Fluorene derivative, method for producing the same, and use thereof

Abstract

To provide a novel compound which exhibits a high refractive index.SOLUTION: The compound of the present disclosure is represented by the following formula (2). (In the formula, Z1a and Z1b each independently represent a naphthalene ring or a biphenyl ring; R1a and R1b each independently represent a linear or branched C1-4 alkyl group; k1 and k2 each independently represent an integer of 0-3; m1 and m2 represent 1; R2a and R2b each independently represent a linear or branched C1-4 alkyl group; n1 and n2 each independently represent an integer of 0-3; A1a and A1b each independently represent a linear or branched C1-6 alkylene group; A2a and A2b each independently represent a linear or branched C2-4 alkylene group; and p1 and p2 each independently represent an integer of 0-3.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a novel di(meth)acrylate compound having a fluorene skeleton, as well as a method for producing the same and uses thereof. [Background technology]

[0002] Compounds having a 9,9-bisarylfluorene skeleton exhibit excellent optical properties such as a high refractive index, and are therefore effectively used in various optical components as optical plastics (or optical resin materials). Numerous compounds, such as (meth)acrylate compounds, are known as compounds having such a 9,9-bisarylfluorene skeleton. Patent Documents 1 and 2 describe (meth)acrylate compounds having a 9,9-bis-fused polycyclic arylfluorene skeleton and curable compositions containing the (meth)acrylate compounds, as (meth)acrylate compounds exhibiting particularly high refractive indexes.

[0003] Patent Document 3 describes the synthesis of 9,9-bis(3-acryloyloxypropyl)fluorene. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-173648 [Patent Document 2] Japanese Patent Application Publication No. 2018-059059 [Patent Document 3] US Patent Application Publication No. 2003 / 0049173 Summary of the Invention [Problem to be solved by the invention]

[0005] In the examples of Patent Documents 1 and 2, compounds exhibiting high refractive indices, such as 9,9-bis[6-(2-acryloyloxyethoxy)-2-naphthyl]fluorene (BNEFA), and curable compositions and cured products thereof are prepared.

[0006] However, in the field of optical components, there is a demand for optical resin materials with even higher refractive indices, and there is a demand for materials with even higher refractive indices.

[0007] It should be noted that Patent Document 3 is a document relating to a quartz crystal microbalance (QCM) sensor element using a molecularly imprinted polymer (MIP), rather than an optical component, and does not describe at all the optical properties of 9,9-bis(3-acryloyloxypropyl)fluorene, such as the refractive index.

[0008] Therefore, an object of the present disclosure is to provide a novel di(meth)acrylate compound that exhibits a high refractive index, as well as a method for producing the same and uses thereof. [Means for solving the problem]

[0009] As a result of extensive research to achieve the above object, the inventors have unexpectedly discovered that a di(meth)acrylate compound having a specific chemical structure in which aryl groups are bonded to positions 1 to 8 of a fluorene skeleton exhibits the above-mentioned remarkably high refractive index, despite not having a 9,9-bisarylfluorene skeleton, and have thus completed the present invention.

[0010] That is, the di(meth)acrylate compound of the present disclosure is represented by the following formula (1).

[0011] [ka]

[0012] (In the formula, Z 1a and Z 1b each independently represents an arene ring, R 1a and R 1beach independently represents a substituent, k1 and k2 each independently represent an integer of 0 or more, m1 and m2 each independently represent an integer of 0 to 4, and at least one of m1 and m2 is 1 or greater; R 2a and R 2b each independently represents a substituent, n1 and n2 each independently represents an integer of 0 to 4, m1+n1 and m2+n2 are each equal to or less than 4, A 1a and A 1b each independently represents a linear or branched alkylene group, A 2a and A 2b each independently represents a linear or branched alkylene group; p1 and p2 each independently represent an integer of 0 or greater; R 3a and R 3b each independently represents a hydrogen atom or a methyl group).

[0013] In the formula (1), Z 1a and Z 1b is C 6-12 is an arene ring, m1 and m2 are integers of about 1 to 2, A 1a and A 1b is linear or branched chain C 1-6 is an alkylene group, A 2a and A 2b is linear or branched chain C 2-4 It is an alkylene group, and p1 and p2 may be integers of about 0 to 10.

[0014] In addition, in the formula (1), Z 1a and Z 1b is a benzene ring or a naphthalene ring, m1 and m2 are 1, A 1a and A 1b is linear or branched chain C 1-4 is an alkylene group, p1 and p2 may be 0.

[0015] The compound may have a refractive index of about 1.65 to 1.75 at a wavelength of 589 nm and a temperature of 20°C.

[0016] The present disclosure includes a method for producing a compound represented by the following formula (2) by reacting the compound with compounds represented by the following formulas (3a) and (3b).

[0017] [ka]

[0018] (In the formula, Z 1a and Z 1b , R 1a and R 1b , k1 and k2, m1 and m2, R 2a and R 2b , n1 and n2, m1+n1 and m2+n2, A 1a and A 1b , A 2a and A 2b , and p1 and p2 are the same as in formula (1) above).

[0019] [ka]

[0020] (In the formula, X 1a and X 1b each independently represents a hydroxyl group, an alkoxy group, or a halogen atom; R 3a and R 3b is the same as the above formula (1).

[0021] The present disclosure also encompasses a curable composition containing a compound represented by formula (1). The curable composition may further contain a compound represented by formula (7):

[0022] [ka]

[0023] (In the formula, Z 2a and Z 2b each independently represents an arene ring, R 5 represents a substituent, r represents an integer of 0 to 8, R 6a and R 6b each independently represents a substituent, s1 and s2 each independently represent an integer of 0 or more, A 4a and A 4b each independently represent a linear or branched alkylene group; t1 and t2 each independently represent an integer of 0 or greater; R 7a and R 7b each independently represents a hydrogen atom or a methyl group).

[0024] In the formula (7), Z 2a and Z 2b is C 6-12 is an arene ring, R 6a and R 6b is a hydrocarbon group, s1 and s2 are integers of about 0 to 2, A 4a and A 4b is linear or branched chain C 2-4 It is an alkylene group, and t1 and t2 may be integers of about 0 to 10.

[0025] The ratio of the compound represented by formula (1) to the compound represented by formula (7) may be the former / latter (mass ratio)=about 10 / 90 to 90 / 10.

[0026] The curable composition may further contain a compound represented by the following formula (8): [ka]

[0027] (wherein Ar represents an arene ring, R 8 represents a substituent, u represents an integer of 0 or more, A 5 represents a linear or branched alkylene group, v represents an integer of 0 or more, R 9 indicates a hydrogen atom or a methyl group).

[0028] In the formula (8), Ar is C 6-12 is an arene ring, R 8 is a hydrocarbon group, and u is an integer of about 0 to 2, A 5 is linear or branched chain C 2-4 It is an alkylene group, and v may be an integer of about 1 to 4.

[0029] The ratio of the compound represented by the formula (1) to the compound represented by the formula (8) may be the former / latter (mass ratio)=about 10 / 90 to 95 / 5.

[0030] The present disclosure also encompasses a cured product obtained by curing the curable composition. The cured product may have a refractive index of about 1.65 to 1.75 at a wavelength of 589 nm and at a temperature of 20°C, a glass transition temperature of about 0 to 50°C, and a 5% mass loss temperature of about 330 to 430°C.

[0031] The present disclosure also includes an optical component comprising the cured product.

[0032] The present disclosure may also solve the following problem as a secondary object: That is, another object of the present disclosure is to provide a di(meth)acrylate compound capable of forming a cured product exhibiting high heat resistance (high 5% mass loss temperature) even without having a 9,9-bisarylfluorene skeleton, as well as a production method and use thereof.

[0033] Still another object of the present disclosure is to provide a di(meth)acrylate compound that can form a cured product having excellent flexibility (or toughness) even if it has a rigid chemical structure such as an aromatic ring skeleton (even if it has a high refractive index or heat resistance), as well as a production method and uses thereof.

[0034] Another object of the present disclosure is to provide a di(meth)acrylate compound that has excellent solubility even when it has many aromatic ring skeletons, as well as a production method and uses thereof.

[0035] In this specification and claims, the number of carbon atoms in a substituent is represented by C1, C6, C 10 For example, an alkyl group with 1 carbon atom is represented as "C1 alkyl," and an aryl group with 6 to 10 carbon atoms is represented as "C 6-10 It is indicated as "aryl". [Effects of the Invention]

[0036] The novel di(meth)acrylate compounds disclosed herein have a remarkably high refractive index despite not having a 9,9-bisarylfluorene skeleton. Furthermore, even without a 9,9-bisarylfluorene skeleton, they can form cured products exhibiting relatively high heat resistance (high 5% mass loss temperature). Compounds with such high refractive indexes and heat resistance generally have rigid chemical structures, such as aromatic ring skeletons (benzene ring skeletons), resulting in hard, brittle cured products with high glass transition temperatures. However, the di(meth)acrylate compounds having the specific chemical structure of the present invention, contrary to expectations, have surprisingly low glass transition temperatures despite their high refractive indexes and 5% mass loss temperatures, making them easy to form cured products with relatively flexible properties (or toughness). Furthermore, while the inclusion of many aromatic ring skeletons in a chemical structure typically tends to reduce the solubility of a compound, these di(meth)acrylate compounds unexpectedly exhibit high solubility. DETAILED DESCRIPTION OF THE INVENTION

[0037] [Di(meth)acrylate compounds] The novel di(meth)acrylate compound of the present disclosure is represented by the following formula (1):

[0038] [ka]

[0039] (In the formula, Z 1a and Z 1b each independently represents an arene ring, R 1a and R 1b each independently represents a substituent, k1 and k2 each independently represent an integer of 0 or more, m1 and m2 each independently represent an integer of 0 to 4, and at least one of m1 and m2 is 1 or greater; R 2a and R 2b each independently represents a substituent, n1 and n2 each independently represents an integer of 0 to 4, m1+n1 and m2+n2 are each equal to or less than 4, A 1a and A 1b each independently represents a linear or branched alkylene group, A 2a and A 2b each independently represents a linear or branched alkylene group; p1 and p2 each independently represent an integer of 0 or greater; R 3a and R 3b each independently represents a hydrogen atom or a methyl group).

[0040] In the formula (1), Z 1a and Z 1b Examples of the arene ring (aromatic hydrocarbon ring) represented by the formula (I) include a monocyclic arene ring such as a benzene ring, a polycyclic arene ring, etc. Examples of the polycyclic arene ring include a fused polycyclic arene ring (fused polycyclic aromatic hydrocarbon ring), a ring-assembled arene ring (ring-assembled polycyclic aromatic hydrocarbon ring), etc.

[0041] Examples of the fused polycyclic arene ring include fused bicyclic arene rings, fused tricyclic arene rings, and other fused bicyclic to tetracyclic arene rings. Examples of the fused bicyclic arene ring include fused bicyclic C rings such as naphthalene rings and indene rings. 10-16 Examples of the fused tricyclic arene ring include fused tricyclic C arene rings such as anthracene rings and phenanthrene rings. 14-20 Preferred fused polycyclic arene rings include fused polycyclic C arene rings such as naphthalene rings. 10-14 It is an arene ring.

