Cured products, molded articles, and optical materials

Abstract

The present invention pertains to: [1] a curable composition comprising a compound (A) having at least two thio(meth)acrylate groups and a compound (B) represented by formula (1); [2] a cured product obtained by curing the curable composition disclosed in [1]; [3] a molded body containing the cured product disclosed in [2]; and [4] an optical material containing the molded body disclosed in [3].

Description

[Technical Field]

[0001] The present invention relates to curable compositions, cured products, molded articles, and optical materials. [Background technology]

[0002] Traditionally, glass has been preferred as an optical material due to its diverse refractive index and minimal fluctuations with temperature and humidity. However, in recent years, resin-cured materials have come into use to meet demands for lighter weight and lower costs.

[0003] For example, camera lens modules used in smartphones are increasingly employing wafer-level lenses to achieve miniaturization and a low profile. Wafer-level lenses require resin cured materials with high refractive index and excellent heat resistance. Furthermore, in so-called hybrid wafer-level lenses, where a resin lens is formed on a glass substrate, a low curing shrinkage rate is required during the curing process to suppress delamination between the glass substrate and the resin lens due to residual stress. As a method for obtaining a resin cured product with a higher refractive index, a method using a transparent material obtained by photocuring a composition containing thio(meth)acrylate or the like has been reported in Patent Documents 1 and 2. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. 98 / 24761 [Patent Document 2] Japanese Patent Application Publication No. 8-325337 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, although the cured resin products obtained by the methods described in Patent Documents 1 and 2 have a high refractive index, they have a large shrinkage rate when cured, resulting in problems with adhesion to glass.

[0006] The present invention has been made in view of the above circumstances, and provides a curable composition that can produce a cured product with an improved balance of high refractive index, low curing shrinkage, and glass adhesion properties, as well as a cured product, molded article, and optical material with an improved balance of high refractive index, low curing shrinkage, and glass adhesion properties. [Means for solving the problem]

[0007] The inventors diligently conducted research to solve the above problems. As a result, they discovered that by using a compound having two or more thio(meth)acrylate groups in combination with a compound having a structural unit derived from a specific fluorene monomer, the balance of performance in the resulting cured product, including high refractive index, low curing shrinkage, and glass adhesion, can be improved, thus completing the present invention. According to the present invention, the following curable compositions, cured products, molded articles, and optical materials are provided.

[0008] [1] A compound (A) having two or more thio(meth)acrylate groups, A curable composition comprising compound (B) represented by the following formula (1). [ka] (In formula (1) above, Z1 and Z2 each independently represent an aromatic carbocyclic ring or an alkylene group, and any hydrogen atom may be substituted with an alkyl group or an alkoxy group; Z3 and Z4 each independently represent an aromatic carbocyclic ring or an alkyl group, and any hydrogen atom may be substituted with an alkyl group or an alkoxy group; R1 and R3 each independently represent an alkylene group having 1 to 10 carbon atoms; R2 and R4 each independently represent a hydrogen atom or a methyl group; R5 and R6 each independently represent an alkyl group; m and n each independently represent an integer of 0 or more; and o, p, q, and r are integers of 0 or more that satisfy the relationships o + q ≤ 4 and p + r ≤ 4.) [2] The curable composition according to [1], wherein compound (A) comprises at least one compound selected from those represented by the following formula (2). [ka] (In formula (2) above, n is an integer between 1 and 5, R1 and R2 each independently represent a hydrogen atom or a methyl group, and X is an alkylene group having 1 to 4 carbon atoms, in which any hydrogen atom may be substituted in the structure shown in formula (3) below.) [ka] (In formula (3) above, R3 represents a hydrogen atom or a methyl group, and multiple R3s may be the same or different, W represents an alkylene group having 1 to 4 carbon atoms, and m is an integer of 1 or more.) [3] The curable composition according to [1] or [2], wherein the compound (A) comprises at least one selected from the group consisting of compounds represented by the following chemical formula. [ka] [4] The curable composition according to any one of [1] to [3], wherein the content of compound (B) in the curable composition is 10 parts by mass or more and 70 parts by mass or less per 100 parts by mass of the curable composition. [5] The aforementioned compound (B) is 9,9-bis(4-(meth)acryloyloxyphenyl)fluorene, 9,9-bis(4-(2-(meth)acryloyloxyethoxy)phenyl)fluorene, 9,9-bis(4-(3-(meth)acryloyloxypropoxy)phenyl)fluorene, 9,9-bis(4-(2-(meth)acryloyloxypropoxy)phenyl)fluorene, 9,9-bis(4-(meth)acryloyloxy-3-methylphenyl)fluorene, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)-3-methylphenyl Fluorene, 9,9-bis[4-(3-(meth)acryloyloxypropoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-(meth)acryloyloxypropoxy)-3-methylphenyl]fluorene, 9,9-bis(4-(meth)acryloyloxy-3-ethylphenyl)fluorene, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)-3-ethylphenyl]fluorene, 9,9-bis[4-(3-(meth)acryloyloxypropoxy)-3-ethylphenyl]fluorene, 9,9-bis[4-( 2-(meth)acryloyloxypropoxy)-3-ethylphenyl]fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-1,8-diphenylfluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-1,8-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-1,8-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-2,7-diphenylfluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-2,7-diphenylfluorene Oren, 9,9-bis(2-(meth)acryloyloxypropyl)-2,7-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-3,6-diphenylfluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-3,6-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-3,6-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-4,5-diphenylfluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-4,5-Diphenylfluorene, 9,9-Bis(2-(meth)acryloyloxypropyl)-4,5-Diphenylfluorene, 9,9-Bis(2-(meth)acryloyloxyethyl)-1,8-Bis(naphtho-1-yl)fluorene, 9,9-Bis(3-(meth)acryloyloxypropyl)-1,8-Bis(naphtho-1-yl)fluorene, 9,9-Bis(2-(meth)acryloyloxypropyl)-1,8-Bis(naphtho-1-yl)fluorene, 9,9-Bis(2-(meth)acryloyloxyethyl)-2,7-Bis(naphtho-1-yl)fluorene Oren, 9,9-bis(3-(meth)acryloyloxypropyl)-2,7-bis(naphtho-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-2,7-bis(naphtho-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-3,6-bis(naphtho-1-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-3,6-bis(naphtho-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-3,6-bis(naphtho-1-yl)fluorene Len, 9,9-bis(2-(meth)acryloyloxyethyl)-4,5-bis(naphtho-1-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-4,5-bis(naphtho-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-4,5-bis(naphtho-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-1,8-bis(naphtho-2-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-1,8-bis(naphtho-2-yl)fluorene , 9,9-bis(2-(meth)acryloyloxypropyl)-1,8-bis(naphtho-2-yl)fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-2,7-bis(naphtho-2-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-2,7-bis(naphtho-2-yl)fluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-2,7-bis(naphtho-2-yl)fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-3,6-bis(naphtho-2-yl)fluorene, 9,At least one selected from the group consisting of 9-bis(3-(meth)acryloyloxypropyl)-3,6-bis(naphthalen-2-yl)fluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-3,6-bis(naphthalen-2-yl)fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-4,5-bis(naphthalen-2-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-4,5-bis(naphthalen-2-yl)fluorene, and 9,9-bis(2-(meth)acryloyloxypropyl)-4,5-bis(naphthalen-2-yl)fluorene, the curable composition according to any one of [1] to [4] above., [6] The curable composition according to any one of [1] to [5] above, further comprising a polymerization initiator. [7] The curable composition according to any one of [1] to [6] above, further comprising at least one selected from the group consisting of a silane coupling agent, an antioxidant, an ultraviolet absorber, and a light stabilizer. [8] Let the specific gravity of the curable composition be d, measured using a pycnometer in accordance with JIS Z 8804:2012 1 and let the specific gravity of a 250-μm-thick test piece made of the cured product of the curable composition be d 2 When this is the case, the curable composition according to any one of [1] to [7] above, wherein the curing shrinkage rate of the curable composition, represented by (1 - d 1 / d 2 ) × 100, is 9.0% or less. [9] The curable composition according to any one of [1] to [8] above, which can be used for an optical material.

