is reacted with the raw material compound in the presence of a base. Method (Japanese Patent Laid-Open No. 2012-072333), a method in which an isocyanate compound having a (meth) acryloyl group is reacted with the raw material compound in the presence of a tin-based catalyst and / or an amine-based catalyst (Voprosy Khimiiiii Khmicheskoi Technologii, 1983, 70, 16 According to −22), the radically polymerizable compound represented by the formula (a1), (a2) or (a3) can be synthesized. In addition, the commercially available compound can also be used for the radically polymerizable compound represented by Formula (a1), (a2) or (a3).

The optical resin composition according to this embodiment further contains (B) a second radical polymerizable component. The second radical polymerizable component is one or more radical polymerizable compounds selected from compounds other than the radical polymerizable compound represented by formula (a1), (a2), or (a2) "Sometimes referred to as" second radical polymerizable compound ").

The second radical polymerizable compound has one or more radical polymerizable groups. The second radical polymerizable component may contain one or more polyfunctional radical polymerizable compounds. When the second radical polymerizable component contains a polyfunctional radical polymerizable compound, a crosslinked polymer is formed, and a resin material having higher heat resistance is formed. It can also be said that the resin material containing the crosslinked polymer is a cured product of the optical resin composition. Here, the “polyfunctional radically polymerizable compound” means a compound having two or more radically polymerizable groups in the molecule. “Monofunctional radically polymerizable compound” means a compound having one radically polymerizable group in the molecule.

The radical polymerizable group of the second radical polymerizable compound can be a (meth) acryl group, a vinyl group (excluding a vinyl group contained in the (meth) acryl group), or a combination thereof. Examples of the second radical polymerizable compound include a sulfide compound having a radical polymerizable group and a diphenyl sulfide skeleton, (meth) acrylic acid, (meth) acrylic acid ester, and other vinyl compounds.

Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) Acrylate, tert-butyl (meth) acrylate, 2-methylbutyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, 3-methylbutyl (meth) acrylate, 1,3-dimethylbutyl (meth) acrylate, pentyl (meth) acrylate , Hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-methoxyethyl acrylate, 2-ethoxy Ethyl acrylate, 3-ethoxypropyl acrylate, 2-ethoxybutyl acrylate, 3-ethoxybutyl acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, phenyl (meth) acrylate, benzyl ( (Meth) acrylate, phenylethyl (meth) acrylate, phenoxyethyl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, isobornyl (meth) acrylate, ethoxy O-phenylphenol (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, trifluoroethyl methacrylate Rate, and the monofunctional (meth) acrylic acid esters such as glycidyl (meth) acrylate; and,
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene Glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1 , 5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, tricyclodecane Methanol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate And other polyfunctional (meth) acrylic acid esters.

Examples of the vinyl compound include styrene, α-methylstyrene, 2,4-dimethylstyrene, α-ethylstyrene, α-butylstyrene, α-hexylstyrene, 4-chlorostyrene, 3-chlorostyrene, and 4-bromostyrene. Monofunctional vinyl compounds such as 4-nitrostyrene, 4-methoxystyrene, vinyltoluene, and cyclohexene, and divinylbenzene, 4-vinylcyclohexene, 5-vinylbicyclo [2,2,1] hept-2-ene And polyfunctional vinyl compounds such as diallyl diphenate and triallyltriazine.

Examples of the sulfide compound having a radical polymerizable group and a diphenyl sulfide skeleton include at least one sulfide compound represented by the following formula (b1) or (b2). Resin materials formed from optical resin compositions containing these sulfide compounds can exhibit a low Abbe number and a higher partial dispersion ratio. In addition, the refractive index of the resin material tends to increase.

In formulas (b1) and (b2), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms, and n is 0 to 10 R ⁵ represents a hydrogen atom or a methyl group. Two R ⁵ in the formula (b2) may be the same or different, and may be the same. N in the formula (b1) may be 0.

The halogen atom represented by R ¹ , R ² , R ³ or R ⁴ in formula (b1) or (b2) may be, for example, a chlorine atom, a bromine atom, or an iodine atom. Examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹ , R ² , R ³ or R ⁴ in the formula (b1) or (b2) include methyl group, ethyl group, n-propyl group, isopropyl Group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group and the like. R ¹ , R ² , R ³ and R ^{4 in} formula (b1) or (b2) may all be hydrogen atoms.

Examples of the sulfide compound represented by the formula (b1) include bis (4-vinylthiophenyl) sulfide, bis (3-methyl-4-vinylthiophenyl) sulfide, and bis (3,5-dimethyl-4-vinyl. Thiophenyl) sulfide, bis (2,3,5,6-tetramethyl-4-vinylthiophenyl) sulfide, bis (3-hexyl-4-vinylthiophenyl) sulfide, bis (3,5-dihexyl-4- Vinylthiophenyl) sulfide, bis (3-chloro-4-vinylthiophenyl) sulfide bis (3,5-dichloro-4-vinylthiophenyl) sulfide, bis (2,3,5,6-tetrachloro-4- Vinylthiophenyl) sulfide, bis (3-bromo-4-vinylthiophenyl) sulfide, bis (3,5-dibromo-4-bi) Thiophenyl) sulfide, and bis (2,3,5,6-tetrabromo-4-vinyl-thio-phenyl) sulfide, and the like. The sulfide compound represented by the formula (b1) is bis (4-vinylthiophenyl) sulfide, bis (3-methyl-4-vinylthiophenyl) sulfide, or bis (3,5-dimethyl-4-vinylthiophenyl). ) Sulfide or bis (4-vinylthiophenyl) sulfide.