[0042] Examples of the ring-assembled arene ring include biarene rings such as biphenyl ring, phenylnaphthalene ring, and binaphthyl ring; and terarene rings such as terphenyl ring. Preferred ring-assembled arene rings include C 12-18 It is a biarene ring.

[0043] In this specification and claims, the term "ring-assembly arene ring" refers to an arene ring in which two or more ring systems (arene ring systems) are directly connected by single bonds or double bonds, and the number of bonds directly connecting the rings is one less than the number of ring systems. For example, as described above, biarene rings such as biphenyl rings, phenylnaphthalene rings, and binaphthyl rings are classified as ring-assembly arene rings even if they have a fused polycyclic arene ring skeleton such as a naphthalene ring skeleton. Therefore, "ring-assembly arene rings" are clearly distinguished from "fused polycyclic arene rings" such as naphthalene rings (non-ring-assembly arene rings).

[0044] Preferred Ring Z 1a and Z 1b As for C 6-14 arene rings, and more preferably C rings such as benzene rings, naphthalene rings, and biphenyl rings. 6-12 C rings such as arene rings, more preferably benzene rings and naphthalene rings 6-10 arene rings, particularly naphthalene rings.

[0045] Ring Z 1a and Z 1bThe types of may be different from each other, but are preferably the same. 1a The types of m2 and Z may be the same or different. 1b The same is true for .

[0046] Also, ring Z 1a and Z 1b may be substituted at any of the 1- to 4-positions and the 5- to 8-positions of the fluorene skeleton, but preferably at the 2-, 3- and / or 7-positions. When m1 and m2 are 1, preferred substitution positions (or bonding positions) are positions that are symmetrical on the paper in formula (1), such as the 1,8-positions, 2,7-positions, 3,6-positions, and 4,5-positions, and the 2,7-positions are particularly preferred.

[0047] R 1a and R 1b Examples of the substituent (non-reactive substituent or non-polymerizable substituent) represented by the formula (I) include a halogen atom, a hydrocarbon group (or a group [-R h ]), the group [-OR h ](where R h represents the hydrocarbon group), the group [—SR h ](where R h represents the above hydrocarbon group), an acyl group, a nitro group, a cyano group, a mono- or di-substituted amino group, and the like.

[0048] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0049] R h Examples of the hydrocarbon group represented by the formula include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

[0050] Examples of the alkyl group include linear or branched C alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, and t-butyl groups. 1-10 alkyl groups, preferably straight-chain or branched-chain C 1-6Alkyl groups, more preferably linear or branched C 1-4 It is an alkyl group.

[0051] Examples of the cycloalkyl group include C cyclopentyl and cyclohexyl groups. 5-10 Cycloalkyl groups are exemplified.

[0052] Examples of the aryl group include C phenyl, alkylphenyl, biphenylyl, and naphthyl groups. 6-12 Examples of the alkylphenyl group include mono- to tri-C alkylphenyl groups such as methylphenyl (or tolyl) and dimethylphenyl (or xylyl). 1-4 Examples include alkyl-phenyl groups.

[0053] Examples of the aralkyl group include C aryl groups such as benzyl and phenethyl groups. 6-10 Aryl-C 1-4 Examples of suitable alkyl groups include:

[0054] The group [-OR h ] includes, for example, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, etc., and specifically, the hydrocarbon group R h Examples of the alkoxy group include a linear or branched C alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group. 1-10 Examples of the cycloalkyloxy group include a C alkoxy group such as a cyclohexyloxy group. 5-10 Examples of the aryloxy group include a C aryloxy group such as a phenoxy group. 6-10 Examples of the aralkyloxy group include C aryloxy groups such as benzyloxy groups. 6-10 Aryl-C 1-4 Examples thereof include alkyloxy groups.

[0055] The group [—SR h] includes, for example, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, etc., and specifically, the hydrocarbon group R h Examples of the alkylthio group include groups corresponding to the following: C methylthio group, ethylthio group, propylthio group, n-butylthio group, t-butylthio group, etc. 1-10 Examples of the cycloalkylthio group include a C alkylthio group such as a cyclohexylthio group. 5-10 Examples of the arylthio group include a C thiophenoxy group (phenylthio group) and the like. 6-10 Examples of the aralkylthio group include a C arylthio group such as a benzylthio group. 6-10 Aryl-C 1-4 Examples include alkylthio groups.

[0056] Acyl groups include C groups such as acetyl groups. 1-6 Examples include alkyl-carbonyl groups.

[0057] Examples of the mono- or di-substituted amino group include a dialkylamino group and a bis(alkylcarbonyl)amino group. Examples of the dialkylamino group include a di-C group such as a dimethylamino group. 1-4 Examples of the bis(alkylcarbonyl)amino group include bis(C acetylamino group, etc. 1-4 alkyl-carbonyl)amino groups.

[0058] These groups R 1a and R 1b Among these, representative examples include hydrocarbon groups, alkoxy groups, acyl groups, nitro groups, cyano groups, and substituted amino groups. When k1 is 1 or more, preferred groups R 1a The alkyl group and the alkoxy group are linear or branched C groups such as methyl groups. 1-6 Linear or branched C such as alkyl group or methoxy group 1-4Alkoxy groups are exemplified, among which alkyl groups, particularly straight or branched C groups such as methyl groups, are preferred. 1-4 Alkyl groups are preferred. k2 and R 1b The same applies to the group R 1a is an aryl group, the group R 1a is Ring Z 1a R may form the ring-assembled arene ring. 1b and Z 1b The same is true for .

[0059] The substitution numbers k1 and k2 are 1a and Z 1b For example, it can be selected from integers of about 0 to 7, and preferred ranges are the following stepwise integers of 0 to 6, 0 to 5, 0 to 4, 0 to 3, and 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0060] base R 1a and R 1b The numbers of substitutions k1 and k2 in the ring Z may be different from each other, but are preferably the same. 1a Two or more groups R 1a The types of k2 and R may be the same or different. 1b The same applies to the group R 1a and R 1b The types of groups R may be different from each other, but are preferably the same. 1a and R 1b The substitution position of ring Z is not particularly limited. 1a and Z 1b The selection may be made depending on the type of

[0061] group [-Z 1a -(R 1a ) k1 ] and the group [-Z 1b -(R 1b ) k2 ] (Hereafter, these are referred to as Z 1The numbers of substitutions m1 and m2 of the substituents (also referred to as containing groups) are each, for example, an integer of about 1 to 3, preferably 1 or 2, and more preferably 1. m1 and m2 may be different from each other, but are preferably the same. At least one of m1 and m2 is an integer of 1 or more, preferably both are integers of 1 or more, such as 1 or 2, and more preferably both are 1.

[0062] When m1 is 2 or more, two or more groups [-Z 1a -(R 1a ) k1 The types of m2 and the group [-Z] may be the same or different. 1b -(R 1b ) k2 The same applies to the group [-Z 1a -(R 1a ) k1 ] and the group [-Z 1b -(R 1b ) k2 ] may be the same or different, and are preferably the same.

[0063] R 2a and R 2b The substituent represented by the formula (non-reactive substituent or non-polymerizable substituent) is 1 Any substituent other than the containing group may be used, and representative examples include hydrocarbon groups such as alkyl groups (excluding aryl groups), halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms, and cyano groups. Examples of alkyl groups include linear or branched C groups such as methyl groups, ethyl groups, and t-butyl groups. 1-6 When the number of substitutions n1 is 1 or more, preferred R 2a is a linear or branched chain C 1-4 alkyl group, more preferably a linear or branched C 1-3 Alkyl groups, especially C groups such as methyl groups 1-2 Alkyl groups are preferred. n2 and R 2b The same is true for .

[0064] R2a and R 2b The numbers of substitutions n1 and n2 are each, for example, an integer of about 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly 0. n1 and n2 may be different from each other, but are preferably the same. When n1 is 2 or more, a plurality of R 2a The types of n2 and R may be the same or different. 2b The same applies to R. In addition, when both n1 and n2 are 1 or more, 2a and R 2b The types of R may be the same or different, and are preferably the same. 2a and R 2b The substitution position of Z is not particularly limited. 1 It is sufficient that the substituent is at a position other than the substitution position of the containing group.

[0065] m1+n1 and m2+n2 are each, for example, an integer of 0 to 4, preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1. m1+n1 and m2+n2 may be different from each other, but are preferably the same.

[0066] A 1a and A 1b Examples of the linear or branched alkylene group represented by the formula (I) include linear or branched C alkylene groups such as methylene, ethylene, trimethylene, propylene, 1,2-butanediyl, and 2-methylpropane-1,3-diyl. 1-12 Preferred alkylene groups include linear or branched C 1-8 Alkylene groups, specifically, linear or branched C groups such as methylene, ethylene, trimethylene, propylene, and 2-methylpropane-1,3-diyl groups 1-6 alkylene groups, more preferably linear or branched C 1-5 Alkylene groups, more preferably linear or branched C 1-4 Alkylene groups, particularly linear or branched C 2-4An alkylene group is preferred, and a trimethylene group is particularly preferred. 1a and A 1b The types may be different from each other, but are preferably the same.

[0067] A 2a and A 2b Examples of the linear or branched alkylene group represented by the formula (I) include linear or branched C alkylene groups such as an ethylene group, a propylene group, a trimethylene group, a 1,2-butanediyl group, a 1,3-butanediyl group, and a tetramethylene group. 2-6 Preferred alkylene groups include linear or branched C 2-4 alkylene group, more preferably a linear or branched C 2-3 Among them, an ethylene group and a propylene group are preferred, and an ethylene group is particularly preferred. 2a and A 2b The types may be different from each other, but are preferably the same.

[0068] Oxyalkylene group (OA 2a ) and (OA 2b The repeating numbers p1 and p2 of the (poly)oxyalkylene group [-(OA) can be selected, for example, from about 0 to 20, and preferred ranges are 0 to 15, 0 to 10, 0 to 8, 0 to 5, 0 to 3, 0 to 2, and 0 to 1, in the following stepwise order, and particularly 0. When p1 is 2 or more, 2a ) p1 -] 2 or more A's 2a The types of p2 and A may be different from each other, but are preferably the same. 2b The same is true for .

[0069] Furthermore, p1 and p2 may be the same or different from each other. The repeating numbers p1 and p2 may be average values ​​(or arithmetic mean values), i.e., average numbers of moles added, and the range thereof, including preferred embodiments, is the same as the range of integers described above.

[0070] The total number of repeating numbers p1 and p2 is determined by the number of oxyalkylene groups (OA) in one molecule of the di(meth)acrylate compound represented by the formula (1). 2a ) and (OA 2b ) (or the average value of the total number of moles added), and may be simply referred to as p1+p2. p1+p2 can be selected, for example, from a range of about 0 to 30, and preferred ranges are the following stepwise ranges: 0 to 25, 0 to 20, 0 to 15, 0 to 12, 0 to 10, 0 to 8, 0 to 6, 0 to 5, 0 to 4, 0 to 3, and 0 to 2, and more preferably 0 to 1, and particularly preferably 0. Furthermore, p1+p2 may be an integer as described above, but may also be the average value of the total number of moles added, and its range, including preferred embodiments, is the same as the range of integers described above.