[10] A cured product obtained by curing the curable composition according to any one of [1] to [9] above.

[11] The cured product according to

[10] above, wherein when a 250-μm-thick test piece made of the cured product is fabricated, the refractive index (nD) of the D line (589.3 nm) of the test piece is 1.600 or more.

[12] The cured material according to

[10] or

[11] , wherein when a test specimen with a thickness of 250 μm is prepared from the cured material, the Abbe number (νD) of the test specimen, as measured in accordance with ASTM D542, is 20 or more.

[13] A molded article comprising a cured product as described in any of the above

[10] to

[12] .

[14] An optical material comprising the molded article described in

[13] above.

[15] Further comprising a glass substrate, The optical material according to

[14] , which is a laminate of the molded body and the glass substrate.

[16] An optical lens, the optical material described in

[14] or

[15] above. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a curable composition that can produce a cured product with an improved balance of high refractive index, low curing shrinkage, and glass adhesion properties, as well as a cured product, molded article, and optical material with an improved balance of high refractive index, low curing shrinkage, and glass adhesion properties. [Modes for carrying out the invention]

[0010] The present invention will be described below based on embodiments. In this specification, "A~B" indicating a numerical range means A or greater and B or less unless otherwise specified. In this specification, "(meth)acrylic" refers to at least one selected from the group consisting of acrylic and methacrylic, and the same applies to similar notations such as "thio(meth)acrylate" and "(meth)acrylate". In this specification, "(meth)acrylic group" refers to at least one selected from the group consisting of an acryloyl group represented by -C(=O)-CH=CH2 and a methacryloyl group represented by -C(=O)-C(CH3)=CH2.

[0011] [Curable composition] The curable composition of the present invention comprises a compound (A) having two or more thio(meth)acrylate groups (hereinafter also simply referred to as "compound (A)") and a compound (B) represented by the following formula (1) (hereinafter also simply referred to as "compound (B)").

[0012] [ka] In formula (1) above, Z1 and Z2 each independently represent an aromatic carbocyclic ring or an alkylene group, and any hydrogen atom may be substituted with an alkyl group or an alkoxy group; Z3 and Z4 each independently represent an aromatic carbocyclic ring or an alkyl group, and any hydrogen atom may be substituted with an alkyl group or an alkoxy group; R1 and R3 each independently represent an alkylene group having 1 to 10 carbon atoms; R2 and R4 each independently represent a hydrogen atom or a methyl group; R5 and R6 each independently represent an alkyl group; m and n each independently represent an integer of 0 or more; and o, p, q, and r are integers of 0 or more that satisfy the relationships o + q ≤ 4 and p + r ≤ 4.

[0013] According to the curable composition of the present invention, it is possible to obtain cured products, molded articles, and optical materials with an improved balance of performance characteristics, including high refractive index, low curing shrinkage, and glass adhesion.

[0014] The following describes each component constituting the curable composition according to the present invention.

[0015] <Compound (A)> Compound (A) is not particularly limited as long as it is a compound having two or more thio(meth)acrylate groups, but from the viewpoint of further improving the balance of high refractive index, low curing shrinkage, and glass adhesion properties of the resulting cured product, it is preferable to include at least one compound selected from those represented by the following formula (2).

[0016] [ka] In formula (2) above, n is an integer from 1 to 5, preferably an integer from 1 to 4, more preferably an integer from 2 to 4, R1 and R2 each independently represent a hydrogen atom or a methyl group, and X is an alkylene group having 1 to 4 carbon atoms in which any hydrogen atom may be substituted with the structure of formula (3) below, preferably an alkylene group having 2 to 4 carbon atoms in which any hydrogen atom may be substituted with the structure of formula (3) below, more preferably an alkylene group having 2 to 3 carbon atoms in which any hydrogen atom may be substituted with the structure of formula (3) below, more preferably an alkylene group having 2 carbon atoms in which any hydrogen atom may be substituted with the structure of formula (3) below, and even more preferably an alkylene group having 2 carbon atoms in which one or two of any hydrogen atoms may be substituted with the structure of formula (3) below. Furthermore, in formula (2), it is preferable that any hydrogen atom in X is substituted with the structure of formula (3) below, and it is more preferable that one hydrogen atom in one or two X in formula (2) is substituted with the structure of formula (3) below.

[0017] [ka] In formula (3) above, R3 represents a hydrogen atom or a methyl group, and multiple R3s may be the same or different, W represents an alkylene group having 1 to 4 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, even more preferably an alkylene group having 1 carbon atom, and m is an integer of 1 or more, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, even more preferably 1 or 2, and even more preferably 1.

[0018] From the viewpoint of further improving the balance of high refractive index, low curing shrinkage, and glass adhesion properties of the resulting cured product, compound (A) preferably contains at least one compound selected from the group consisting of compounds represented by the following chemical formula.

[0019] [ka]

[0020] The content of compound (A) in the curable composition according to the present invention is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 50 parts by mass or more, even more preferably 55 parts by mass or more, and preferably 90 parts by mass or less, more preferably 85 parts by mass or less, even more preferably 80 parts by mass or less, even more preferably 70 parts by mass or less, even more preferably 65 parts by mass or less, and even more preferably 60 parts by mass or less, from the viewpoint of further improving the balance of performance of the high refractive index, low curing shrinkage and glass adhesion of the resulting cured product, per 100 parts by mass of the curable composition according to the present invention.

[0021] <Compound (B)> Compound (B) is represented by the following formula (1).