Examples of the sulfide compound represented by the formula (b2) include S, S ′-(thiodi-p-phenylene) bis (thio (meth) acrylate), S, S ′-[4,4′-thiobis (2 -Chlorobenzene)] bis (thio (meth) acrylate), S, S '-[4,4'-thiobis (3-chlorobenzene)] bis (thio (meth) acrylate), S, S'-[4,4 ' -Thiobis (2,6-dichlorobenzene)] bis (thio (meth) acrylate), S, S '-[4,4'-thiobis (3,5-dichlorobenzene)] bis (thio (meth) acrylate), S, S ′-[4,4′-thiobis (2-bromobenzene)] bis (thio (meth) acrylate), S, S ′-[4,4′-thiobis (3-bromobenzene)] bis (thio (Meth) acrylate), S, '-[4,4'-thiobis (2,6-dibromobenzene)] bis (thio (meth) acrylate), S, S'-[4,4'-thiobis (3,5-dibromobenzene)] bis ( Thio (meth) acrylate), S, S ′-[4,4′-thiobis (2-methylbenzene)] bis (thio (meth) acrylate), S, S ′-[4,4′-thiobis (3- Methylbenzene)] bis (thio (meth) acrylate), S, S ′-[4,4′-thiobis (2,6-dimethylbenzene)] bis (thio (meth) acrylate), S, S ′-[4 , 4′-thiobis (3,5-dimethylbenzene)] bis (thio (meth) acrylate), and S, S ′-[4,4′-thiobis (2-tert-butylbenzene)] bis (thio (meta ) Acrylate) and the like. The sulfide compound represented by the formula (b2) is S, S ′-(thiodi-p-phenylene) bis (thiomethacrylate), S, S ′-[4,4′-thiobis (3,5-dibromobenzene) ] Bis (thiomethacrylate), S, S ′-[4,4′-thiobis (3,5-dimethylbenzene)] bis (thiomethacrylate), or S, S ′-(thiodi-p-phenylene) bis (thio Acrylate) or S, S ′-(thiodi-p-phenylene) bis (thiomethacrylate).

The sulfide compound represented by the formula (b1) is, for example, a bis (4-vinylthiophenyl) sulfide in which R ¹ to R ⁴ are all hydrogen atoms and n is 0 in the formula (b1). It can be obtained by reacting dihaloethane with '-thiodibenzenethiol and then dehydrohalogenating the product in a polar solvent such as dimethyl sulfoxide (Жypнa Op Opafa ничecкoй Xимии, т.28, вып.9 1905, 1992). it can. In this method, by changing reaction conditions such as the amount of dihaloethane used and the charging method, vinyl sulfide compounds having different values of n in formula (b1) can be obtained. Alternatively, a method of reacting a mercaptan compound and vinyl halide in the presence of a base (Japanese Patent Laid-Open No. 3-287572), or a mercaptan compound and 2-halogenoethanol as disclosed in Japanese Patent Laid-Open No. 2004-51488, Is reacted in the presence of an alkali metal compound, and then the product is reacted with a halogenating agent to form a dihalide, and the obtained dihalide is disclosed in JP-A No. 2003-183246. As described above, a sulfide compound represented by the formula (b1) may be obtained by a method including reacting with an alkali metal compound aqueous solution in a heterogeneous system in the presence of a phase transfer catalyst in an aliphatic hydrocarbon solvent. it can.

The sulfide compound represented by the formula (b2) is, for example, S, S ′-(thiodi-p-phenylene) in which R ¹ to R ⁴ are all hydrogen atoms and R ⁵ is a methyl group in the formula (b2) In the case of bis (thiomethacrylate), an alkali metal salt of 4,4′-thiodibenzenethiol obtained by reacting 4,4′-thiodibenzenethiol with an alkali metal compound and methacryloyl chloride are converted into nonpolar organic compounds. It can be obtained by a reaction in a solvent.

The second radically polymerizable component is a radical compound selected from the sulfide compound represented by formula (b1) or (b2), (meth) acrylic acid, (meth) acrylic acid ester, and other vinyl compounds. And a polymerizable compound. Examples of (meth) acrylic acid, (meth) acrylic acid ester, and other vinyl compounds used in combination with the sulfide compound represented by the formula (b1) or (b2) as the second radical polymerizable component are described above. Is the same as

The content of each radical polymerizable compound in the optical resin composition is adjusted so that the Abbe number νd and the partial dispersion ratio θg, F of the resin material containing these polymers satisfy the above formula. For example, when the ratio of the first radical polymerizable component is large, the Abbe number νd tends to decrease and the partial dispersion ratio θg, F tends to increase. Further, when the ratio of the second radical polymerizable component is large, the partial dispersion ratio θg, F tends to decrease. More specifically, for example, a resin material exhibiting an Abbe number νd and a partial dispersion ratio θg, F satisfying the above formula by adjusting the content of each radical polymerizable compound with reference to the numerical ranges exemplified below. Can be found.

(A) The total content of the first radical polymerizable component is 3 to 80 parts by mass, 5 to 5 parts per 100 parts by mass of the total amount of the first radical polymerizable component and the second radical polymerizable component. It may be 70 parts by mass or 5 to 60 parts by mass.