[0071] If the value of p1, p2, or p1+p2 is too large, the refractive index and heat resistance may decrease.

[0072] Incidentally, p1+p2 can be measured by a conventional method. For example, in the preparation of a compound (diol compound) represented by formula (2) described later, which is a raw material for the di(meth)acrylate compound represented by formula (1), p1+p2 can be measured by an addition reaction of a compound (diol compound) represented by formula (4) described later with an alkylene oxide (alkylene carbonate or haloalkanol) to form a (poly)alkyleneoxy group [-(OA 2a ) p1 -] and [-(OA 2b ) p2 -], it can be measured by a method of calculating the arithmetic mean or the arithmetic mean value from the ratio of the amount of diol compound (or hydroxyl value) to the amount of alkylene oxide (alkylene carbonate or haloalkanol) consumed in the reaction, specifically, by the method described in JP 2013-53310 A.

[0073] R 3a and R 3b R may be either a hydrogen atom or a methyl group, but is preferably a hydrogen atom in terms of improving reactivity (or curability) and refractive index. 3a and R 3bThe types may be the same or different from each other, and are preferably the same.

[0074] Representative di(meth)acrylate compounds represented by the formula (1) include, for example, di(meth)acrylate compounds in which m1 and m2 are 1 and p1 and p2 are 0, i.e., 9,9-bis[(meth)acryloyloxyalkyl]-diarylfluorenes, and more specifically, 9,9-bis[(meth)acryloyloxyalkyl]-diphenylfluorene, 9,9-bis[(meth)acryloyloxyalkyl]-dinaphthylfluorene, etc.

[0075] Examples of 9,9-bis[(meth)acryloyloxyalkyl]-diphenylfluorene include 9,9-bis[(meth)acryloyloxyalkyl]-diphenylfluorene such as 9,9-bis[3-(meth)acryloyloxypropyl]-1,8-diphenylfluorene, 9,9-bis[3-(meth)acryloyloxypropyl]-2,7-diphenylfluorene, 9,9-bis[3-(meth)acryloyloxypropyl]-3,6-diphenylfluorene, and 9,9-bis[3-(meth)acryloyloxypropyl]-4,5-diphenylfluorene. 1-6 alkyl]-diphenylfluorene, and the like.

[0076] Examples of 9,9-bis[(meth)acryloyloxyalkyl]-dinaphthylfluorene include 9,9-bis[3-(meth)acryloyloxypropyl]-1,8-di(2-naphthyl)fluorene, 9,9-bis[3-(meth)acryloyloxypropyl]-2,7-di(2-naphthyl)fluorene, 9,9-bis[3-(meth)acryloyloxypropyl]-3,6-di(2-naphthyl)fluorene, 9,9-bis[3-(meth)acryloyloxypropyl]-4,5-di(2-naphthyl)fluorene, and 9,9-bis[3-(meth)acryloyloxypropyl]-2,7-di(1-naphthyl)fluorene. 1-6 alkyl]-dinaphthylfluorene and the like.

[0077] Among these di(meth)acrylate compounds represented by the formula (1), 9,9-bis[(meth)acryloyloxypropyl]-2,7-diphenylfluorene and other 9,9-bis[(meth)acryloyloxypropyl]-2,7-diphenylfluorene are preferred. 1-4 Alkyl]-2,7-diphenylfluorene;9,9-bis[(meth)acryloyloxypropyl C 1-4 alkyl]-2,7-dinaphthylfluorene is preferred, and 9,9-bis[(meth)acryloyloxy C 2-4 More preferred are 9,9-bis[(meth)acryloyloxy]-2,7-di(2-naphthyl)fluorenes, and among these, 9,9-bis[(meth)acryloyloxy]-2,7-di(2-naphthyl)fluorenes are preferred. 2-3 Alkyl]-2,7-di(2-naphthyl)fluorene is particularly preferred.

[0078] The di(meth)acrylate compound represented by the formula (1) has a high refractive index, and the refractive index nD (refractive index before curing) at a temperature of 25°C and a wavelength of 589 nm may be, for example, about 1.6 to 1.8, and preferred ranges are the following stepwise ranges: 1.63 to 1.77, 1.65 to 1.75, 1.655 to 1.72, 1.66 to 1.7, 1.665 to 1.695, 1.67 to 1.69, and 1.675 to 1.685.

[0079] The melting point of the di(meth)acrylate compound represented by the formula (1) may be, for example, about 50 to 200°C, and preferably is 80 to 160°C, 100 to 140°C, 110 to 130°C, and 115 to 125°C in the following stepwise manner.

[0080] The di(meth)acrylate compound represented by formula (1) tends to have excellent solubility even when its chemical structure contains many aromatic ring skeletons (benzene ring skeletons), which tend to reduce solubility. For example, compared to conventional polyfunctional (meth)acrylates having the same number of aromatic ring skeletons (benzene ring skeletons) (such as the polyfunctional (meth)acrylates described in JP 2018-059059 A), the compound is easily soluble in many solvents even at relatively high concentrations of about 20 to 50% by mass, preferably 25 to 40% by mass, and more preferably 30 to 35% by mass. Therefore, it is possible to achieve both a high refractive index and / or high heat resistance and high solubility, and even when the compound represented by formula (1) is a solid that does not exhibit fluidity at room temperature of about 25°C, it tends to effectively improve handleability.

[0081] The melt viscosity of the di(meth)acrylate compound represented by the formula (1) may be, for example, about 10 to 1000 mPa·s at 150°C, and preferably ranges from 50 to 500 mPa·s, 100 to 400 mPa·s, 150 to 350 mPa·s, and 200 to 300 mPa·s in the following stepwise manner.

[0082] In this specification and claims, the refractive index, melting point and melt viscosity of the di(meth)acrylate compound represented by the formula (1) can be measured by the method described in the examples below.

[0083] [Method for producing di(meth)acrylate compound] The method for producing the di(meth)acrylate compound represented by the formula (1) is not particularly limited, and the compound may be prepared, for example, by the following reaction steps.

[0084] [ka]

[0085] (In the formula, X 1a and X 1b each independently represents a hydroxyl group, an alkoxy group, or a halogen atom, R 4a and R4b each independently represents a hydrogen atom or an alkyl group, A 3a and A 3b each independently represents a linear or branched alkylene group, q1 and q2 each independently represent 0 or 1; X 2a and X 2b each independently represents a reactive group capable of forming a carbon-carbon bond (or a direct bond) by a coupling reaction; X 3a is the reactive group X 2a and X 3b is the reactive group X 2b and each represents a reactive group capable of forming a carbon-carbon bond by a coupling reaction, Z 1a and Z 1b , R 1a and R 1b , k1 and k2, m1 and m2, R 2a and R 2b , n1 and n2, m1+n1 and m2+n2, A 1a and A 1b , A 2a and A 2b , p1 and p2, and R 3a and R 3b is the same as the formula (1) above, including preferred embodiments).

[0086] (Preparation of Compound Represented by Formula (5)) The compound represented by the formula (5) can be prepared by a coupling reaction (or cross-coupling reaction) between the compound represented by the formula (6) and the compounds represented by the formulas (7a) and (7b).

[0087] The coupling reaction is not particularly limited and includes conventional coupling reactions, such as coupling reactions using a palladium catalyst (or a palladium(0) catalyst) such as the Suzuki-Miyaura coupling reaction, the Migita-Kosugi-Stille coupling reaction, the Negishi coupling reaction, and the Hiyama coupling reaction, and coupling reactions using a nickel catalyst (or a nickel(0) catalyst) such as the Kumada-Tamao-Corriu coupling reaction. Of these coupling reactions, the Suzuki-Miyaura coupling reaction is preferred.

[0088] Reactive Group X 2a and X 2b and X 3a and X 3b can be appropriately selected depending on the type of the coupling reaction. When synthesis is carried out by Suzuki-Miyaura coupling reaction, one reactive group (or first reactive group), for example, group X 2a and X 2b Examples of the fluorinated alkanesulfonyloxy group include a halogen atom or a fluorinated alkanesulfonyloxy group. Examples of the halogen atom include an iodine atom, a bromine atom, and a chlorine atom. Examples of the fluorinated alkanesulfonyloxy group include a fluorinated alkanesulfonyloxy group such as a trifluoromethanesulfonyloxy group (or a group [-OTf]). 1-4 Examples include an alkanesulfonyloxy group.

[0089] These one reactive groups may be used alone or in combination of two or more. Of these one reactive groups, a halogen atom is preferred, an iodine atom or a bromine atom is more preferred, and a bromine atom is particularly preferred.

[0090] In the Suzuki-Miyaura coupling reaction, the one reactive group (or the first reactive group) can be coupled with another reactive group (or a second reactive group), such as a group X 3a and X 3bExamples of the boronic acid group include a boronic acid group (dihydroxyboryl group or group [-B(OH)2]), a boronate ester group, etc. Examples of the boronic acid ester group include a dialkoxyboryl group such as a dimethoxyboryl group, a diisopropoxyboryl group, and a dibutoxyboryl group; a pinacolatoboryl group (or group [-Bpin]), a 1,3,2-dioxaborinan-2-yl group, and a 5,5-dimethyl-1,3,2-dioxaborinan-2-yl group, etc.

[0091] These other reactive groups may be used alone or in combination of two or more. Of the other reactive groups, the group [—B(OH) 2 ] is preferred.

[0092] In addition, the group X 2a and X 2b and group X 3a and X 3b The groups X may be any reactive groups as long as they are a pair of reactive groups capable of coupling reaction with each other. 2a and X 2b is the second reactive group, such as a boronic acid group, and group X 3a and X 3b may be the first reactive group such as a halogen atom, but the group X 2a and X 2b is the first reactive group such as a halogen atom, and group X 3a and X 3b is preferably said second reactive group such as a boronic acid group.

[0093] In the formula (6), the group X 2a and X 2b The substitution position of Z in the formula (1) 1 It corresponds to the substitution position of the containing group, and is the same as above, including preferred embodiments.

[0094] In the formula (6) [and formulas (5) and (5A)], A 3a and A 3b The linear or branched alkylene group represented by A 1a and A 1bThe alkylene groups A and B have one less carbon atom. 3a and A 3b Examples of the alkyl group include linear or branched C alkyl groups such as methylene, ethylene, trimethylene, propylene, 1,2-butanediyl, and 2-methylpropane-1,3-diyl groups. 1-11 The alkylene group is preferably a linear or branched C 1-5 alkylene group, more preferably a linear or branched C 1-4 Alkylene groups, particularly linear or branched C 1-3 An alkylene group is preferred, and an ethylene group is particularly preferred. When q1 and q2 are both 1, A 3a and A 3b The types may be different from each other, but are preferably the same.

[0095] In the formula (6) [and formulas (5) and (5A)], R 4a and R 4b Examples of the alkyl group represented by the formula (I) include a linear or branched C alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and a t-butyl group. 1-6 alkyl groups, and preferably straight-chain or branched-chain C 1-4 Alkyl groups, more preferably linear or branched C 1-3 Alkyl groups, especially C groups such as methyl groups 1-2 Alkyl groups are preferred.