[0022] [ka] In formula (1), Z1 and Z2 each independently represent an aromatic carbocyclic ring or an alkylene group, and any hydrogen atom may be substituted with an alkyl group or an alkoxy group. Z1 and Z2 each independently are preferably a benzene ring, a naphthalene ring, or an alkylene group having 1 to 4 carbon atoms, more preferably a benzene ring or an alkylene group having 1 to 3 carbon atoms. In formula (1), Z3 and Z4 each independently represent an aromatic carbocyclic ring or an alkyl group, and any hydrogen atom may be substituted with an alkyl group or an alkoxy group. Z3 and Z4 each independently are preferably an aromatic carbocyclic ring, more preferably a benzene ring or a naphthalene ring, and even more preferably a naphthalene ring. In formula (1) above, R1 and R3 each independently represent an alkylene group having 1 to 10 carbon atoms. R1 and R3 each independently preferably represent an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms, even more preferably an alkylene group having 2 to 3 carbon atoms, and even more preferably an alkylene group having 2 carbon atoms. In formula (1) above, R2 and R4 each independently represent a hydrogen atom or a methyl group. R2 and R4 are each independently preferably hydrogen atoms. In formula (1) above, R5 and R6 each independently represent an alkyl group. R5 and R6 each independently are preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, and even more preferably an alkyl group having 1 carbon atom. In formula (1) above, m and n each represent an integer greater than or equal to 0. m and n are each independently preferably integers between 0 and 4, more preferably between 0 and 2, and even more preferably 0 or 1. In formula (1) above, o, p, q, and r are integers greater than or equal to 0 that satisfy the relationships o + q ≤ 4 and p + r ≤ 4. Q and r are each independently preferably integers between 0 and 2, more preferably 0 or 1. O and p are each independently preferably integers between 0 and 2, more preferably 0 or 1, and even more preferably 0. As for compound (B), from the viewpoint of further improving the balance of performance of the resulting cured product, high refractive index, low curing shrinkage, and glass adhesion, it is preferably a compound represented by formula (1) in which Z1 and Z2 are benzene rings, naphthalene rings, or alkylene groups having 1 to 4 carbon atoms, Z3 and Z4 are benzene rings or naphthalene rings, R1 and R3 are alkylene groups having 1 to 4 carbon atoms, R2 and R4 are hydrogen atoms or methyl groups, m and n are integers from 0 to 4, q and r are 0 or 1, and o and p are 0. More preferably, as for compound (B), it is a compound represented by formula (1) in which Z1 and Z2 are benzene rings or alkylene groups having 1 to 3 carbon atoms, Z3 and Z4 are naphthalene rings, R1 and R3 are alkylene groups having 1 to 3 carbon atoms, R2 and R4 are hydrogen atoms or methyl groups, m and n are 0 or 1, q and r are 0 or 1, and o and p are 0.

[0023] As for compound (B), from the viewpoint of further improving the balance of performance of the resulting cured product, such as high refractive index, low curing shrinkage, and glass adhesion, 9,9-bis(4-(meth)acryloyloxyphenyl)fluorene, 9,9-bis(4-(2-(meth)acryloyloxyethoxy)phenyl)fluorene, 9,9-bis(4-(3-(meth)acryloyloxypropoxy)phenyl)fluorene, 9,9-bis(4-(2-(meth)acryloyloxypropoxy)phenyl)fluorene, and 9,9-bis(4-(meth)acryloyloxy-3-methylphenyl) )Fluorene, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(3-(meth)acryloyloxypropoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-(meth)acryloyloxypropoxy)-3-methylphenyl]fluorene, 9,9-bis(4-(meth)acryloyloxy-3-ethylphenyl)fluorene, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)-3-ethylphenyl]fluorene, 9,9-bis[4-(3- [(meth)acryloyloxypropoxy)-3-ethylphenyl]fluorene, 9,9-bis[4-(2-(meth)acryloyloxypropoxy)-3-ethylphenyl]fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-1,8-diphenylfluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-1,8-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-1,8-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-2,7-diphenyl Fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-2,7-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-2,7-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-3,6-diphenylfluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-3,6-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-3,6-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-4,5-Diphenylfluorene, 9,9-Bis(3-(meth)acryloyloxypropyl)-4,5-Diphenylfluorene, 9,9-Bis(2-(meth)acryloyloxypropyl)-4,5-Diphenylfluorene, 9,9-Bis(2-(meth)acryloyloxyethyl)-1,8-Bis(naphtho-1-yl)fluorene, 9,9-Bis(3-(meth)acryloyloxypropyl)-1,8-Bis(naphtho-1-yl)fluorene, 9,9-Bis(2-(meth)acryloyloxypropyl)-1,8-Bis(naphtho-1-yl)fluorene, 9,9-Bis(2-(meth)acryloyloxyethyl)-2,7-bis(naphtho-1-yl)fluorene, 9,9-Bis(3-(meth)acryloyloxypropyl)-2,7-bis(naphtho-1-yl)fluorene, 9,9-Bis(2-(meth)acryloyloxypropyl)-2,7-bis(naphtho-1-yl)fluorene, 9,9-Bis(2-(meth)acryloyloxyethyl)-3,6-bis(naphtho-1-yl)fluorene, 9,9-Bis(3-(meth)acryloyloxypropyl)-3,6-bis(naphtho-1-yl)fluorene, 9 ,9-bis(2-(meth)acryloyloxypropyl)-3,6-bis(naphtho-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-4,5-bis(naphtho-1-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-4,5-bis(naphtho-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-4,5-bis(naphtho-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-1,8-bis(naphtho-2-yl)fluorene, 9, 9-Bis(3-(meth)acryloyloxypropyl)-1,8-bis(naphtho-2-yl)fluorene, 9,9-Bis(2-(meth)acryloyloxypropyl)-1,8-bis(naphtho-2-yl)fluorene, 9,9-Bis(2-(meth)acryloyloxyethyl)-2,7-bis(naphtho-2-yl)fluorene, 9,9-Bis(3-(meth)acryloyloxypropyl)-2,7-bis(naphtho-2-yl)fluorene, 9,9-Bis(2-(meth)acryloyloxyethyl)-3,6-bis(naphtho-2-yl)fluorene, 9,9-Bis(3-(meth)acryloyloxypropyl)-3,6-bis(naphtho-2-yl)fluorene, 9,9-Bis(2-(meth)acryloyloxypropyl)-3,6-bis(naphtho-2-yl)fluorene, 9,9-Bis(2-(meth)acryloyloxyethyl)-4,5-bis(naphtho-2-yl)fluorene, and At least one selected from the group consisting of 9,9-bis(2-(meth)acryloyloxypropyl)-4,5-bis(naphtho-2-yl)fluorene, more preferably 9,9-bis(4-(meth)acryloyloxyphenyl)fluorene, 9,9-bis(4-(2-(meth)acryloyloxyethoxy)phenyl)fluorene, 9,9-bis(4-(3-(meth)acryloyloxypropoxy)phenyl)fluorene, 9,9-bis(4-(2-(meth)acryloyloxypropoxy)phenyl)fluorene, 9,9-bis(2-( 9,9-bis(3-(meth)acryloyloxyethyl)-2,7-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-2,7-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-3,6-diphenylfluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-3,6-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-3,6-diphenylfluorene, 9, 9-Bis(2-(meth)acryloyloxyethyl)-2,7-bis(naphtho-1-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-2,7-bis(naphtho-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-2,7-bis(naphtho-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-3,6-bis(naphtho-1-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-3,6-bis(naphtho-1-yl)fluorene, 9,9-Bis(2-(meth)acryloyloxypropyl)-3,6-bis(naphtho-1-yl)fluorene, 9,9-Bis(2-(meth)acryloyloxyethyl)-2,7-bis(naphtho-2-yl)fluorene, 9,9-Bis(3-(meth)acryloyloxypropyl)-2,7-bis(naphtho-2-yl)fluorene, 9,9-Bis(2-(meth)acryloyloxypropyl)-2,7-bis(naphtho-2-yl)fluorene, 9,9-Bis(2-(meth)acryloyloxyethyl)-3,6-bis(naphtho-2-yl)fluorene, 9,9- At least one selected from the group consisting of bis(3-(meth)acryloyloxypropyl)-3,6-bis(naphtho-2-yl)fluorene and 9,9-bis(2-(meth)acryloyloxypropyl)-3,6-bis(naphtho-2-yl)fluorene, more preferably 9,9-bis(4-(2-(meth)acryloyloxyethoxy)phenyl)fluorene, 9,9-bis(4-(3-(meth)acryloyloxypropoxy)phenyl)fluorene, 9,9-bis(4-(2-(meth)acryloyloxypropoxy)phenyl)fluorene 9,9-bis(2-(meth)acryloyloxyethyl)-2,7-bis(naphtho-1-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-2,7-bis(naphtho-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-2,7-bis(naphtho-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-3,6-bis(naphtho-1-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-3,6-bis(naphtho-1-yl)fluorene, 9,9-Bis(2-(meth)acryloyloxypropyl)-3,6-bis(naphtho-1-yl)fluorene, 9,9-Bis(2-(meth)acryloyloxyethyl)-2,7-bis(naphtho-2-yl)fluorene, 9,9-Bis(3-(meth)acryloyloxypropyl)-2,7-bis(naphtho-2-yl)fluorene, 9,9-Bis(2-(meth)acryloyloxypropyl)-2,7-bis(naphtho-2-yl)fluorene, 9,9-Bis(2-(meth)acryloyloxyethyl)-3,6-bis(naphtho-2-yl)fluorene, 9,It is at least one selected from the group consisting of 9-bis(3-(meth)acryloyloxypropyl)-3,6-bis(naphtho-2-yl)fluorene and 9,9-bis(2-(meth)acryloyloxypropyl)-3,6-bis(naphtho-2-yl)fluorene.