The content of the radical polymerizable compound represented by the formula (a1) is a viewpoint of maintaining a high light transmittance with respect to 100 parts by mass of the total amount of the first radical polymerizable component and the second radical polymerizable component. To 60 parts by mass or less, 50 parts by mass or less, or 30 parts by mass or less, or 3 parts by mass or more, or 5 parts by mass or more from the viewpoint of increasing the partial dispersion ratio θg, F. The content of the radical polymerizable compound represented by the formula (a2) is a viewpoint of maintaining a high light transmittance with respect to 100 parts by mass of the total amount of the first radical polymerizable component and the second radical polymerizable component. From the viewpoint of increasing the partial dispersion ratio θg, F, it may be 30 parts by mass or more. The content of the radical polymerizable compound represented by the formula (a3) is a viewpoint of maintaining a high light transmittance with respect to 100 parts by mass of the total amount of the first radical polymerizable component and the second radical polymerizable component. From the viewpoint of increasing the partial dispersion ratio θg, F, it may be 20 parts by mass or more.

(B) The total content of the second radical polymerizable component increases the partial dispersion ratio θg, F with respect to 100 parts by mass of the total amount of the first radical polymerizable component and the second radical polymerizable component. From the viewpoint, it may be 97 parts by mass or less, 95 parts by mass or less, or 90 parts by mass or less, and from the viewpoint of maintaining high light transmittance, it is 5 parts by mass or more, 10 parts by mass or more, or 20 parts by mass or more. May be.

The total content of the sulfide compound represented by the formula (b1) or (b2) is the light resistance of the resin material with respect to 100 parts by mass of the total amount of the first radical polymerizable component and the second radical polymerizable component. 95 parts by mass or less, or 90 parts by mass or less from the viewpoint of improving the properties, and 5 parts by mass for obtaining a resin material having a high refractive index (for example, 1.630 or more, or 1.650 or more). It may be 15 or more parts by mass. The ratio of the sulfide compound represented by the formula (b1) or (b2) in the (B) second radical polymerizable compound is 15 based on the total mass of the (B) second radical polymerizable component. It may be ˜100 mass%, 20˜100 mass%, or 25˜100 mass%. When the ratio of the sulfide compound represented by the formula (b1) or (b2) is within these ranges, a resin material having a high refractive index as well as a low Abbe number νd and a high light transmittance is easily obtained.

The optical resin composition according to the present embodiment may further contain a radical polymerization initiator for causing the radical polymerization of the first and second radical polymerizable components to proceed. The radical polymerization initiator can be a photo radical polymerization initiator, a thermal radical polymerization initiator, or a combination thereof.

Examples of photo radical polymerization initiators include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 1-hydroxycyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1 -Phenyl-propan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 4-phenylbenzophenone, 4-phenoxybenzophenone, 4,4'-diphenylbenzophenone, and 4,4'- Examples include diphenoxybenzophenone. A radical photopolymerization initiator can be used alone or in combination of two or more.

The content of the photo radical polymerization initiator can be appropriately selected according to the light irradiation amount, the additional heating temperature, and the like. The content of the radical photopolymerization initiator can be adjusted according to the target average molecular weight of the polymer to be formed. The content of the photo radical polymerization initiator is 0.1 to 10 parts by weight, 0 parts by weight based on 100 parts by weight of the total amount of the first radical polymerizable component and the second radical polymerizable component in the optical resin composition. It may be 2 to 8 parts by mass, or 0.3 to 7 parts by mass. If the content of the photo radical polymerization initiator is less than 0.1 parts by mass, the polymerization reaction may not proceed sufficiently. If the content of the photo radical polymerization initiator exceeds 10 parts by mass, the resin material to be formed may be colored, and the light transmittance may be reduced.

Examples of thermal radical polymerization initiators include azobisoisobutyl nitrile, benzoyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxyneohexanoate, tert-hexylperoxyneohexanoate, tert-butyl Peroxyneodecanoate, tert-hexylperoxyneodecanoate, cumylperoxyneohexanoate, cumylperoxyneodecanoate, and 1,1,3,3-tetramethylbutylperoxy-2- Examples include ethyl hexanoate. The thermal radical polymerization initiator can be used alone or in combination of two or more.

The content of the thermal radical polymerization initiator can be appropriately selected according to the heating temperature, the amount of oxygen present during radical polymerization, and the like. The content of the thermal radical polymerization initiator can be adjusted according to the target degree of polymerization of the polymer to be formed. The content of the thermal radical polymerization initiator is 0.05 to 10 parts by mass with respect to 100 parts by mass of the total amount of the first radical polymerizable component and the second radical polymerizable component in the optical resin composition. It may be 1 to 8 parts by mass, or 0.2 to 6 parts by mass. If the content of the thermal radical polymerization initiator is less than 0.05 parts by mass, the polymerization reaction may not proceed sufficiently. When the content of the thermal radical polymerization initiator exceeds 10 parts by mass, the formed resin material may be colored and the light transmittance may be reduced.

As a polymerization initiator other than the radical polymerization initiator, for example, a photocationic polymerization initiator or a thermal cationic polymerization initiator can be used.

The optical resin composition according to the present embodiment contains fine particles such as inorganic fine particles dispersed in a homogeneous phase containing the first and second radical polymerizable components as long as the required optical properties are maintained. May be. However, from the viewpoint of maintaining a high light transmittance of the resin material, the content of the fine particles may be 0 to 15% by mass, 0 to 10% by mass, 0 to 5% by mass, or 0 to 2% by mass. Good.

The optical resin composition according to the present embodiment may further contain other components as necessary. Examples include polymerization inhibitors, antioxidants, light stabilizers, plasticizers, leveling agents, antifoaming agents, UV absorbers, coupling agents, sensitizers, metal deactivators, chain transfer agents, antiblocking agents. And additives such as an agent and a release agent. The content of these additives is 0 to 50 parts by mass, 0 to 30 parts by mass with respect to 100 parts by mass of the total amount of the first radical polymerizable component and the second radical polymerizable component in the optical resin composition. Part, or 0 to 20 parts by mass.