[0096] R 4a and R 4b may be either a hydrogen atom or an alkyl group, but is preferably an alkyl group. 4a and R 4b The types may be different from each other, but are preferably the same.

[0097] In the formula (6) [and formula (5)], the group [-A 3a -C(=O)-OR 4a ] and [-A3b -C(=O)-OR 4b The coefficients q1 and q2 in

[0049] may each be either 0 or 1, but are preferably 1. Furthermore, q1 and q2 may be different from each other, but are preferably the same.

[0098] Representative compounds represented by the formula (6) include, for example, dihalo-9H-fluorene, 9,9-bis(alkoxycarbonylalkyl)dihalofluorene, and the like.

[0099] Examples of dihalo-9H-fluorene include 2,7-dibromo-9H-fluorene, etc. Commercially available dihalo-9H-fluorenes may be used.

[0100] Examples of the 9,9-bis(alkoxycarbonylalkyl)dihalofluorene include 9,9-bis(C ) such as 9,9-bis(2-methoxycarbonylethyl)-2,7-dibromofluorene, 9,9-bis(2-ethoxycarbonylethyl)-2,7-dibromofluorene, and 9,9-bis(2-methoxycarbonylpropyl)-2,7-dibromofluorene. 1-4 Alkoxy-carbonyl-C 2-6 9,9-bis(alkoxycarbonylalkyl)dihalofluorenes may be prepared, for example, in accordance with the method described in JP-A-2005-89422, specifically by reacting a 9H-fluorene unsubstituted at the 9-position, such as 2,7-dibromofluorene, with an acrylic acid ester, such as methyl acrylate, or a haloacetic acid ester, such as methyl bromoacetate, in the presence of a base catalyst, such as trimethylbenzylammonium hydroxide.

[0101] Of these compounds represented by the formula (6), 9,9-bis(alkoxycarbonylalkyl)dihalofluorene is preferred.

[0102] The compounds represented by the formulas (7a) and (7b) include Z in the di(meth)acrylate represented by the formula (1). 1a and Z 1b , R 1a and R 1b and compounds corresponding to preferred embodiments of k1 and k2, for example, arylboronic acids such as phenylboronic acid, 1-naphthylboronic acid, and 2-naphthylboronic acid, with 2-naphthylboronic acid being preferred. The compounds represented by formulas (7a) and (7b) are preferably the same compound. The compounds represented by formulas (7a) and (7b) can be commercially available products.

[0103] The ratio of the compound represented by formula (6) to the total amount of the compounds represented by formulas (7a) and (7b) may be, for example, the former / latter (molar ratio) = about 1 / 2 to 1 / 10, and preferred ranges are 1 / 2.2 to 1 / 8, 1 / 2.5 to 1 / 5, and 1 / 2.7 to 1 / 3.3 in the following stepwise manner.

[0104] When the synthesis is carried out by the Suzuki-Miyaura coupling reaction, the reaction is carried out in the presence of a palladium catalyst, such as a conventional coupling catalyst, for example, a palladium(0) catalyst or a palladium(II) catalyst.

[0105] Examples of palladium(0) catalysts include palladium(0)-phosphine complexes such as tetrakis(triphenylphosphine)palladium(0) [or Pd(PPh3)4] and bis(tri-t-butylphosphine)palladium(0) [or Pd(P(t-Bu)3)2].

[0106] Examples of palladium(II) catalysts include palladium(II)-phosphine complexes such as [1,2-bis(diphenylphosphino)ethane]palladium(II) dichloride (or PdCl(dppe)], [1,3-bis(diphenylphosphino)propane]palladium(II) dichloride (or PdCl(dppp)], [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride (or PdCl(dppf)], bis(triphenylphosphine)palladium(II) dichloride (or PdCl(PPh)), and bis(tri-o-tolylphosphine)palladium(II) dichloride (or PdCl(P(o-Tol)). When a palladium(II) catalyst is used, the reaction begins by reduction to a zero-valent complex with a reducing compound in the reaction system, such as a phosphine, amine, or organometallic reagent.

[0107] The palladium catalyst may be prepared in situ by adding a catalyst precursor such as tris(dibenzylideneacetone)dipalladium(0) chloroform complex [or Pd2(dba)3·CHCl3] to a ligand such as a phosphine or carbene.

[0108] These catalysts can be used alone or in combination of two or more. Among these catalysts, palladium(0)-phosphine complexes such as Pd(PPh3)4 are preferred. The proportion of the catalyst, calculated as metal, may be, for example, about 0.01 to 0.1 moles, preferably 0.03 to 0.07 moles, per mole of the compound represented by formula (6).

[0109] The Suzuki-Miyaura coupling reaction may be carried out in the presence of a base, such as a metal carbonate or hydrogen carbonate, a metal hydroxide, a metal fluoride, a metal phosphate, a metal organic acid salt, or a metal alkoxide.

[0110] Examples of metal carbonates or hydrogen carbonates include alkali metal carbonates or hydrogen carbonates such as sodium carbonate, potassium carbonate, cesium carbonate, and sodium hydrogen carbonate, and thallium (I) carbonate.

[0111] Examples of metal hydroxides include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and cesium hydroxide, alkaline earth metal hydroxides such as barium hydroxide, and thallium(I) hydroxide.

[0112] Examples of metal fluorides include alkali metal fluorides such as potassium fluoride and cesium fluoride.

[0113] Examples of metal phosphates include alkali metal phosphates such as tripotassium phosphate.

[0114] Examples of metal organic acid salts include alkali metal acetates such as potassium acetate.

[0115] Examples of metal alkoxides include alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-butoxide.

[0116] These bases can be used alone or in combination of two or more, and metal carbonates such as potassium carbonate are preferred. The proportion of the base may be, for example, about 0.1 to 50 mol, preferably 1 to 25 mol, per mol of the compound represented by formula (6).

[0117] The coupling reaction may be carried out in the presence or absence of a phase transfer catalyst. Examples of the phase transfer catalyst include tetraalkylammonium halides such as tetrabutylammonium bromide (TBAB) and trioctylmethylammonium chloride. These phase transfer catalysts can be used alone or in combination. Among these phase transfer catalysts, TBAB is preferred.

[0118] The coupling reaction may be carried out in the absence or presence of an inert solvent, such as water; alcohols such as methanol and ethanol; ethers such as cyclic ethers and chain ethers; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; nitriles such as acetonitrile and benzonitrile; amides such as N,N-dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxides such as dimethyl sulfoxide; and hydrocarbons such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.

[0119] Examples of cyclic ethers include dioxane and tetrahydrofuran. Examples of chain ethers include dialkyl ethers such as diethyl ether and diisopropyl ether, and glycol ethers. Examples of glycol ethers include (poly)alkylene glycol monoalkyl ethers such as methyl cellosolve and methyl carbitol, and (poly)alkylene glycol dialkyl ethers such as dimethoxyethane.

[0120] Examples of aliphatic hydrocarbons include hexane and dodecane. Examples of alicyclic hydrocarbons include cyclohexane. Examples of aromatic hydrocarbons include toluene and xylene.

[0121] These solvents can be used alone or in combination of two or more. Among these solvents, a mixed solvent of water and a chain ether such as dimethoxyethane is preferred.

[0122] The coupling reaction may be carried out under an inert gas atmosphere, for example, under an atmosphere of nitrogen gas or a rare gas such as helium or argon. The reaction temperature is, for example, 50 to 200° C., preferably 60 to 100° C. The reaction time is not particularly limited and may be, for example, about 1 to 10 hours.

[0123] After completion of the reaction, the reaction mixture may be separated and purified, if necessary, by a conventional separation and purification method, such as washing, extraction, filtration, dehydration, concentration, decantation, recrystallization, reprecipitation, chromatography, or a combination thereof.

[0124] (Compound represented by formula (5A)) The compound represented by formula (5A) is a compound in which q1 and q2 in formula (5) are 1, and can be prepared by using, as a raw material, a compound represented by formula (6) in which q1 and q2 are 1. Furthermore, when at least one of q1 and q2 in formula (5) is 0, particularly when q1 and q2 are 0, the compound represented by formula (5A) may be prepared by reacting this compound with a (meth)acrylic acid ester or a haloacetic acid alkyl ester according to, for example, the method described in JP-A-2005-89422.

[0125] (Preparation of Compound Represented by Formula (4)) The compound represented by formula (4) can be prepared by reducing the compound represented by formula (5A). A conventional reducing agent may be used for the reduction. Examples of the reducing agent include metal hydrides such as metal borohydrides, metal aluminum hydrides, boranes, aluminum hydrides, organosilicon compounds, and organotin compounds.

[0126] Examples of metal borohydrides include alkali metal borohydrides; zinc borohydrides such as zinc borohydride (Zn(BH4)2); and the like. Examples of alkali metal borohydrides include lithium borohydrides such as lithium borohydride (LiBH), lithium triethylborohydride (LiBH(C2H5)3), lithium tri-s-butylborohydride (LiBH(s-C4H9)3), and bis(2,4,6-trimethylphenyl)lithium borohydride (LiBH(Mes)2); sodium borohydrides such as sodium borohydride (NaBH4), sodium cyanoborohydride (NaBH3CN), sodium trimethoxyborohydride (NaBH(OCH3)3), sodium triacetoxyborohydride (NaBH(OCOCH3)3), and sodium borohydride sulfide (NaBH2S3); and potassium borohydrides such as potassium tri-s-butylborohydride (KBH(s-C4H9)3).

[0127] Examples of the metal aluminum hydrides include alkali metal aluminum hydrides, such as lithium aluminum hydrides (LiAlH), lithium trimethoxyaluminum hydride (LiAlH(OCH)), and lithium tri-t-butoxyaluminum hydride (LiAlH(Ot-CH)); and sodium aluminum hydrides such as sodium aluminum hydride (NaAlH) and sodium bis(2-methoxyethoxy)aluminum hydride ([(CHOCHCHO)AlH]Na).

[0128] Examples of boranes include diborane; borane complexes such as borane-tetrahydrofuran complex and borane-dimethylsulfide complex; and 9-borabicyclo[3.3.1]nonane (9-BBN).

[0129] Examples of aluminum hydrides include aluminum hydride (AlH3) and diisobutylaluminum hydride ((i-C4H9)2AlH).

[0130] Examples of the organosilicon compound include trialkylsilanes such as triethylsilane, diarylsilanes such as diphenylsilane, and aryldialkylsilanes such as phenyldimethylsilane.

[0131] Examples of the organotin compound include trialkylstannanes such as tri-n-butylstannane, dialkylstannanes such as di-n-butylstannane, and diarylstannanes such as diphenylstannane.

[0132] These reducing agents can be used alone or in combination of two or more. Preferred reducing agents are metal borohydrides such as alkali metal borohydrides, and more preferred are sodium borohydrides such as sodium borohydride (NaBH).

[0133] The amount of the reducing agent used is, for example, 2 to 10 mol, preferably 3 to 5 mol, and more preferably 3.5 to 4.5 mol, relative to 1 mol of the compound represented by the formula (5A).