[0024] The content of compound (B) in the curable composition according to the present invention is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, even more preferably 20 parts by mass or more, even more preferably 30 parts by mass or more, even more preferably 35 parts by mass or more, even more preferably 40 parts by mass or more, and preferably 70 parts by mass or less, more preferably 60 parts by mass or less, even more preferably 50 parts by mass or less, and even more preferably 45 parts by mass or less, from the viewpoint of further improving the balance of performance of the resulting cured product, high refractive index, low curing shrinkage, and glass adhesion, per 100 parts by mass of the curable composition according to the present invention.

[0025] (Method of synthesizing compound (B)) Examples of commercially available compounds (B) include the bifunctional acrylate "A-BPEF" manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd., and the bifunctional acrylates "OGSOL EA-0200" and "OGSOL EA-0300" manufactured by Osaka Gas Chemical Co., Ltd. Furthermore, compound (B) can be synthesized by (meth)acryloyl esterification of a commercially available fluorene derivative diol using (meth)acrylic anhydride or (meth)acryloyl chloride, etc. Examples of commercially available fluorene derivative diols include BPEF (bisphenoxyethanol fluorene) and BPF (bisphenol fluorene) manufactured by Osaka Gas Chemical Co., Ltd. Furthermore, 9,9-bis(2-(meth)acryloyloxyethyl)-2,7-bis(naphtho-2-yl)fluorene (DNEOA) can be synthesized by the following synthesis scheme. More specifically, it can be synthesized by the method of Synthesis Example 1 described in the Examples.

[0026] [ka]

[0027] <Other ingredients> The curable composition according to the present invention may contain other components besides compound (A) and compound (B). Examples of other components include polymerization initiators, ultraviolet absorbers, resin modifiers, internal mold release agents, silane coupling agents, antioxidants, light stabilizers, processing stabilizers, bluing agents, polymerization metal deactivators, flame retardants, lubricants, antistatic agents, heat shielding agents, fluorescent dyes (including fluorescent whitening agents), pigments, light scattering agents, reinforcing fillers, surfactants, antibacterial agents, plasticizers, compatibilizers, other resins and elastomers, etc. Among these, the curable composition according to the present invention preferably contains a polymerization initiator from the viewpoint of further improving curability. Furthermore, the curable composition according to the present invention preferably further contains at least one selected from the group consisting of silane coupling agents, antioxidants, ultraviolet absorbers and light stabilizers.

[0028] The curable composition according to the present invention preferably contains a polymerization initiator from the viewpoint of further improving the balance of performance of the resulting cured product, including high refractive index, low curing shrinkage, and glass adhesion. Examples of polymerization initiators include thermal radical polymerization initiators, photoradical polymerization initiators, and combinations thereof. Examples of thermal radical polymerization initiators include dialkyl peroxides such as dicumyl peroxide, t-butylcumyl peroxide, 2,5-bis(t-butylperoxy)2,5-dimethylhexane, 2,5-bis(t-butylperoxy)2,5-dimethylhexine-3, di-t-butyl peroxide, isopropylcumyl-t-butyl peroxide, and bis(α-t-butylperoxyisopropyl)benzene; 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, n-butyl-4,4-bis(t-butylperoxy)valerate, and ethyl-3,3-bis(t-butylperoxy) Examples include peroxyketals such as (c) butyrate and 3,3,6,6,9,9-hexamethyl-1,2,4,5-tetraoxycyclononane; peroxyesters such as bis(t-butylperoxy)isophthalate, t-butylperoxybenzoate, and t-butylperoxyacetate; hydroperoxides such as t-butyl hydroperoxide, t-hexyl hydroperoxide, cumin hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, diisopropylbenzene hydroperoxide, and p-menthane hydroperoxide; bibenzyl compounds such as 2,3-dimethyl-2,3-diphenylbutane; and 3,3,5,7,7-pentamethyl-1,2,4-trioxepane.

[0029] Examples of photoradical polymerization initiators include benzoin alkyl ethers, benzyldimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, methylbenzoylformate, isopropylthioxanthone, and mixtures of two or more of these. Sensitizers can also be used together with these photoradical polymerization initiators. Examples of sensitizers include carbonyl compounds such as anthraquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, benzantrone, p,p'-tetramethyldiaminobenzophenone, and chloranil; nitro compounds such as nitrobenzene, p-dinitrobenzene, and 2-nitrofluorene; aromatic hydrocarbons such as anthracene and chrysene; sulfur compounds such as diphenyl disulfide; and nitrogen compounds such as nitroaniline, 2-chloro-4-nitroaniline, 5-nitro-2-aminotoluene, and tetracyanoethylene.