The Abbe number νd of the resin material formed from the optical resin composition in the present embodiment may be 18 ≦ νd ≦ 25, 18 ≦ νd ≦ 24, or 18 ≦ νd ≦ 23. The partial dispersion ratio θg, F of the resin material is 0.700 or more, and may be 0.710 or more, or 0.720 or more. When the Abbe number νd and the partial dispersion ratios θg, F are within these ranges, a sufficient chromatic aberration correction capability can be more easily imparted to the resin material. The upper limit of the partial dispersion ratio θg, F is not particularly limited, but is usually about 0.900.

In this specification, the Abbe number νd and the partial dispersion ratio θg, F mean values calculated by the following equations.
Abbe number νd = (nd−1) / (nF−nC)
Partial dispersion ratio θg, F = (ng−nF) / (nF−nC)
In the formula, ng is a refractive index at a wavelength of 435.8 nm which is a g-line, nF is a refractive index at a wavelength of 486.1 nm which is an F-line, nd is a refractive index at a wavelength of 587.6 nm which is a d-line, and nC is a C-line. The refractive index at a certain wavelength of 656.3 nm is shown.

When the resin material formed from the optical resin composition according to the present embodiment is subjected to a light resistance test, the difference ΔT in the light transmittance of the resin material at a wavelength of 400 nm before and after the light resistance test is 5%. It may be the following. When ΔT exceeds 5%, there is a possibility that the reliability of an optical system configured using the resin material is lowered. The lower limit of ΔT is not particularly limited, but ideally 0%.

The light resistance test here uses a xenon weather meter (for example, model number: X25 manufactured by Suga Test Instruments Co., Ltd.), integrated illuminance in the wavelength range of 300 to 400 nm is 60 W / m ² , and black panel temperature is 63 ° C. This is a test in which light is irradiated for 100 hours under the above conditions. The thickness of the sheet-shaped test piece (molded body) of the resin material used for the light resistance test is 190 to 210 μm. When the light transmittance at a wavelength of 400 nm of the test piece after the light resistance test is T2, and the light transmittance at a wavelength of 400 nm of the test piece before the light resistance test is T1, the difference between T1 and T2 is ΔT. As T1 and T2, values converted to a thickness of 200 μm are used.

For example, using the sulfide compound represented by the above formula (b1) or (b2) and setting its content within the above range can contribute to making ΔT 5% or less.

The glass transition temperature (Tg) of the resin material formed from the optical resin composition according to this embodiment may be 100 ° C. or higher, or 110 ° C. or higher. Tg is one of indices indicating heat resistance. When Tg is less than 100 ° C., the molded body of the resin material is likely to be deformed particularly in a high temperature range, and there is a possibility that the reliability of the optical system configured using the resin material is lowered in a high heat environment. Although the upper limit of Tg is not specifically limited, Usually, it is about 300 degreeC. However, the resin material may not exhibit a glass transition temperature.

In this specification, Tg indicates the dynamic viscoelasticity of a resin material in a tensile mode using a dynamic viscoelasticity measuring device (for example, model number: RSA-G2 manufactured by TA Instruments Japan). It means the temperature at the peak top of tan δ when measured under conditions of a heating rate of 10 ° C./min and a frequency of 1 Hz.

When the resin material formed from the optical resin composition according to this embodiment is subjected to a boiling test, the difference Δnd before and after the boiling test of the refractive index nd at d-line (wavelength 587.6 nm) is 0.0007 or less. Or 0.0005 or less. When Δnd exceeds 0.0007, there is a possibility that the reliability of the optical system constituted by using the resin material in a high temperature and high humidity environment, that is, the resistance to moist heat is lowered. The lower limit of Δnd is not particularly limited, but ideally 0.

Here, the boiling test is a test in which a sheet-shaped test piece (molded body) having a thickness of 1.9 to 2.0 mm is immersed in a hot water bath maintained at 100 ° C. for 24 hours. The refractive index nd of each test piece before and after the boiling test is measured, and the difference between them is Δnd.

The refractive index nd of the resin material formed from the optical resin composition according to the present embodiment may be 1.550 or more, 1.600 or more, 1.630 or more, or 1.650 or more. When the resin material has a high refractive index as described above, the degree of freedom in optical design when applied to an optical system material such as a lens is improved. The upper limit of the refractive index nd is not particularly limited, but is usually about 1.800.

Internal transmittance T _i of the resin material formed from an optical resin composition according to the present embodiment, 50% or more, 60% or more, or may be 75% or more. When _Ti is less than 50%, color reproducibility when a resin material is applied to an imaging optical system such as a lens is impaired, and the degree of freedom in optical design may be reduced. The upper limit of the internal transmittance T _i is not particularly limited and is ideally 100%.

The internal transmittance Ti here is a value converted into a thickness of 200 μm of internal transmittance at a wavelength of 400 nm. The external transmittance at a wavelength of 400 nm of a test piece (molded body) having a thickness of 90 to 110 μm and a test piece having a thickness of 190 to 200 μm is measured, and the internal transmittance Ti is calculated from the following formula.
log (T _i / 100) = − [{log (T ₃ ) −log (T ₄ )} / (d ₄ −d ₃ )] × 200
Here, d ₃ is the measured thickness of the test piece having a thickness of 90 to 110 μm, d ₄ is the measured thickness of the test piece having a thickness of 190 to 210 μm, T ₃ is the external transmittance at a wavelength of 400 nm of the test piece having a thickness of 90 to 110 μm, T ₄ is the external transmittance at a wavelength of 400 nm of a test piece having a thickness of 190 to 210 μm. The external transmittance is a light transmittance including a surface reflection loss.