[0134] The reducing agent may be used together with other reagents (or activators) depending on the type of reducing agent and the compound represented by formula (5A). For example, when a sodium borohydride such as sodium borohydride (NaBH4) is used as the reducing agent, it may be used together with a boron trifluoride ether complex such as boron trifluoride diethyl ether complex. The ratio of the activator to 1 mole of the reducing agent is, for example, 0.1 to 10 moles, preferably 0.5 to 5 moles, and more preferably 0.8 to 1.2 moles.

[0135] The reaction may be carried out in the absence or presence of an inert solvent, such as water, alcohols, ethers such as cyclic ethers and chain ethers, and hydrocarbons such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.

[0136] Examples of alcohols include C 10 alcohols such as methanol, ethanol, and isopropanol. 1-6 Alcohol, etc.

[0137] Examples of cyclic ethers include dioxane and tetrahydrofuran (THF). Examples of chain ethers include dialkyl ethers such as diethyl ether and diisopropyl ether, and glycol ethers. Examples of glycol ethers include (poly)alkylene glycol monoalkyl ethers such as methyl cellosolve and methyl carbitol, and (poly)alkylene glycol dialkyl ethers such as dimethoxyethane.

[0138] Examples of aliphatic hydrocarbons include hexane and dodecane. Examples of alicyclic hydrocarbons include cyclohexane. Examples of aromatic hydrocarbons include benzene, toluene, and xylene.

[0139] The solvents may be used alone or in combination of two or more. Preferred solvents are ethers, and more preferred are cyclic ethers such as THF.

[0140] The reaction may be carried out under an inert gas atmosphere, for example, under an atmosphere of nitrogen gas or a rare gas such as helium or argon. The reaction temperature is, for example, 0 to 50° C., preferably 5 to 35° C. The reaction time is not particularly limited and may be, for example, about 1 to 48 hours.

[0141] After completion of the reaction, the reaction mixture may be separated and purified, if necessary, by a conventional separation and purification method, such as washing, extraction, filtration, dehydration, drying, concentration, decantation, recrystallization, reprecipitation, chromatography, or a combination thereof.

[0142] (Compound represented by formula (2)) In the compound represented by formula (2), when p1 and p2 are 1 or more, A 2a and A 2bThe alkylene oxide (alkylene carbonate or haloalkanol) can be added to the compound represented by formula (4) to form a linear or branched alkylene group. The addition reaction of the alkylene oxide (alkylene carbonate or haloalkanol) may be carried out by a conventional method, for example, a method similar to that described in WO 2013 / 022065, specifically, a method in which an alkylene oxide such as ethylene oxide is added to the compound represented by formula (4) in the presence of a base catalyst such as potassium hydroxide. 2a and A 2b and a method of reacting the corresponding alkylene oxide with the

[0143] Furthermore, when p1 and p2 are 0, that is, when the above-mentioned addition reaction is not carried out, the compound represented by formula (4) may be used as it is as the compound represented by formula (2) to prepare the di(meth)acrylate compound represented by formula (1).

[0144] (Preparation of di(meth)acrylate compound represented by formula (1)) The di(meth)acrylate compound represented by the formula (1) can be prepared by reacting the compound represented by the formula (2) (the compound represented by the formula (4) when p1 and p2 are 0) with the compound represented by the formulas (3a) and (3b) ((meth)acrylic acid or its ester-forming derivative). Unless otherwise specified in the present specification and claims, the term "ester-forming derivative" refers to an alkyl ester (or lower alkyl ester), specifically, a C ester such as a methyl ester or an ethyl ester. 1-4 It means alkyl esters and the like; acid halides such as acid chlorides; and acid anhydrides.

[0145] Examples of the compound represented by the formula (2) include compounds corresponding to the compounds specifically exemplified as the di(meth)acrylate compound represented by the formula (1).

[0146] In the formulas (3a) and (3b), X 1a and X 1bExamples of the halogen atom represented by X include a chlorine atom, a bromine atom, and an iodine atom, and preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom. 1a and X 1b The alkoxy group represented by the formula (I) is a lower alkoxy group, for example, a straight-chain or branched C alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, an s-butoxy group, or a t-butoxy group. 1-4 alkoxy groups, and preferably C groups such as methoxy groups. 1-2 is an alkoxy group. X 1a and X 1b is preferably a hydroxyl group.

[0147] Examples of the compounds represented by the formulas (3a) and (3b) include (meth)acrylic acid or anhydride thereof; (meth)acrylic acid halides such as (meth)acrylic acid chloride and (meth)acrylic acid bromide; (meth)acrylic acid alkyl esters, specifically (meth)acrylic acid C such as methyl (meth)acrylate, ethyl (meth)acrylate, and t-butyl (meth)acrylate. 1-4 Examples include alkyl esters. These compounds represented by the formulas (3a) and (3b) are commercially available products. Of the compounds represented by the formulas (3a) and (3b), (meth)acrylic acid is preferred. Although the compounds represented by the formulas (3a) and (3b) may be different compounds, they are preferably the same compound.

[0148] The total amount of the compounds represented by the formulas (3a) and (3b) is, for example, 1 to 10 mol, preferably 1.05 to 5 mol, more preferably 1.1 to 2 mol, and even more preferably 1.2 to 1.5 mol, relative to 1 mol of the hydroxyl groups in the compound represented by the formula (2).

[0149] In the formulas (3a) and (3b), X 1a and X 1bWhen is a halogen atom [when the compounds represented by the formulas (3a) and (3b) are (meth)acrylic acid halides], the reaction may be carried out in the presence of a base to trap the hydrogen halide produced by the reaction. The base can be broadly classified into, for example, inorganic bases and organic bases.

[0150] Examples of inorganic bases include metal hydroxides, specifically alkali metal or alkaline earth metal hydroxides such as sodium hydroxide and calcium hydroxide; metal carbonates, specifically alkali metal or alkaline earth metal carbonates such as sodium carbonate and calcium carbonate; and metal hydrogen carbonates, specifically alkali metal or alkaline earth metal hydrogen carbonates such as sodium hydrogen carbonate.

[0151] Examples of organic bases include amines, specifically trialkylamines such as triethylamine, aromatic tertiary amines such as benzyldimethylamine, and heterocyclic amines such as pyridine and N-methylmorpholine.

[0152] The base may be used alone or in combination of two or more. Among these bases, amines, for example, trialkylamines such as triethylamine, are preferred. The amount of the base used is not particularly limited, but is, for example, 1 to 2 moles, preferably 1.05 to 1.5 moles, and more preferably 1.1 to 1.2 moles per mole of the (meth)acrylic acid halide.

[0153] In addition, in the formulas (3a) and (3b), X 1a and X 1b When R is a hydroxyl group or an alkoxy group [when the compounds represented by formulas (3a) and (3b) are (meth)acrylic acid (or its anhydride) or (meth)acrylic acid alkyl esters], the reaction may be carried out using a conventional esterification catalyst. Examples of the catalyst include acid catalysts, base catalysts, and metal catalysts such as metal alkoxides, specifically titanium(IV) alkoxides such as titanium(IV) tetraisopropoxide. Of these catalysts, acid catalysts are preferred.

[0154] The acid catalyst is not particularly limited and may include inorganic acids, organic acids, Lewis acids such as boron trifluoride etherate and tin tetrachloride, and solid acid catalysts such as cation exchange resins. These acid catalysts may be used alone or in combination. These acid catalysts may also be hydrates.

[0155] Examples of the inorganic acid include strong acids, specifically sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, etc.; and homo- or heteropoly acids, specifically tungstophosphoric acid, molybdophosphoric acid, tungstosilicic acid, molybdosilicic acid, etc.

[0156] Examples of the organic acid include sulfonic acids, specifically, alkanesulfonic acids such as methanesulfonic acid and ethanesulfonic acid, fluorinated alkanesulfonic acids such as trifluoromethanesulfonic acid, and arenesulfonic acids such as p-toluenesulfonic acid. The acid catalyst is preferably an arenesulfonic acid such as p-toluenesulfonic acid monohydrate.

[0157] The proportion of the catalyst is not particularly limited, and is, for example, 0.001 to 1 mole, and preferably 0.01 to 0.5 mole, per mole of the compound represented by the formula (2).

[0158] The reaction may be carried out in the presence of a polymerization inhibitor. Alternatively, the polymerization inhibitor may be added after the reaction is complete. Examples of polymerization inhibitors include benzoquinone; hydroquinones such as hydroquinone, hydroquinone monomethyl ether (MEHQ), t-butylhydroquinone, and p-benzoquinone; catechols such as pt-butylcatechol and 2-methoxyphenol; amines such as N,N-diethylhydroxylamine; 1,1-diphenyl-2-picrylhydrazyl; tri-p-nitrophenylmethyl; and phenothiazine. The polymerization inhibitor may be used alone or in combination of two or more. Among these polymerization inhibitors, catechols such as 2-methoxyphenol are preferred.

[0159] The proportion of the polymerization inhibitor may be, for example, about 0.001 to 10 parts by mass relative to 100 parts by mass of the total amount of the compounds represented by the formulas (3a) and (3b), or may be, for example, about 0.0001 to 0.1 parts by mass relative to 100 parts by mass of the di(meth)acrylate compound represented by the formula (1) obtained by the reaction.

[0160] The reaction may be carried out in the presence of a solvent. Examples of solvents include hydrocarbons, specifically aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons, specifically methylene chloride, chloroform, 1,2-dichloroethane, and chlorobenzene; ethers, specifically dialkyl ethers such as diethyl ether, and cyclic ethers such as tetrahydrofuran (THF) and 1,4-dioxane; ketones, specifically acetone and methyl ethyl ketone; sulfoxides, specifically dimethyl sulfoxide; amides, specifically N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; and nitriles such as acetonitrile. The solvent may be used alone or in combination. Among these solvents, aromatic hydrocarbons such as toluene are preferred. The proportion of the solvent is not particularly limited, and may be, for example, about 10 to 1000 parts by mass, and preferably 50 to 150 parts by mass, relative to 100 parts by mass of the total amount of the compound represented by formula (2) and the compounds represented by formulas (3a) and (3b).

[0161] The reaction temperature and reaction time can be appropriately selected depending on the types of raw materials used, and when the compounds represented by formulas (3a) and (3b) are (meth)acrylic acid halides, the reaction temperature is, for example, -10 to 30°C, preferably 0 to 20°C, and more preferably 2 to 10°C. When the compounds represented by formulas (3a) and (3b) are (meth)acrylic acid (or its anhydride) or (meth)acrylic acid alkyl esters, the reaction temperature is, for example, 50 to 150°C, preferably 80 to 130°C, and more preferably 100 to 120°C. The reaction may be carried out at reflux temperature. The reaction time is not particularly limited and may be, for example, about 1 to 24 hours.

[0162] The reaction can be carried out in air or in an inert atmosphere such as nitrogen gas or a rare gas with stirring, and may be carried out under normal pressure, elevated pressure, or reduced pressure. In addition, in order to effectively prevent unintended polymerization during the reaction, the reaction may be carried out while blowing air into the reaction solution.