[0030] The content of the polymerization initiator in the curable composition according to the present invention is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 1.0 part by mass or more, even more preferably 1.5 parts by mass or more, even more preferably 2.0 parts by mass or more, even more preferably 2.5 parts by mass or more, and preferably 10 parts by mass or less, more preferably 8.0 parts by mass or less, even more preferably 5.0 parts by mass or less, and even more preferably 4.0 parts by mass or less, when the total amount of compound (A) and compound (B) in the curable composition according to the present invention is 100 parts by mass, from the viewpoint of further improving the balance of performance of the resulting cured product, such as high refractive index, low curing shrinkage, and glass adhesion.

[0031] The curable composition according to the present invention preferably includes a silane coupling agent from the viewpoint of further improving the balance of performance of the resulting cured product, such as high refractive index, low curing shrinkage, and glass adhesion. Examples of silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(amino Examples of silane coupling agents include ethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, and 3-trimethoxysilylpropyl succinic anhydride. These silane coupling agents are readily available on the market, for example, as they are sold by Shin-Etsu Chemical Co., Ltd. and others.

[0032] The content of the silane coupling agent in the curable composition according to the present invention is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, even more preferably 0.1 parts by mass or more, even more preferably 0.5 parts by mass or more, and preferably 10 parts by mass or less, more preferably 5.0 parts by mass or less, even more preferably 3.0 parts by mass or less, and even more preferably 1.5 parts by mass or less, when the total amount of compound (A) and compound (B) in the curable composition according to the present invention is 100 parts by mass, from the viewpoint of further improving the balance of performance of the resulting cured product, such as high refractive index, low curing shrinkage, and glass adhesion.

[0033] The curable composition according to the present invention preferably contains an ultraviolet absorber from the viewpoint of further improving ultraviolet resistance. Examples of ultraviolet absorbers include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and benzoxazine-based ultraviolet absorbers. Examples of benzophenone-based ultraviolet absorbers include 4-methoxy-2-hydroxybenzophenone (molecular weight 228), 4-methoxy-2-hydroxybenzophenone-5-sulfonic acid (molecular weight 308), 2,4-dihydroxybenzophenone (molecular weight 214), 4,4'-dimethoxy-2,2'-dihydroxybenzophenone (molecular weight 274), and 4,4'-dimethoxy-2,2'-dihydroxy-5,5'-disulfonic acid benzophenone disodium (molecular weight Examples include 478), 2,2'-4,4'-tetrahydroxybenzophenone (molecular weight 246), sodium hydroxymethoxybenzophenone sulfonate (molecular weight 376), octabenzone (molecular weight 326), 2-hydroxy-4-m-octoxybenzophenone (molecular weight 345), 2-hydroxy-4-n-octoxybenzophenone (molecular weight 326), and bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane (molecular weight 468). Furthermore, examples of benzotriazole-based UV absorbers include 2-(2H-benzotriazole-2-yl)-p-cresol (molecular weight 225), 2-(2H-benzotriazole-2-yl)-4-6-bis(1-methyl-1-phenylethyl)phenol (molecular weight 448), 2-[5-chloro(2H)-benzotriazole-2-yl]-4-methyl-6-(tert-butyl)phenol (molecular weight 316), 2,4-di-tert-butyl-6-(5-chloro-2H-1,2,3-benzotriazole-2-yl)phenol (molecular weight 358), 2-(2H-benzotriazole-2-yl)-4,6-tert-pentylphenol (molecular weight 352), and 2-(2H-benzotriazole Examples include 2-yl-4-(1,1,3,3-tetramethylbutyl)phenol (molecular weight 323), 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] (molecular weight 659), 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'5-di-tert-butyl-phenyl)-5-chlorobenzotriazole (molecular weight 357), 2-(2'-hydroxy-5'-methylphenyl)benzotriazole (molecular weight 225), and 2-(2-hydroxy-5-octylphenyl)-benzotriazole (molecular weight 323). Furthermore, examples of triazine-based UV absorbers include 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[(hexyl)oxy]-phenol (molecular weight 426), 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-(octyloxy)phenol (molecular weight 509), and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl). Examples include phenyl)-1,3,5-triazine (molecular weight 700), 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol (molecular weight 512), 1,6-hexanediamine, N,N'-bis(1,2,2,6,6-pentamethyl-4-piperidyl), polymersmorpholine-2,4,6-trichloro-1,3,5-triazine, etc. Furthermore, an example of a benzoxazine-based UV absorber is 2,2'-(1,4-phenylene)bis(4H-3,1-benzoxazine-4-one) (molecular weight 368). Other examples include tetra-ethyl-2,2-(1,4-phenylene-dimethylidene-bismalonic acid) (molecular weight 418), which has a malonic acid ester structure, and 2-ethyl,2'-ethoxy-oxamide (molecular weight 312), which has an oxalic acid anilide structure. Two or more of the above components can also be used in combination.

[0034] The amount of ultraviolet absorber in the curable composition according to the present invention is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, even more preferably 0.01 parts by mass or more, and preferably 1.0 part by mass or less, more preferably 0.5 parts by mass or less, even more preferably 0.2 parts by mass or less, and even more preferably 0.1 parts by mass or less, when the total amount of compound (A) and compound (B) in the curable composition according to the present invention is 100 parts by mass, from the viewpoint of further improving the balance of performance of the resulting cured product, such as high refractive index, low curing shrinkage, glass adhesion, and ultraviolet resistance.

[0035] The curable composition according to the present invention preferably contains an antioxidant from the viewpoint of further improving oxidation resistance. Examples of antioxidants include triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 1,3,5-trimethyl-2,4,6-tris(3,5-di-ter Examples include t-butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, and 3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane.

[0036] The content of the antioxidant in the curable composition according to the present invention is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, and preferably 5.0 parts by mass or less, more preferably 2.0 parts by mass or less, and even more preferably 1.0 part by mass or less, when the total amount of compound (A) and compound (B) in the curable composition according to the present invention is 100 parts by mass, from the viewpoint of further improving the balance of performance of the resulting cured product, such as high refractive index, low curing shrinkage, glass adhesion, and oxidation resistance.

[0037] The curable composition according to the present invention preferably contains a light stabilizer, and more preferably a hindered amine-based light stabilizer, from the viewpoint of further improving weather resistance. Examples of hindered amine-based light stabilizers include 70% by weight of the reaction product of methacrylic acid (1,2,2,6,6-pentamethyl-piperidine-4-yl), decandioate bis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidinyl) ester, 1,1-dimethylethyl hydroperoxide, and octane, and 30% by weight of polypropylene; bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate; bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate; and methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate mixture. Examples include compounds, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, mixtures of 2,2,6,6-tetramethyl-4-piperidyl-1,2,3,4-butanetetracarboxylate and tridecyl-1,2,3,4-butanetetracarboxylate, and mixtures of 1,2,2,6,6-pentamethyl-4-piperidyl-1,2,3,4-butanetetracarboxylate and tridecyl-1,2,3,4-butanetetracarboxylate.