The optical resin composition according to the present embodiment is, for example, a method of mixing the first and second polymerizable components and, if necessary, other components (polymerization initiator, additive, etc.) and stirring the mixture. Can be obtained. Each component may be mixed simultaneously or sequentially. The temperature during stirring is not particularly limited, but is usually 0 to 120 ° C., and may be 10 to 100 ° C. The stirring time may be 0.1 to 24 hours, or 0.1 to 6 hours. Depending on the type of the polymerization initiator, the temperature and the stirring time during stirring are appropriately adjusted.

A molded body of a resin material having an arbitrary shape can be manufactured using the optical resin composition according to the present embodiment. The molded body of the resin material is, for example, a resin material containing these polymers by radical polymerization of the first radical polymerizable component and the second radical polymerizable component in the optical resin composition filled in the mold. Can be manufactured by a method including forming the molded body of the resin material and removing the molded body of the formed resin material from the mold.

When it is desired to improve the viscosity of the optical resin composition for the purpose of improving operability before filling the optical resin composition into the mold, the first radical polymerizable component is used as a prepolymerization until the desired viscosity is reached. Further, the radical polymerization of the second radical polymerizable component may proceed to some extent.

The optical resin composition before filling into the mold may be degassed and degassed. Thereby, radical polymerization can be advanced efficiently, maintaining the state where an optical resin composition does not touch air (oxygen). The method for degassing and defoaming the optical resin composition is not particularly limited. For example, bubbling with an inert gas such as nitrogen and argon, vacuum degassing, ultrasonic degassing, hollow fiber membrane degassing, or these The combination of can be adopted.

The radical polymerization of the first radical polymerizable component and the second radical polymerizable component can proceed by thermal polymerization, photopolymerization, or a combination thereof.

The polymerization temperature and polymerization time for thermal polymerization vary depending on the type and blending ratio of the radical polymerizable component, the type and amount of the thermal radical polymerization initiator, and the like. Usually, the polymerization temperature may be 0 to 180 ° C., or 20 to 150 ° C., and the polymerization time may be 0.1 to 30 hours, or 0.1 to 12 hours.

In the case of photopolymerization, the optical resin composition filled in the mold is irradiated with light such as ultraviolet rays. Examples of light sources used for photopolymerization include low-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal halide lamps, deuterium lamps, argon lamps, xenon lamps, LEDs, halogen lamps, excimer lasers, and helium-cadmium lasers. Is mentioned. The integrated amount of light to be irradiated varies depending on the type and ratio of the radical polymerizable component, the type and amount of the radical photopolymerization initiator, and the shape and the like of the molded body. Usually, the integrated light quantity may be 0.01 to 100 J / cm ² , or 0.1 to 50 J / cm ² .

Since the molded body of the resin material obtained from the optical resin composition according to the present embodiment shows a low Abbe number and a high partial dispersion ratio, it is applied as an optical member constituting an imaging optical system such as an optical lens. Thus, it is possible to highly correct the chromatic aberration of the optical system. Optical lens The optical lens formed from the optical resin composition according to the present embodiment may be used in an imaging optical system such as a camera lens for optical equipment, a camera lens for vehicle mounting, a camera lens for smartphone, a lens for digital camera, and the like. it can. The thickness of the optical lens can be appropriately set as desired, and is not particularly limited, but is usually 1 μm to 10 mm, and may be 1 μm to 5 mm. FIG. 1 is a cross-sectional view showing an embodiment of an optical lens. An optical lens 1 shown in FIG. 1 is formed of a molded body of a resin material formed from the optical resin composition according to this embodiment.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples.

1. Preparation of raw materials (A) First radical polymerizable component / compound A-1: 2- [2-hydroxy-5- [2- (methacryloyloxy) ethyl] phenyl] -2H-benzotriazole (formula (a1- 1) Compound represented by Tokyo Chemical Industry)

Compound A-2: 2-hydroxy-4-methacryloyloxybenzophenone (compound represented by the following formula (a2-1), manufactured by Alfa Aesar)

Compound A-3: Compound represented by the following formula (a3-1) synthesized in the following Production Example 1

[Production Example 1]
To a 500 mL four-necked flask equipped with a stirrer, a dropping funnel and a thermometer, TINUVIN479 (manufactured by BASF, compound name: 2- [4- (4,6-bis-biphenyl-4-yl- [1,3 , 5] triazin-2-yl) -3-hydroxy-phenoxy] -propionic acid 6-methyl-heptyl ester) 70 g (0.10 mol), DMF (dehydrated grade) 70 g, tin (II) 2-ethylhexanoate 0.42 g (0.001 mol) and tert-butylxylenol 0.01 g (0.0001 mol) were charged, and these were stirred at 60 ° C. for 30 minutes. Next, 15.2 g (0.11 mol) of Karenz AOI (manufactured by Showa Denko, compound name: 2-acryloyloxyethyl isocyanate) was added dropwise over 10 minutes. Diazabicycloundecene (DBU) 0.16 g (0.001 mol) was further added to the reaction solution in the flask, the reaction solution was heated to 110 ° C., and the reaction was allowed to proceed at 110 ° C. for 6 hours. Next, 120 g of toluene and 70 g of water were added, and the mixed solution in the flask was stirred at 85 ° C. for 2 hours. The organic layer taken out from the mixed solution by liquid separation was washed twice with 100 g of water. The organic layer after washing was concentrated, and the resulting crude product was purified by column chromatography to obtain 25.5 g of Compound A-3. The obtained compound A-3 had an HPLC purity of 97%. The yield based on TINUVIN479 was 30%.