[0163] After completion of the reaction, the produced di(meth)acrylate compound represented by the formula (1) may be separated and purified by a conventional method, for example, a separation and purification means such as neutralization, washing, dehydration, filtration, adsorption, concentration, extraction, crystallization, recrystallization, reprecipitation, centrifugation, column chromatography, or a combination of these means.

[0164] [Curable composition and cured product thereof] The present disclosure encompasses a curable composition containing a di(meth)acrylate compound (also referred to as a first multifunctional (meth)acrylate) represented by formula (1) and a cured product thereof. The curable composition only needs to contain at least the first multifunctional (meth)acrylate, and may or may not contain other polymerization components, such as a second multifunctional (meth)acrylate different from formula (1) or a monofunctional polymerization component (or reactive diluent) such as a monofunctional (meth)acrylate.

[0165] (Second Multifunctional (Meth)acrylate) The second polyfunctional (meth)acrylate is not particularly limited as long as it is a compound having a plurality (two or more) of (meth)acryloyl groups. The number of (meth)acryloyl groups per molecule is, for example, 2 to 10, preferably 2 to 6, more preferably 2 to 4, particularly preferably 2 to 3, and particularly preferably 2.

[0166] Examples of the second polyfunctional (meth)acrylate include epoxy (meth)acrylates (vinyl ester resins) such as aliphatic epoxy (meth)acrylates, alicyclic epoxy (meth)acrylates, aromatic epoxy (meth)acrylates, and poly(meth)acrylates of novolac epoxy resins; urethane (meth)acrylates; polyester (meth)acrylates (poly(meth)acrylates of polyester polyols having two or more hydroxyl groups); alkylene glycol di(meth)acrylates; polyalkylene glycol di(meth)acrylates; di(meth)acrylates of alicyclic diols; di(meth)acrylates of biphenols or bisphenols or their alkylene oxide (alkylene carbonate or haloalkanol) adducts; and poly(meth)acrylates of low-molecular-weight polyol compounds having about 3 to 6 hydroxyl groups or their alkylene oxide (alkylene carbonate or haloalkanol) adducts. These second multifunctional (meth)acrylates may be used alone or in combination of two or more. Commercially available products may be used as these second multifunctional (meth)acrylates.

[0167] Examples of the aliphatic epoxy (meth)acrylate include di(meth)acrylates of (poly)alkylene glycol diglycidyl ethers such as di(meth)acrylate of 1,6-hexanediol diglycidyl ether and di(meth)acrylate of polypropylene glycol diglycidyl ether.

[0168] Examples of the alicyclic epoxy (meth)acrylate include C 1,4-cyclohexanedimethanol diglycidyl ether di(meth)acrylate.5-10 Examples include di(meth)acrylates of epoxy compounds having an aliphatic ring.

[0169] Examples of the aromatic epoxy (meth)acrylate include di(meth)acrylates of diglycidyl ethers of bisphenols or biphenols, or their alkylene oxide (alkylene carbonate or haloalkanol) adducts, such as di(meth)acrylate of bisphenol A diglycidyl ether. Examples of bisphenols include bisphenol A, bisphenol F, bisphenol AD, and bisphenol S. Examples of biphenols include p,p'-biphenol, m,m'-biphenol, and o,o'-biphenol.

[0170] Examples of the alkylene glycol di(meth)acrylate include C alkylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, etc. 2-10 Examples include alkylene glycol di(meth)acrylate.

[0171] Examples of the polyalkylene glycol di(meth)acrylate include di- to hexa-C di(meth)acrylates such as diethylene glycol di(meth)acrylate. 2-10 Examples include alkylene glycol di(meth)acrylate.

[0172] Examples of the di(meth)acrylate of the alicyclic diol include C di(meth)acrylate of 1,4-cyclohexanedimethanol. 5-10 Examples include di(meth)acrylates of diol compounds having an aliphatic ring.

[0173] In the di(meth)acrylates of biphenols or bisphenols or their alkylene oxide (alkylene carbonate or haloalkanol) adducts, examples of the biphenols or bisphenols include the biphenols or bisphenols exemplified in the section on aromatic epoxy (meth)acrylates, 9,9-bis[hydroxyaryl]fluorene, etc.

[0174] Examples of the poly(meth)acrylate of the low molecular weight polyol compound having about 3 to 6 hydroxyl groups or its alkylene oxide (alkylene carbonate or haloalkanol) adduct include glycerin tri(meth)acrylate, diglycerin tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and sorbitol tri- to hexa(meth)acrylate.

[0175] Among these second polyfunctional (meth)acrylates, di(meth)acrylates of biphenols or bisphenols or their alkylene oxide (alkylene carbonate or haloalkanol) adducts are preferred, and di(meth)acrylates of 9,9-bis[hydroxyaryl]fluorene represented by the following formula (7) or its alkylene oxide (alkylene carbonate or haloalkanol) adducts are even more preferred because they have an excellent balance of high refractive index, high heat resistance, flexibility (toughness), and high curability.

[0176] [ka]

[0177] (In the formula, Z 2a and Z 2b each independently represents an arene ring, R 5 represents a substituent, r represents an integer of 0 to 8, R 6a and R 6b each independently represents a substituent, s1 and s2 each independently represent an integer of 0 or more, A 4a and A 4b each independently represent a linear or branched alkylene group; t1 and t2 each independently represent an integer of 0 or greater; R 7a and R 7b each independently represents a hydrogen atom or a methyl group).

[0178] In the formula (7), Z 2a and Z 2b The arene ring represented by the formula (1) includes Z 1a and Z 1b Preferred rings include the arene rings exemplified as 2a and Z 2b C such as benzene ring, naphthalene ring, biphenyl ring 6-12 C rings such as arene rings, more preferably benzene rings and naphthalene rings 6-10 An arene ring, especially a benzene ring.

[0179] R 5 Examples of the substituent (non-reactive substituent or non-polymerizable substituent) represented by the formula (I) include hydrocarbon groups such as alkyl groups and aryl groups; cyano groups; and halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Examples of the alkyl groups include linear or branched C alkyl groups such as methyl groups, ethyl groups, propyl groups, isopropyl groups, n-butyl groups, and t-butyl groups. 1-6 Examples of the aryl group include a C alkyl group such as a phenyl group. 6-10 Examples include an aryl group.

[0180] When r is 1 or greater, the preferred group R 5is an alkyl group, a cyano group, or a halogen atom, more preferably an alkyl group, particularly a linear or branched C 1-4 Alkyl groups are preferred.

[0181] base R 5 The number of substitutions r is, for example, an integer of about 0 to 7, and preferred ranges are, in the following stepwise order, integers of 0 to 6, integers of 0 to 4, integers of 0 to 3, and integers of 0 to 2, more preferably 0 or 1, and particularly preferably 0. When r is 2 or more, two or more groups R 5 The types of groups R may be the same or different. 5 The substitution position of is not particularly limited, and is, for example, the 2- to 7-positions of the fluorene ring, preferably the 2-, 3- and / or 7-positions, and more preferably the 2- or 2,7-positions.

[0182] R 6a and R 6b Examples of the substituent (non-reactive substituent or non-polymerizable substituent) represented by the formula (1) include R 1a and R 1b Examples of the substituents include the same groups as those exemplified as the substituents.

[0183] These groups R 6a and R 6b Among these, representative examples include hydrocarbon groups, alkoxy groups, acyl groups, nitro groups, cyano groups, and substituted amino groups. When s1 is 1 or more, preferred groups R 6a The alkyl group, aryl group, and alkoxy group are specifically linear or branched C 1-6 Linear or branched C such as alkyl group or methoxy group 1-4 Alkoxy groups are preferred, among which alkyl and aryl groups are preferred, and in particular, straight-chain or branched C C groups such as methyl groups are preferred. 1-4 C such as alkyl group and phenyl group 6-10 An aryl group is preferred. 6b The same applies to the group R 6a is an aryl group, the group R 6a are rings Z 2aR may form the ring-assembled arene ring. 6b and Z 2b The same is true for .

[0184] base R 6a and R 6b The substitution numbers s1 and s2 of the ring Z 2a or Z 2b The integer can be appropriately selected depending on the type of the group, for example, an integer of about 0 to 8, preferably an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2, in the following stepwise order, with 0 or 1 being preferred, and 0 being particularly preferred.

[0185] Although s1 and s2 may be different from each other, they are preferably the same. 6a The types of s2 and R may be the same or different. 6b The same applies to the group R 6a and R 6b The types of groups R may be the same or different. 6a and R 6b The substitution position of ring Z is not particularly limited. 2a and Z 2b and the ether bond (-O-) and the 9-position of the fluorene ring, and 2a and Z 2b In the formula (I), it is preferable that the substituent is at the ortho position (the carbon atom adjacent to the bonding position of the ether bond) relative to the ether bond (—O—).

[0186] A 4a and A 4b Examples of the linear or branched alkylene group represented by the formula (1) include A 2a and A 2b The alkylene groups exemplified as A are similar to those in preferred embodiments, and an ethylene group is particularly preferred. 4a and A 4b The types may be different from each other, but are preferably the same.

[0187] Oxyalkylene group (OA 4a ) and (OA 4b The repeating numbers t1 and t2 of the polyoxyalkylene group [-(OA) can be selected from the range of about 0 to 20, and preferred ranges for applications where high refractive index and heat resistance are important are 0 to 15, 0 to 10, 0 to 6, and 0 to 2, particularly 0 to 1, in the following stepwise order. Preferred ranges for applications where low viscosity or flexibility (toughness) are important are 1 to 10, 3 to 8, and 4 to 7, particularly 5 to 6, in the following stepwise order. When t1 is 2 or more, the polyoxyalkylene group [-(OA) 4a ) t1 -] 2 or more A's 4a The types of t2 and A may be different from each other, but are preferably the same. 4b The same is true for .

[0188] Furthermore, t1 and t2 may be the same or different from each other. The repeating numbers t1 and t2 may be average values ​​(or arithmetic mean values), i.e., average numbers of moles added, and the range thereof, including preferred embodiments, is the same as the range of integers described above.

[0189] The total number of repeating numbers t1 and t2 is determined by the number of oxyalkylene groups (OA) in one molecule of the di(meth)acrylate compound represented by the formula (7). 4a ) and (OA 4b ) (or the average of the total number of moles added), and may be simply referred to as t1+t2. t1+t2 can be selected, for example, from a range of about 0 to 30. For applications where high refractive index and heat resistance are important, preferred ranges are 0 to 20, 0 to 12, and 0 to 4, particularly 0 to 2, in the following stepwise order. For applications where low viscosity or flexibility (toughness) are important, preferred ranges are 2 to 20, 6 to 16, and 8 to 14, particularly 10 to 12, in the following stepwise order. t1+t2 may be an integer as described above, but it may also be the average of the total number of moles added, and its range, including preferred embodiments, is the same as the range of integers described above. t1+t2 can be measured in accordance with the method for measuring p1+p2 in formula (1) above.

[0190] If the value of t1, t2, or t1+t2 is too large, it may be difficult to improve the refractive index or heat resistance, and if it is too small, it may be difficult to improve the handleability or flexibility.