[0038] The content of the hindered amine-based light stabilizer in the curable composition according to the present invention is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, even more preferably 0.05 parts by mass or more, and preferably 5.0 parts by mass or less, more preferably 1.0 part by mass or less, even more preferably 0.5 parts by mass or less, and even more preferably 0.2 parts by mass or less, when the total amount of compound (A) and compound (B) in the curable composition according to the present invention is 100 parts by mass, from the viewpoint of further improving the balance of performance of the resulting cured product, such as high refractive index, low curing shrinkage, glass adhesion, and weather resistance.

[0039] In the curable composition according to the present invention, the specific gravity of the curable composition, measured using a specific gravity bottle in accordance with JIS Z 8804:2012, is d 1 And the specific gravity of a test piece with a thickness of 250 μm made of the cured product of the curable composition according to the present invention is d 2 When, (1 - d 1 / d 2 ) × 100, the cure shrinkage rate of the curable composition is preferably 9.0% or less, more preferably 8.0% or less, still more preferably 7.5% or less, still more preferably 7.0% or less, still more preferably 6.5% or less. The lower limit of the cure shrinkage rate is not particularly limited, but for example, it may be 0.1% or more, 1.0% or more, 3.0% or more, 4.0% or more, or 5.0% or more. In the present embodiment, a test piece with a thickness of 250 μm made of the cured product of the curable composition according to the present invention can be obtained, for example, by irradiating ultraviolet rays to a curable film made of the curable composition applied on a glass substrate so that the exposure amount at 365 nm becomes 1000 mJ / cm 2 And then heating the obtained cured product at 80°C for 30 minutes in a nitrogen gas atmosphere.

[0040] <Method for producing a curable composition> The curable composition according to the present invention can be obtained by mixing a compound (A), a compound (B), and, if necessary, other components by a conventionally known method.

[0041] In the curable composition according to the present invention, the total content of the compound (A) and the compound (B), when the whole curable composition is 100% by mass, is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, and preferably 100% by mass or less, from the viewpoint of further improving the performance balance of high refractive index, low cure shrinkage, and glass adhesiveness of the obtained cured product

[0042] [Cured product] The cured product according to the present invention is obtained by curing the curable composition according to the present invention. Because the cured product according to the present invention has an improved balance of high refractive index, low curing shrinkage, and glass adhesion properties, it can be suitably used in optical materials.

[0043] In this embodiment, when a test piece with a thickness of 250 μm is prepared from the cured material, the refractive index (nD) of the D line (589.3 nm) of the test piece is preferably 1.600 or higher, more preferably 1.610 or higher, even more preferably 1.620 or higher, even more preferably 1.630 or higher, even more preferably 1.635 or higher, even more preferably 1.638 or higher, and even more preferably 1.640 or higher, from the viewpoint of further improving the optical properties of the cured material. The upper limit of the refractive index (nD) of the D line (589.3 nm) of the test piece is not particularly limited, but for example it may be 1.700 or lower, 1.680 or lower, 1.655 or lower, 1.650 or lower, or 1.645 or lower.

[0044] In this embodiment, when a test specimen with a thickness of 250 μm is prepared from the cured material, the Abbe number (νD) of the test specimen, measured in accordance with ASTM D542, is preferably 20 or higher, more preferably 25 or higher, even more preferably 28 or higher, and still more preferably 30 or higher, from the viewpoint of further improving the optical properties of the cured material. The upper limit of the Abbe number (νD) of the test specimen is not particularly limited, but for example it may be 45 or less, 42 or less, 39 or less, 37 or less, 35 or less, or 33 or less.

[0045] [Molded body] The molded article according to the present invention is a molded article containing a cured product according to the present invention, and can be obtained, for example, by molding a curable composition according to the present invention into a predetermined shape while curing it. Because the molded article according to the present invention contains the cured product according to the present invention, the balance of performance characteristics such as high refractive index, low curing shrinkage, and glass adhesion is improved, making it suitable for use as an optical material.

[0046] From the viewpoint of further improving the balance of performance of high refractive index, low curing shrinkage, and glass adhesion, the content of the cured product according to the present invention in the molded article according to the present invention is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 97% by mass or more, and preferably 100% by mass or less, when the total mass of the molded article is considered to be 100% by mass.

[0047] [Optical materials] The optical material according to the present invention includes a molded article according to the present invention, which can be obtained, for example, by molding a curable composition according to the present invention into a predetermined shape while curing it. The optical material according to the present invention includes cured products and molded articles according to the present invention, and therefore has an improved balance of performance in terms of high refractive index, low curing shrinkage, and glass adhesion. Examples of applications include various optical lenses such as lenses for various sensors, pickup lenses, projector lenses, prisms, fθ lenses, imaging lenses, camera lenses, light guide plates, lenses for head-mounted displays, plastic eyeglass lenses, goggles, eyeglass lenses for vision correction, lenses for imaging equipment, Fresnel lenses for liquid crystal projectors, lenticular lenses, and contact lenses; encapsulating materials for light-emitting diodes (LEDs); optical waveguides; optical adhesives used for joining wafer-level optical components (WLOs) and optical waveguides; anti-reflective coatings used for optical lenses, etc.; transparent coatings used for liquid crystal display device components (substrates, light guide plates, films, sheets, etc.); sheets and films that can be attached to car windshields or motorcycle helmets; and transparent substrates. The optical material according to the present invention has an improved balance of high refractive index, low curing shrinkage, and glass adhesion properties, making it more suitable for use as various optical lenses. Furthermore, because the optical material according to the present invention has an improved balance of high refractive index, low curing shrinkage, and glass adhesion properties, it can be suitably used as a laminate of a molded body and a glass substrate, further containing a glass substrate, and can also be suitably used as a so-called hybrid type optical lens in which a resin lens is formed on the glass substrate.

[0048] The embodiments of the present invention have been described above, but these are merely examples, and various other configurations can also be adopted. Furthermore, the present invention is not limited to the embodiments described above, and any modifications, improvements, etc., that can achieve the objectives of the present invention are included in the present invention. [Examples]

[0049] This embodiment will be described in detail below with reference to examples and other relevant information. However, this embodiment is not limited in any way to the descriptions of these examples.

[0050] <Example 1> (Preparation of curable composition) In a sample bottle, GSTA (60 parts by mass) was added as compound (A) having two or more thio(meth)acrylate groups, A-BPEF (40 parts by mass) as compound (B), and Irg184 (1-hydroxycyclohexyl phenyl ketone, manufactured by BASF, 3 parts by mass) was added as a polymerization initiator. The mixture was then mixed using a mixing rotor until the appearance was uniform to obtain a curable composition.