(B) Second radical polymerizable component / compound B-1: bis (4-vinylthiophenyl) sulfide synthesized in the following Production Example 2 (radical polymerizable compound represented by the formula (b1))
Compound B-2: S, S ′-(thiodi-p-phenylene) bis (thiomethacrylate) synthesized in the following Production Example 3 (radically polymerizable compound represented by the formula (b2))
Compound B-3: Methyl methacrylate (manufactured by Tokyo Chemical Industry)
Compound B-4: Styrene (manufactured by Tokyo Chemical Industry)
Compound B-5: Ethoxylated bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: ABE-300)
Compound B-6: trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-TMPT)
Compound B-7: Triethylene glycol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light acrylate 3EG-A)

[Production Example 2]
To a 2 L four-necked flask equipped with a stirrer, a dropping funnel and a thermometer, 250.4 g (1.0 mol) of 4,4′-thiodibenzenethiol and 480.0 g of a 17 mass% aqueous sodium hydroxide solution (2 0.0 moles) was added and these were stirred at 60 ° C. for 1 hour. Subsequently, 169.1 g (2.1 mol) of 2-chloroethanol was added dropwise at 60 ° C. over 1.5 hours. After completion of dropping, the reaction was allowed to proceed at 60 ° C. over 1.5 hours. After completion of the reaction, the reaction solution was cooled to 20 ° C., and the precipitated crystals were taken out by filtration. The crystals were washed twice with 400 g of water to obtain 492.5 g of a wet cake containing bis [4- (2-hydroxyethylthio) phenyl] sulfide.

492.5 g of the obtained wet cake and 1500 g of toluene were charged into a 3 L four-necked flask equipped with a stirrer, a dropping funnel and a thermometer, and this was heated at 110 ° C. to distill off water by azeotropic distillation. . During the distillation, toluene distilled off by azeotropy with water was separated from water and returned to the flask. The remaining solution was cooled to 70 ° C., and 249.9 g (2.1 mol) of thionyl chloride was added dropwise at 70 ° C. over 2 hours. After completion of dropping, the reaction was allowed to proceed by heating at 70 ° C. for 2 hours. After completion of the reaction, 600 g (1.5 mol) of a 10% by mass aqueous sodium hydroxide solution was added to the reaction solution, and the formed mixture was separated at 70 ° C. The organic layer obtained by liquid separation was cooled to 10 ° C. to precipitate crystals. The crystals were removed by filtration and washed with 600 g of n-heptane. The washed crystals were dried by heating to 50 ° C. under reduced pressure to obtain 348.0 g (0.93 mol) of bis [4- (2-chloroethylthio) phenyl] sulfide.

Next, 348.0 g (0.93 mol) of bis [4- (2-chloroethylthio) phenyl] sulfide, 780 g of n-heptane, 14.9 g (0.046 mol) of tetrabutylammonium bromide, and 48% by mass hydroxide 232.5 g (2.8 mol) of an aqueous sodium solution was charged into a 3 L four-necked flask equipped with a stirrer and a thermometer, and these were heated at 75 to 85 ° C. for 5.5 hours to proceed the reaction. . After completion of the reaction, 428 g of water was added to the reaction solution in the flask, and the formed mixture was separated at 60 ° C. The organic layer obtained by separation was washed twice with 372 g of water to obtain 1050 g of an n-heptane solution of bis (4-vinylthiophenyl) sulfide.

To the obtained n-heptane solution, 1.4 g of 2,6-di-tert-butyl-4-methylphenol was added, and n-heptane was distilled off under the conditions of 0.6 kPa and 40 ° C. to give bis (4 -275.3 g (0.91 mol) of -vinylthiophenyl) sulfide (compound B-1) was obtained. The obtained compound B-1 had an HPLC purity of 99%. The yield based on 4,4'-thiodibenzenethiol was 91%.

[Production Example 3]
Under a nitrogen atmosphere, 250.4 g (1 mol) of 4,4′-thiodibenzenethiol and 800 g of monochlorobenzene were charged into a 2 L four-necked flask equipped with a stirrer, a dropping funnel and a thermometer. While the flask was heated to 60 to 65 ° C., 114.3 g (2.8 mol) of 98% by mass sodium hydroxide and 1.9 g (0.05 mol) of sodium borohydride were converted to 546.8 g of water. 663.0 g of the dissolved aqueous solution was added dropwise over 1 hour. After completion of dropping, the reaction was allowed to proceed by heating for 1 hour at the same temperature. After completion of the reaction, the reaction solution was separated to obtain 910.6 g (aqueous layer) of an aqueous solution containing a sodium salt of 4,4′-thiodibenzenethiol.

A 3 L four-necked flask equipped with a stirrer, a dropping funnel and a thermometer was charged with 230.0 g (2.2 mol) of methacryloyl chloride, 450 g of n-heptane, 900 g of cyclohexane and 2.0 g of p-methoxyphenol. Was cooled to 5 ° C. Thereto was added 910.6 g of an aqueous solution containing the sodium salt of 4,4'-thiodibenzenethiol cooled to 5 ° C. over 5 minutes. After completion of the dropwise addition, the reaction was allowed to proceed by heating the reaction solution at 55-60 ° C. for 1 hour. After completion of the reaction, the reaction solution was separated to obtain an organic layer. The obtained organic layer was washed twice with 140 g of water. To the organic layer after washing, 2.0 g of p-methoxyphenol and 1.5 g of activated carbon were added, and the organic layer was stirred at 55-60 ° C. for 30 minutes. Thereafter, insoluble materials were removed by hot filtration. Crystals were precipitated by crystallization by cooling the remaining organic layer to 0 ° C. The precipitated crystals were separated by filtration. The obtained crystals were washed with a mixed solution consisting of 170 g of n-heptane, 340 g of cyclohexane and 0.13 g of p-methoxyphenol, dried under reduced pressure, and white S, S ′-(thiodi-p-phenylene) bis 325.5 g (0.84 mol) of (thiomethacrylate) (Compound B-2) was obtained. The obtained compound B-1 had an HPLC purity of 99%. The yield based on 4,4'-thiodibenzenethiol was 84%.