[0191] The group [-O-(A 4a O) t1 -] and [-O-(A 4b O) t2 -] Ring Z 2a and Z 2b The substitution position of the group [—O—(A 4a O) t1 -] is substituted at the ring Z 2a When the ring Z is a benzene ring, it is preferably at the 2-, 3- or 4-position of the phenyl group bonded to the 9-position of the fluorene ring, more preferably at the 3- or 4-position, and even more preferably at the 4-position. 2a When is a naphthalene ring, the group [-O-(A 4a O) t1 The substitution position of -] is preferably any one of the 5th to 8th positions of the naphthyl group bonded to the 9th position of the fluorene ring, and in particular, the 9th position of the fluorene ring is substituted with the 1st or 2nd position of the naphthalene ring (substitution in a 1-naphthyl or 2-naphthyl relationship), and the substitution is preferably in a 1,5-position or 2,6-position relationship relative to this substitution position, particularly in a 2,6-position relationship. 2a is a ring-assembled arene ring, the group [-O-(A 4a O) t1 The substitution position of -] is not particularly limited, and may be, for example, 2a is a biphenyl ring (or ring Z 2a is a benzene ring, s1 is 1, R 6a is a phenyl group), the 9-position of the fluorene ring is bonded to the 3-position of the biphenyl ring, and the group [-O-(A 4a O) t1 -] is preferably substituted at the 6- or 4'-position of the biphenyl ring, particularly at the 6-position.

[0192] R 7a and R 7b R may be either a hydrogen atom or a methyl group, but is preferably a hydrogen atom in terms of ease of improving reactivity (or curability) and refractive index.7a and R 7b The types may be the same or different from each other, and are preferably the same.

[0193] Representative di(meth)acrylate compounds represented by the formula (7) include Z 2a and Z 2b C 6-12 arene ring, R 6a and R 6b represents a hydrocarbon group, s1 and s2 are integers of 0 to 2, and A 4a and A 4b is linear or branched C 2-4 Examples include di(meth)acrylate of 9,9-bis[hydroxyaryl]fluorene [or its alkylene oxide (alkylene carbonate or haloalkanol) adduct], which is an alkylene group and in which t1 and t2 are integers of 0 to 10.

[0194] Representative examples of the 9,9-bis[hydroxyaryl]fluorene constituting the di(meth)acrylate compound represented by formula (7) include 9,9-bis(hydroxyphenyl)fluorene, 9,9-bis(alkyl-hydroxyphenyl)fluorene, 9,9-bis(aryl-hydroxyphenyl)fluorene, and 9,9-bis(hydroxynaphthyl)fluorene.

[0195] Examples of 9,9-bis(hydroxyphenyl)fluorene include 9,9-bis(4-hydroxyphenyl)fluorene.

[0196] Examples of the 9,9-bis(alkyl-hydroxyphenyl)fluorene include 9,9-bis[(mono- or di-)C]fluorene such as 9,9-bis(4-hydroxy-3-methylphenyl)fluorene and 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene. 1-4 alkyl-hydroxyphenyl]fluorene and the like.

[0197] Examples of 9,9-bis(aryl-hydroxyphenyl)fluorene include 9,9-bis(C 6-10 aryl-hydroxyphenyl)fluorene.

[0198] Examples of 9,9-bis(hydroxynaphthyl)fluorene include 9,9-bis(6-hydroxy-2-naphthyl)fluorene and 9,9-bis(5-hydroxy-1-naphthyl)fluorene.

[0199] Representative alkylene oxides (alkylene carbonates or haloalkanols) that may be added to the 9,9-bis[hydroxyaryl]fluorene include C alkylene oxides such as ethylene oxide and propylene oxide. 2-3 Alkylene oxide (C 2-3 Alkylene carbonate or C 2-3 The number of moles added (or the average number of moles added) t1+t2 of the alkylene oxide (alkylene carbonate or haloalkanol) may be, for example, about 0 to 20, and is preferably 0 to 2 when a high refractive index or heat resistance is important, and is preferably 9 to 13 when a low viscosity or flexibility (toughness) is important.

[0200] These di(meth)acrylate compounds represented by the formula (7) can be used alone or in combination of two or more. 2a and Z 2b is a benzene ring, and A 4a and A 4b is linear or branched C 2-3 A compound which is an alkylene group and in which t1+t2 is 10 to 12 is preferred.

[0201] When the curable composition contains a second multifunctional (meth)acrylate, the proportion of the di(meth)acrylate compound represented by the formula (7) can be selected, for example, from a range of about 30 to 100% by mass relative to the entire second multifunctional (meth)acrylate.Preferred ranges are 50% by mass or more, 70% by mass or more, 90% by mass or more, in the following stepwise order, and more preferably substantially 100% by mass. In other words, it is preferable that the second multifunctional (meth)acrylate contains only the di(meth)acrylate compound represented by the formula (7).

[0202] Furthermore, when the curable composition contains the compound represented by formula (7), the ratio of the compound represented by formula (1) to the compound represented by formula (7) may be selected from the range of about 10 / 90 to 90 / 10, for example, about 20 / 80 to 80 / 20, with the former / latter (mass ratio) being preferably 30 / 70 to 70 / 30. From the viewpoint of adjusting the balance of refractive index, heat resistance, flexibility (or toughness), curability, and the like depending on the application, the ratio is preferably 50 / 50 to 80 / 20, more preferably 60 / 40 to 75 / 25, for applications where a higher refractive index is important, and is preferably 20 / 80 to 50 / 50, more preferably 25 / 75 to 40 / 60, for applications where flexibility (toughness) and / or handleability (viscosity or solubility) are important. If the proportion of the compound represented by formula (7) is too large, the refractive index may not be sufficiently high, and if it is too small, it may be difficult to improve the flexibility (toughness) and / or handling properties (viscosity or solubility).

[0203] The proportion of the first multifunctional (meth)acrylate represented by formula (1) relative to the total amount of the first and second multifunctional (meth)acrylates can be, for example, 10% by mass or more, specifically, selected from a range of about 30 to 100% by mass. Preferred ranges are, in the following stepwise order, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, and even more preferably 90% by mass or more. It is particularly preferred that the proportion be substantially 100% by mass, i.e., that the first multifunctional (meth)acrylate is the only multifunctional polymerization component. The proportion may be, for example, selected from a range of about 60 to 99% by mass, specifically, 80 to 97% by mass. If the proportion of the first multifunctional (meth)acrylate is too low, the refractive index and heat resistance may be reduced.

[0204] (Monofunctional polymerization component) The monofunctional polymerization component (or reactive diluent) may be a compound having one polymerizable group (or polymerizable unsaturated bond), such as a vinyl group, an alkenyl group such as an allyl group, or a (meth)acryloyl group. Specific examples include monofunctional vinyl monomers and monofunctional (meth)acrylic monomers. Examples of monofunctional vinyl monomers include α-olefin monomers such as ethylene and propylene; styrene monomers such as styrene, α-methylstyrene, and vinyltoluene; vinyl ester monomers such as vinyl acetate; and N-vinylpyrrolidone. Examples of monofunctional (meth)acrylic monomers include (meth)acrylic acid; (meth)acrylamide; N-substituted (meth)acrylamides such as N-methylol(meth)acrylamide and N,N-dimethyl(meth)acrylamide; (meth)acrylonitrile; and monofunctional (meth)acrylates.

[0205] These monofunctional polymerization components can be used alone or in combination of two or more. Among these monofunctional polymerization components, monofunctional (meth)acrylic monomers, particularly monofunctional (meth)acrylates, are preferred.

[0206] Examples of the monofunctional (meth)acrylate include aliphatic monofunctional (meth)acrylate, alicyclic monofunctional (meth)acrylate, aromatic monofunctional (meth)acrylate, and sulfur atom-containing monofunctional (meth)acrylate. These monofunctional (meth)acrylates can be used alone or in combination of two or more.

[0207] Examples of the aliphatic monofunctional (meth)acrylate include C acrylates such as methyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. 1-20 Examples include alkyl(meth)acrylates.

[0208] Examples of the alicyclic monofunctional (meth)acrylate include C 111 (meth)acrylate, such as cyclohexyl (meth)acrylate. 5-10 Examples include bridged cyclic (meth)acrylates such as cycloalkyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and isobornyl (meth)acrylate.

[0209] Examples of aromatic monofunctional (meth)acrylates include aryl (meth)acrylates such as phenyl (meth)acrylate; aralkyl (meth)acrylates such as benzyl (meth)acrylate; and aryloxyalkyl (meth)acrylates, specifically, C 2 alkyl (meth)acrylates such as 2-phenoxyethyl (meth)acrylate, 2-(2-naphthoxy)ethyl (meth)acrylate, and 2-(o-phenylphenoxy)ethyl (meth)acrylate. 6-12 Aryloxy C 2-4 Alkyl(meth)acrylates; mono(meth)acrylates of bisphenols or biphenols (or alkylene oxide adducts thereof), such as the mono(meth)acrylate of an ethylene oxide adduct of bisphenol A; and (meth)acrylates having a fluorene skeleton, such as 9-(meth)acryloyloxymethylfluorene.

[0210] Examples of the monofunctional (meth)acrylate containing a sulfur atom include alkylthio(meth)acrylate, arylthio(meth)acrylate, aralkylthio(meth)acrylate, and arylthioalkyl(meth)acrylate. Examples of the alkylthio(meth)acrylate include C alkylthio(meth)acrylates such as methylthio(meth)acrylate. 1-6 Examples of the arylthio(meth)acrylate include C thio(meth)acrylates such as phenylthio(meth)acrylate. 6-10 Examples of aralkylthio(meth)acrylates include C thio(meth)acrylates such as benzylthio(meth)acrylate. 6-10 Aryl C 1-6 Examples of the arylthioalkyl(meth)acrylate include C alkylthio(meth)acrylates such as phenylthioethyl(meth)acrylate. 6-10 Arylthio C 2-4 Examples include alkyl(meth)acrylates.

[0211] Among these monofunctional (meth)acrylates, aromatic monofunctional (meth)acrylates are preferred because they can easily be made low in viscosity while maintaining a high refractive index, and among these, compounds represented by the following formula (8) are preferred.

[0212] [ka]

[0213] (wherein Ar represents an arene ring, R 8 represents a substituent, u represents an integer of 0 or more, A 5 represents a linear or branched alkylene group, v represents an integer of 0 or more, R 9 indicates a hydrogen atom or a methyl group).

[0214] In the formula (8), the arene ring represented by Ar includes Z in the formula (1). 1aand Z 1b Preferred rings Ar include C arenes such as benzene rings, naphthalene rings, and biphenyl rings. 6-12 An arene ring is more preferred, and a benzene ring or a biphenyl ring is more preferred. A biphenyl ring is particularly preferred because it has a high refractive index and is excellent in curability when combined with the (meth)acrylate represented by the formula (1).

[0215] R 8 Examples of the substituent represented by the formula (I) include hydrocarbon groups, and preferably alkyl groups. Examples of the alkyl group include linear or branched C alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, octyl group, 2-ethylhexyl group, and decyl group. 1-12 Preferably, the alkyl group is a linear or branched C 1-9 Alkyl groups, linear or branched C 1-6 Alkyl groups, linear or branched C 1-4 It is an alkyl group.