[0051] (Preparation of hardened film) A 0.5 mL curable composition was applied to an Eagle-XG (CORNING alkali-free glass substrate, 70 × 70 × 0.7 mmT) that had been demolded using Novec1720 (3M fluoride silane coating agent). This was then sandwiched between another demolded glass substrate via a 250 μm thick spacer, and the edges were secured with clips. An electrodeless lamp (H-bulb) was used to expose one side of the resulting laminate to an exposure dose of 1000 mJ / cm² at 365 nm. 2 After irradiating with ultraviolet light to achieve the desired result, the cured material was released from the glass substrate, and the resulting cured material was heated in a nitrogen gas atmosphere at 80°C for 30 minutes to obtain a cured film with a thickness of 250 μm. The refractive index and shrinkage rate during curing of the obtained cured film were measured using the method described below. The results are shown in Table 1.

[0052] <Measurement of refractive index (nD) and Abbe number (νD)> The refractive index (nD) and Abbe number (νD) were measured in accordance with ASTM D542 as follows. The refractive index (nD) of the cured film at the D line (589.3 nm) was measured using an Abbe refractometer (DR-M2, manufactured by Atago Corporation). RE-3520 (D line, manufactured by Atago Corporation) was used as the interference filter, and RE-1196 (monobromonaphthalene, manufactured by Atago Corporation) was used as the intermediate solution. The sample temperature was set to 25°C for the measurement. Furthermore, the refractive index (nC) of the C-line (wavelength 656.3 nm) of the cured film was measured using an Abbe refractometer (DR-M2, manufactured by Atago Co., Ltd.), with RE-3522 (C-line, manufactured by Atago Co., Ltd.) as the interference filter and RE-1196 (monobromonaphthalene, manufactured by Atago Co., Ltd.) as the intermediate solution, and the sample temperature was set to 25°C. Furthermore, the refractive index (nF) of the F-line (wavelength 486.1 nm) of the cured film was measured using a refractometer (DR-M2, manufactured by Atago Co., Ltd.), with RE-3521 (F-line, manufactured by Atago Co., Ltd.) as the interference filter and RE-1196 (monobromonaphthalene, manufactured by Atago Co., Ltd.) as the intermediate solution, and the sample temperature was set to 25°C. Then, the Abbe number of the cured film was calculated according to the following formula. Abbe number = (nD-1) / (nF-nC)

[0053] <Measurement of hardening shrinkage rate> Specific gravity d of the curable composition 1 The specific gravity was measured using a specific gravity bottle (JIS Z 8804:2012). The specific gravity of the cured film was also measured. 2 The specific gravity was measured using the Archimedes method (JIS Z 8807:2012). Using these specific gravity values, the curing shrinkage rate (%) was calculated using the following formula. Formula: Curing shrinkage rate (%) = (1-d 1 / d 2 ) × 100

[0054] <Evaluation of glass adhesion> A 0.5 mL curable composition was applied to an Eagle-XG (CORNING alkali-free glass substrate, 70 × 70 × 0.7 mmT) that had been demolded using Novec1720 (3M fluoride silane coating agent). This was then sandwiched between two undemolished Eagle-XG (CORNING alkali-free glass substrate, 70 × 70 × 0.7 mmT) substrates, separated by a 250 μm thick spacer, and the ends were secured with clips. An electrodeless lamp (H-bulb) was used to expose one side of the resulting laminate to an exposure dose of 1000 mJ / cm² at 365 nm. 2 After irradiating with ultraviolet light to achieve the desired result, the cured material was released from the release-treated glass substrate, and the resin cured material / glass substrate laminate was obtained by heating at 80°C for 30 minutes under a nitrogen gas atmosphere. The resulting laminates were evaluated for glass adhesion based on the following evaluation criteria. The evaluation results are shown in Table 1. (Evaluation Criteria) PASS (Good): No delamination or cracking of the resin was observed at the resin / glass substrate interface. FAIL (bad): Delamination at the resin / glass substrate interface and cracks in the resin were observed.

[0055] <Examples 2-7 and Comparative Example 1> Except for changing the composition of the curable composition to the composition shown in Table 1, each evaluation was carried out in the same manner as in Example 1. The composition of the curable composition and the results of each evaluation are shown in Table 1.

[0056] [Table 1]

[0057] The details of each component shown in Table 1 are as follows: (Compound (A)) GSTA: 1,8-Bisacryloylthio-(4-acryloylthiomethyl-3,6-dithiaoctane (a compound with the following structure synthesized in reference to Japanese Patent Publication No. 4-29967) [ka] • FSHA: 1,11-bisacryloylthio-(4,8-bisacryloylthiomethyl-3,6,9-trithiaundecane (a compound with the following structure synthesized in reference to Japanese Patent Publication No. 9-132563)) [ka]

[0058] (Compound (B)) A-BPEF (fluorene-based acrylate monomer (9,9-bis(4-(2-acryloyloxyethoxy)phenyl)fluorene), manufactured by Shin-Nakamura Kagaku Co., Ltd., compound with the structure shown below)

[0059] [ka]

[0060] • DNPOA(9,9-bis(3-(meth)acryloyloxypropyl)-2,7-bis(naphtho-2-yl)fluorene): A compound with the following structure synthesized with reference to International Publication No. 2021 / 131942A1.

[0061] [ka]

[0062] • DNEOA(9,9-bis(2-(meth)acryloyloxyethyl)-2,7-bis(naphtho-2-yl)fluorene): A compound with the following structure, synthesized by the method shown in Synthesis Example 1.

[0063] [ka]

[0064] Synthesis Example 1 Step (i) Preparation of 9,9-bis[2'-(3"-chloropropionyloxy)ethyl]-2,7-dinaphthalene-2-yl-9H-fluorene A mixture consisting of 3.5 g (6.9 mmol) of 9,9-bis(2'-hydroxyethyl)-2,7-dinaphthalen-2-yl-9H-fluorene, 1.93 g (15.2 mmol) of 3-chloropropionyl chloride, and 45 g of chloroform was heated to 60°C and stirred for 6 hours. The hydrochloric acid generated during the reaction was absorbed using an alkaline trap. The reaction mixture was then concentrated using an evaporator, and toluene was added to the concentrate. The toluene solution was washed three times with water. The toluene solution was concentrated using an evaporator, and diisopropyl ether was added to the residue to obtain a crystallized solid. 4.28 g of the target product was obtained as colorless crystals by filtration. The yield was 90%, the HPLC purity was 95Area%, and the melting point was 107°C.

[0065] Step (ii) Preparation of 9,9-bis(2'-acryloyloxyethyl)-2,7-dinaphthalen-2-yl-9H-fluorene A mixture consisting of 3.03 g (4.4 mmol) of 9,9-bis[2'-(3"-chloropropionyloxy)ethyl]-2,7-dinaphthalen-2-yl-9H-fluorene, 15 mg of methylhydroquinone, and 25 g of dichloromethane was added over 5 minutes at 2°C (ice bath) to a mixture of 1.0 g (9.9 mmol) of triethylamine and 3.0 g of chloroform. The mixture was then stirred overnight at room temperature, and the dichloromethane solution was washed with distilled water until neutral. The dichloromethane layer was separated, concentrated using an evaporator, and methanol was added to the residue to crystallize it. The crystals were filtered off to obtain 2.58 g of colorless crystals, which also yielded the target product. The yield was 95%, the HPLC purity was 97.5 Area%, and the melting point was 142°C.