2. Optical resin composition and molded article of resin material (Example 1)
Compound A-1 and Compound B-4 were mixed at a mass ratio shown in Table 1, and the mixture was stirred at 60 ° C. for 30 minutes. After cooling to 25 ° C., 3 parts by weight of IRGACURE 1173 (manufactured by BASF, 2-hydroxy-2-methyl-1-phenyl-propan-1-one) is dissolved in the mixture as a radical photopolymerization initiator for 100 parts by weight of the mixture. The obtained mixed liquid (optical resin composition) was sufficiently deaerated. Next, the optical resin composition was separated into a glass mold in which two glass plates of 76 × 52 mm were arranged with a gap of 200 μm, and a glass mold in which two glass plates of 76 × 52 mm were arranged with a gap of 100 μm. Filled. Radical polymerization of compound A-1 and compound B-4 by irradiating the optical resin composition filled in the glass mold with light of 5000 mJ / cm ² (integrated illuminance with a 365 nm sensor) by a high-pressure mercury lamp. A molded body of a resin material containing the polymer formed by the above was formed. The formed molded body was taken out from the glass mold. As a result, sheet-like molded articles for evaluation having a thickness of about 200 μm and a thickness of about 100 μm were obtained.

Instead of the radical photopolymerization initiator, 0.5 parts by mass of Perocta O (Nippon Yushi Co., Ltd., 1,1,3,3-tetramethyl) is added to 100 parts by mass of the mixture of Compound A-1 and Compound B-4. Butyl peroxy 2-ethylhexanoate) was added as a thermal radical polymerization initiator to prepare an optical resin composition, which was thoroughly deaerated. Then. The optical resin composition was filled in the gap of a glass mold in which two circular glass molds having a diameter of 73 mm were arranged with a gap of 2 mm. A glass mold filled with the optical resin composition was heated at 55 ° C. for 2 hours, then heated from 55 ° C. to 95 ° C. over 12 hours, and then heated at 95 ° C. for 2 hours to obtain Compound A-1. And a molded body of a resin material containing a polymer formed from Compound B-4 was formed. The formed molded body was taken out from the glass mold. As a result, a disk-shaped molded product for evaluation having a thickness of about 2 mm was obtained.

(Examples 2 to 16, Comparative Examples 1 to 3)
An optical resin composition was prepared in the same manner as in Example 1 except that each raw material was used in the ratio shown in Table 1, and three types of molded articles for evaluation were produced using this.

3. Evaluation <refractive index nd, Abbe number νd, partial dispersion ratio θg, F>
G-line (wavelength 435.8 nm), F-line (wavelength 486.1 nm), d-line (wavelength 587.6 nm), and C-line (wavelength) of a disk-shaped evaluation specimen (molded body) having a thickness of about 2 mm The refractive indexes ng, nd, nF and nC at 656.3 nm were measured at 25 ° C. using a refractometer PR-2 (V block system) manufactured by Carl Zeiss Jena. From the obtained refractive index, the Abbe number and θg, F were calculated by the following equations.
Abbe number νd = (nd−1) / (nF−nC)
Partial dispersion ratio θg, F = (ng−nF) / (nF−nC)

<Heat resistance>
Using a dynamic viscoelasticity measuring device (manufactured by TA Instruments Japan, model number: RSA-G2), the temperature change of the dynamic viscoelasticity of the test specimen (molded body) having a thickness of about 200 μm is used. Then, measurement was performed under the conditions of a tensile mode, a heating rate of 10 ° C./min, and a frequency of 1 Hz. The temperature at the peak top of tan δ was recorded as the glass transition temperature Tg of the molded product. Based on the value of Tg, the heat resistance of the molded product was determined according to the following criteria.
AA: Tg ≧ 110 ° C.
A: 100 ≦ Tg <110 ° C.
C: Tg <100 ° C.

<Heat and heat resistance>
A test piece (molded body) for evaluation having a thickness of about 2 mm was subjected to a boiling test where it was immersed in a hot water bath maintained at 100 ° C. for 24 hours. The refractive index nd of the test pieces before and after the boiling test was measured, and the difference Δnd between them was determined. Based on the value of Δnd, the wet heat resistance of the molded body was determined according to the following criteria.
AA: Δnd ≦ 0.0005
A: 0.0005 <Δnd ≦ 0.0007
C: Δnd> 0.0007

<Internal transmittance>
The transmittance at a wavelength of 400 nm of an evaluation test piece (molded body) of about 200 μm thickness and an evaluation test piece (molded body) of about 100 μm thickness was measured with a spectrophotometer (manufactured by Hitachi, Ltd., model number: UH- 4150). The measured value obtained here is the external transmittance including the surface reflection loss. The measured values obtained by using the actually measured thickness of each specimen was calculated internal transmittance T _i at wavelength 400nm which is converted to a thickness 200μm from the following equation.
log (T _i / 100) = − [{log (T ₃ ) −log (T ₄ )} / (d ₄ −d ₃ )] × 200
d ₃ : Measured thickness of a molded body having a thickness of about 100 μm d ₄ : Measured thickness of a molded body having a thickness of about 200 μm T ₃ : External transmittance T ₄ of a molded body having a thickness of about 100 μm at a wavelength of 400 nm: External transmittance at a wavelength of 400 nm