[0066] (Other ingredients) • Irg184: Polymerization initiator (1-hydroxycyclohexylphenyl ketone, manufactured by BASF, compound with the structure shown below) [ka] • KBM-5103: Silane coupling agent (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., compound with the structure shown below) [ka] • AO-60: Antioxidant (Pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by ADEKA Corporation, compound with the structure shown below) [ka] • LA-82: Hindered amine-based photostabilizer (1,2,2,6,6-pentamethyl-piperidine-4-yl methacrylate, manufactured by ADEKA Corporation, compound with the structure shown below) [ka] • LA-46: UV absorber (2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, a compound with the structure shown below, manufactured by ADEKA Corporation) [ka]

[0067] This application claims priority based on Japanese Patent Application No. 2022-052317, filed on 28 March 2022, and incorporates all of its disclosures herein.

Claims

1. A compound (A) having three or more thio(meth)acrylate groups, A curable composition containing compound (B) represented by the following formula (1) is cured, The content of compound (B) in the curable composition is 30 parts by mass or more and 70 parts by mass or less per 100 parts by mass of the curable composition. A hardened material used in optical lenses. 【Chemistry 1】 (In the above formula (1), Z １ and Z ２ each independently represent an aromatic carbon ring or an alkylene group, and any hydrogen atom may be substituted with an alkyl group or an alkoxy group. Z ３ and Z ４ each independently represent an aromatic carbon ring or an alkyl group, and any hydrogen atom may be substituted with an alkyl group or an alkoxy group. R １ and R ３ each independently represent an alkylene group having 1 to 10 carbon atoms. R ２ and R ４ each independently represent a hydrogen atom or a methyl group. R ５ and R ６ each independently represent an alkyl group. m and n each independently represent an integer of 0 or more. o, p, q, and r are each an integer of 0 or more that satisfies the relationships o + q ≤ 4 and p + r ≤ 4.)

2. The cured product according to claim 1, wherein the compound (A) comprises at least one selected from the compounds represented by the following formula (2). 【Chemistry 2】 (In the above formula (2), n is an integer between 1 and 5, and R １ and R ２ Each of these independently represents either a hydrogen atom or a methyl group, and X is an alkylene group having 1 to 4 carbon atoms, in which any hydrogen atom may be substituted in the structure shown in formula (3) below. 【Transformation 3】 (In formula (3) above, R ３ R represents a hydrogen atom or a methyl group, and there are multiple R ３ These elements may be the same or different, W represents an alkylene group with 1 to 4 carbon atoms, and m is an integer of 1 or more.

3. The cured product according to claim 1 or 2, wherein the compound (A) comprises at least one selected from the group consisting of compounds represented by the following chemical formula. 【Chemistry 4】

4. The aforementioned compound (B) is 9,9-bis(4-(meth)acryloyloxyphenyl)fluorene, 9,9-bis(4-(2-(meth)acryloyloxyethoxy)phenyl)fluorene, 9,9-bis(4-(3-(meth)acryloyloxypropoxy)phenyl)fluorene, 9,9-bis(4-(2-(meth)acryloyloxypropoxy)phenyl)fluorene, 9,9-bis(4-(meth)acryloyloxy-3-methylphenyl)fluorene, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)-3-methylphenyl Fluorene, 9,9-bis[4-(3-(meth)acryloyloxypropoxy)-3-methylphenyl]Fluorene, 9,9-bis[4-(2-(meth)acryloyloxypropoxy)-3-methylphenyl]Fluorene, 9,9-bis(4-(meth)acryloyloxy-3-ethylphenyl)Fluorene, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)-3-ethylphenyl]Fluorene, 9,9-bis[4-(3-(meth)acryloyloxypropoxy)-3-ethylphenyl]Fluorene, 9,9-bis[4-( 2-(meth)acryloyloxypropoxy)-3-ethylphenyl]fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-1,8-diphenylfluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-1,8-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-1,8-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-2,7-diphenylfluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-2,7-diphenylfluorene Oren, 9,9-bis(2-(meth)acryloyloxypropyl)-2,7-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-3,6-diphenylfluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-3,6-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-3,6-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-4,5-diphenylfluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-4,5-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-4,5-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-1,8-bis(naphtho-1-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-1,8-bis(naphtho-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-1,8-bis(naphtho-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-2,7-bis(naphtho-1-yl)fluorene Oren, 9,9-bis(3-(meth)acryloyloxypropyl)-2,7-bis(naphtho-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-2,7-bis(naphtho-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-3,6-bis(naphtho-1-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-3,6-bis(naphtho-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-3,6-bis(naphtho-1-yl)fluorene Len, 9,9-bis(2-(meth)acryloyloxyethyl)-4,5-bis(naphtho-1-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-4,5-bis(naphtho-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-4,5-bis(naphtho-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-1,8-bis(naphtho-2-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-1,8-bis(naphtho-2-yl)fluorene , 9,9-bis(2-(meth)acryloyloxypropyl)-1,8-bis(naphtho-2-yl)fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-2,7-bis(naphtho-2-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-2,7-bis(naphtho-2-yl)fluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-2,7-bis(naphtho-2-yl)fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-3,6-bis(naphtho-2-yl)fluorene, 9,The cured product according to claim 1 or 2, comprising at least one selected from the group consisting of 9-bis(3-(meth)acryloyloxypropyl)-3,6-bis(naphtho-2-yl)fluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-3,6-bis(naphtho-2-yl)fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-4,5-bis(naphtho-2-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-4,5-bis(naphtho-2-yl)fluorene, and 9,9-bis(2-(meth)acryloyloxypropyl)-4,5-bis(naphtho-2-yl)fluorene.

5. The cured product according to claim 1 or 2, further comprising a polymerization initiator.

6. The cured product according to claim 1 or 2, further comprising at least one selected from the group consisting of a silane coupling agent, an antioxidant, an ultraviolet absorber, and a light stabilizer.

7. When the specific gravity of the curable composition, measured using a specific gravity bottle in accordance with JIS Z 8804:2012, is d1, and the specific gravity of a 250 μm thick test piece made of the cured product of the curable composition is d2, then (1-d １ / d ２ The cured product according to claim 1 or 2, wherein the curing shrinkage rate of the curable composition, represented by ) × 100, is 9.0% or less.

8. The cured material according to claim 1 or 2, wherein when a test piece with a thickness of 250 μm is prepared from the cured material, the refractive index (nD) of the D line (589.3 nm) of the test piece is 1.600 or more.

9. The cured material according to claim 1 or 2, wherein when a test specimen with a thickness of 250 μm is prepared from the cured material, the Abbe number (νD) of the test specimen, measured in accordance with ASTM D542, is 20 or more.

10. The cured product comprises the product described in claim 1 or 2, A molded body used in optical lenses.

11. The molded body includes the one described in claim 10, Optical materials used as optical lenses.

12. Further comprising a glass substrate, The optical material according to claim 11, wherein the molded body and the glass substrate are laminated.

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