Based on the value of the internal transmittance Ti, the internal transmittance of the molded body was determined according to the following criteria.
AA: T _i ≧ 75%
A: 60% ≦ T _i <75%
B: 50% ≦ T _i <60%
C: T _i <50%

<Light resistance>
About 200μm thick test piece for evaluation of (molded body), xenon weather meter (Suga Test Instruments Co., Ltd., model number: X25) with (integrated at a wavelength of 300 ~ 400 nm band) radiation intensity 60 W / ^{m 2,} The sample was subjected to a light resistance test in which light was irradiated for 100 hours at a black panel temperature of 63 ° C. The transmittance of each molded body before and after the light resistance test at a wavelength of 400 nm was measured using a spectrophotometer (manufactured by Hitachi, Ltd., model number: UH-4150). Using these values and the actually measured thickness of the molded body, the transmittance converted to 200 μm thickness was calculated from the Lambert-Beer formula. A difference ΔT before and after the light resistance test of the transmittance at a wavelength of 400 nm was determined, and the light resistance was determined based on the value according to the following criteria.
A: ΔT = 0 to 5%
C: ΔT> 5%

1 ... Optical lens.

Claims (7)

1. (A) a first radical polymerizable component comprising at least one radical polymerizable compound represented by the following formula (a1), (a2) or (a3);
   (B) a second radical polymerizable component comprising at least one radical polymerizable compound different from the first radical polymerizable component;
   An optical resin composition comprising:
   When the first radical polymerizable component and the second radical polymerizable component are radically polymerized, a resin material containing these polymers is formed,
   The Abbe number νd and the partial dispersion ratio θg, F of the resin material are expressed by the following formula:
   18 ≦ νd ≦ 25; and θg, F ≧ 0.700
   An optical resin composition satisfying
   

   

   [In the formula (a1),
   X ¹ represents a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, an optionally substituted alkoxycarbonylalkyl group having 1 to 18 carbon atoms, or , A group having a (meth) acryloyl group,
   X ² and X ³ each independently represent a hydrogen atom, a halogen atom, or an optionally substituted hydrocarbon group having 1 to 18 carbon atoms,
   X ⁴ represents a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, or a group having a (meth) acryloyl group,
   X ⁵ represents a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, or a group having a (meth) acryloyl group,
   At least one of X ¹ , X ⁴ or X ⁵ is a group having a (meth) acryloyl group. ]
   

   

   [In the formula (a2),
   Y ¹ and Y ² each independently represent a hydrogen atom, a hydroxyl group, an optionally substituted alkoxy group having 1 to 8 carbon atoms, or a group having a (meth) acryloyl group,
   Y ³ and Y ⁴ each independently represent a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, or a group having a (meth) acryloyl group,
   At least one of Y ¹ , Y ² , Y ³ or Y ⁴ is a group having a (meth) acryloyl group. ]
   

   

   [In the formula (a3),
   Z ¹ has an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, an optionally substituted alkylcarbonyloxyalkyl group having 1 to 18 carbon atoms, and a substituent. An optionally substituted alkoxycarbonylalkyl group having 1 to 18 carbon atoms, or an optionally substituted alkoxyalkyl group having 1 to 18 carbon atoms;
   Z ² , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁸ and Z ⁹ are each independently a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, or a substituent. An alkoxy group having 1 to 8 carbon atoms which may be present;
   Z ³ represents a hydrogen atom or a group having a (meth) acryloyl group,
   Z ⁷ represents a hydrogen atom, a hydroxyl group, an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, an optionally substituted alkoxy group having 1 to 8 carbon atoms, or (meth) A group having an acryloyl group;
   At least one of Z ^{3 and} Z ⁷ is a group having a (meth) acryloyl group. ]
2. For a light resistance test in which a sheet-shaped molded body of the resin material having a thickness of 190 to 210 μm is irradiated with light for 100 hours under the conditions of an integrated illuminance of 60 W / m ² in a wavelength range of 300 to 400 nm and a black panel temperature of 63 ° C. 2. The optical resin composition according to claim 1, wherein when provided, the difference ΔT between the transmittance of the molded body at a wavelength of 400 nm before and after the light resistance test is 5% or less.
3. The optical resin composition according to claim 1 or 2, wherein the glass transition temperature of the resin material is 100 ° C or higher.
4. When the sheet-shaped molded body having a thickness of 1.9 to 2.0 mm of the resin material was subjected to a boiling test in which it was immersed in a hot water bath maintained at 100 ° C. for 24 hours, the d-line (wavelength 587) of the molded body. The optical resin composition according to any one of claims 1 to 3, wherein a difference Δnd of the refractive index nd at .6 nm) before and after the boiling test is 0.0007 or less.
5. The optical resin composition according to any one of claims 1 to 4, wherein (B) the second radical polymerizable component contains at least one sulfide compound represented by the following formula (b1) or (b2). object.
   

   

   [In the formulas (b1) and (b2), R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms, and n is 0 to 10 represents an integer, R ⁵ represents a hydrogen atom or a methyl group, and two R ^{5 in} formula (b2) may be the same or different. ]
6. The optical resin composition according to any one of claims 1 to 5, wherein the optical resin composition may contain fine particles.
7. A resin material comprising a polymer formed by radical polymerization of a first radical polymerizable component and a second radical polymerizable component in the optical resin composition according to any one of claims 1 to 6. Optical lens.

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