[0216] base R 8 The number of substitutions u may be an integer of 0 or 1 or more, and can be selected depending on the type of ring Ar, and is, for example, an integer of about 0 to 4, preferably an integer of about 0 to 2, more preferably 0 or 1, and particularly preferably 0. When u is 2 or more, two or more groups R 8 The types of groups R may be the same or different. 8 The substitution position of is not particularly limited.

[0217] A 5 Examples of the linear or branched alkylene group represented by the formula (1) include A 2a and A 2b The alkylene groups exemplified above are similar to the alkylene groups exemplified above, including preferred embodiments, and an ethylene group is particularly preferred.

[0218] Oxyalkylene group (OA 5The repeat number v of the polyoxyalkylene group [-(OA) can be selected, for example, from about 0 to 10, and is preferably 0 to 4, 1 to 3, 1 to 2, and particularly 1 in the following stepwise order. If v is too large, it may be difficult to improve the refractive index and heat resistance, and if v is too small, it may be difficult to improve the handling properties. When v is 2 or more, 5 ) v -] 2 or more A's 5 The types may be different from each other, but are preferably the same.

[0219] R 9 may be either a hydrogen atom or a methyl group, but is preferably a hydrogen atom in terms of ease of improving the reactivity (or curability) and refractive index.

[0220] Group [-O-(A 5 O) v -CO-CR 9 The bonding position of the group [-O-(A 5 O) v -CO-CR 9 =CH2] is preferably bonded.

[0221] Representative compounds represented by the formula (8) include those in which Ar is a C ring such as a benzene ring, a naphthalene ring, or a biphenyl ring. 6-12 arene ring, R 8 is a hydrocarbon group such as an alkyl group, u is an integer of 0 to 2, and A 5 is linear or branched C 2-4 and a compound in which Ar is an alkylene group and v is an integer of 1 to 4. Specific examples of the compound include a compound in which Ar is a benzene ring and A 5 is linear or branched C 2-3 A compound in which v is an alkylene group and v is an integer of 1 to 2, for example, a phenoxy C such as 2-phenoxyethyl (meth)acrylate 2-3 Alkyl (meth)acrylate, etc.; Ar is a biphenyl ring, and A 5 is linear or branched C 2-3A compound in which v is an alkylene group and v is an integer of 1 to 2, for example, biphenylyloxy C such as 2-(o-phenylphenoxy)ethyl (meth)acrylate 2-3 Alkyl (meth)acrylate, etc.; Ar is a naphthalene ring, and A 5 is linear or branched C 2-3 A compound in which v is an alkylene group and v is an integer of 1 to 2, for example, a naphthoxy C such as 2-(2-naphthoxy)ethyl (meth)acrylate 2-3 Alkyl (meth)acrylates and the like.

[0222] These compounds represented by the formula (8) can be used alone or in combination of two or more. Among them, biphenylyloxy C is preferred because it easily achieves both a high refractive index and curability. 2-3 Alkyl (meth)acrylates are preferred.

[0223] When the curable composition contains the compound represented by formula (8), the ratio of the compound represented by formula (1) to the compound represented by formula (8) may be selected from a range of about 10 / 90 to 95 / 5 (former / latter by mass), for example, about 30 / 70 to 90 / 10, and preferably the following stepwise ratios: 50 / 50 to 85 / 15, 60 / 40 to 80 / 20, and 65 / 35 to 75 / 25. If the ratio of the compound represented by formula (8) is too high, the refractive index and curability may decrease, and if it is too low, the handleability may not be sufficiently improved.

[0224] When the curable composition contains a compound represented by formula (8), the proportion of the compound represented by formula (8) relative to the total amount of monofunctional (meth)acrylates can be selected, for example, from a range of about 30 to 100% by mass, with preferred ranges being 50% by mass or more, 70% by mass or more, 90% by mass or more, and more preferably substantially 100% by mass, i.e., the monofunctional (meth)acrylate is preferably composed solely of the compound represented by formula (8). When the curable composition contains a monofunctional (meth)acrylate, the proportion of the monofunctional (meth)acrylate relative to the total amount of monofunctional polymerization components can be selected, for example, from a range of about 30 to 100% by mass, with preferred ranges being 50% by mass or more, 70% by mass or more, 90% by mass or more, and more preferably substantially 100% by mass.

[0225] When the curable composition contains a monofunctional polymerization component, the ratio of the monofunctional polymerization component to the total amount of polyfunctional (meth)acrylates (total amount of the first and second polyfunctional (meth)acrylates) is, for example, about 10 / 90 to 95 / 5 by mass, preferably 30 / 70 to 90 / 10, 50 / 50 to 85 / 15, or 60 / 40 to 80 / 20. The ratio may be the ratio of the total amount of polyfunctional (meth)acrylates to the monofunctional (meth)acrylate, or the ratio of the total amount of polyfunctional (meth)acrylates to the compound represented by formula (8). If the ratio of the monofunctional polymerization component, particularly the monofunctional (meth)acrylate such as the compound represented by formula (8), is too high, the refractive index may decrease, while if it is too low, it may be difficult to improve the handling properties (low viscosity).

[0226] (components other than polymerized components) The curable composition may further contain a polymerization initiator, a solvent, an additive, and the like in addition to the polymerization component (or the monomer component).

[0227] The polymerization initiator may be a thermal polymerization initiator (thermal radical generator) or a photopolymerization initiator (photoradical generator).

[0228] Examples of thermal polymerization initiators include organic peroxides and azo compounds. Examples of organic peroxides include dialkyl peroxides such as di-t-butyl peroxide; diacyl peroxides such as lauroyl peroxide and benzoyl peroxide; peracids (or peresters) such as t-butyl hydroperoxide, cumene hydroperoxide, and t-butyl peracetate; ketone peroxides; peroxycarbonates; and peroxyketals. Examples of azo compounds include azonitrile compounds such as 2,2'-azobis(isobutyronitrile), azoamide compounds, and azoamidine compounds. These thermal polymerization initiators can be used alone or in combination of two or more.

[0229] Examples of photopolymerization initiators include benzoins, specifically benzoin alkyl ethers such as benzoin and benzoin ethyl ether; acetophenones such as acetophenone and 2-hydroxy-2-methyl-1-phenylpropan-1-one; aminoacetophenones such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoaminopropanone-1; anthraquinones such as anthraquinone and 2-methylanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; and xanthones. These photopolymerization initiators may be used alone or in combination of two or more.

[0230] The proportion of the polymerization initiator (thermal and / or photopolymerization initiator) is, for example, 0.1 to 15 parts by mass, preferably 0.5 to 10 parts by mass, more preferably 1 to 8 parts by mass, and even more preferably 2 to 5 parts by mass, relative to 100 parts by mass of the total amount of the polymerization components.

[0231] The photopolymerization initiator may be combined with a photosensitizer. Typical examples of the photosensitizer include tertiary amines, such as trialkylamines; trialkanolamines such as triethanolamine; dialkylaminobenzoic acid alkyl esters, specifically, N,N-dimethylaminobenzoic acid ethyl esters such as p-(dimethylamino)benzoic acid ethyl esters, N,N-dimethylaminobenzoic acid amyl esters such as p-(dimethylamino)benzoic acid amyl esters; bis(dialkylamino)benzophenones such as 4,4-bis(diethylamino)benzophenone; and dialkylaminobenzophenones such as 4-(dimethylamino)benzophenone. These photosensitizers may be used alone or in combination of two or more.

[0232] The proportion of the photosensitizer is, for example, 1 to 200 parts by mass, preferably 5 to 150 parts by mass, and more preferably 10 to 100 parts by mass, relative to 100 parts by mass of the polymerization initiator.

[0233] The curable composition may not contain a solvent, but since the di(meth)acrylate compound represented by the formula (1) has unexpectedly high solubility, a solvent may be contained as necessary to adjust handling. The solvent is not particularly limited, and examples thereof include hydrocarbons, specifically, aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons, specifically, methylene chloride, chloroform, 1,2-dichloroethane, and chlorobenzene; ethers, specifically, chain ethers such as diethyl ether, and cyclic ethers such as tetrahydrofuran and 1,4-dioxane; ketones, specifically, dialkyl ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK); and cyclohexanone. Examples of suitable solvents include cyclic ketones such as methyl acetate, ethyl acetate, and butyl acetate; glycol ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) and diethylene glycol monobutyl ether acetate (poly)alkylene glycol monoalkyl ether acetates; sulfoxides such as dimethyl sulfoxide; amides such as dimethylformamide (DMF), dimethylacetamide, and N-methyl-2-pyrrolidone; and nitriles such as acetonitrile. These solvents can be used alone or in combination as a mixed solvent of two or more. Among these solvents, hydrocarbons, ketones, esters, glycol ether acetates, and amides are preferred, and aromatic hydrocarbons, ketones, acetate esters, and amides are preferred.

[0234] The proportion of the solvent is not particularly limited, and the solvent may be contained so that the concentration of the solid content (components other than the solvent) is, for example, about 0.1 to 50 mass%, specifically about 20 to 50 mass%, preferably 25 to 40 mass%, and more preferably 30 to 35 mass%, relative to the entire curable composition.

[0235] The curable composition may contain conventional additives such as colorants, stabilizers, fillers, antistatic agents, flame retardants, surfactants, plasticizers, curing agents, and polymerization inhibitors. Examples of the stabilizers include heat stabilizers, antioxidants, and ultraviolet absorbers. These additives can be used alone or in combination of two or more.

[0236] The total proportion of the additives is, for example, about 30% by mass or less, preferably 20% by mass or less, 10% by mass or less, and 5% by mass or less, stepwise, relative to the total curable composition. The proportion may be 0.001 to 15% by mass, specifically 0.01 to 3% by mass.

[0237] (cured product) The curable composition of the present disclosure can be easily cured by applying active energy (or active energy rays) to produce a cured product. The active energy can be thermal energy and / or light energy, such as ultraviolet light or X-rays.

[0238] When heat treatment is carried out using thermal energy, the heating temperature is, for example, 50 to 200°C, preferably 60 to 150°C, and more preferably 70 to 120°C.

[0239] When light energy such as ultraviolet light is used for light irradiation, the amount of light irradiation energy can be appropriately selected depending on the application, for example, 50 to 10,000 mJ / cm 2 , preferably 70 to 8000 mJ / cm 2 , and more preferably 100 to 5000 mJ / cm 2 , especially 500-3000mJ / cm 2 is.

[0240] The shape of the cured product is not particularly limited, and may be a three-dimensional cured product such as a lens or tube; a two-dimensional cured product (or cured film) such as a film, sheet, or plate; or a one-dimensional cured product such as a line, fiber, or rod.

[0241] The method for producing the cured product is not particularly limited, and for example, the curable composition may be molded or poured (injected) into a predetermined mold depending on the shape of the cured product, followed by a curing treatment (heating and / or light irradiation). Furthermore, in the case of a two-dimensional cured product, the curable composition may be applied to a substrate or base, for example, a metal such as aluminum; an inorganic material or ceramic such as titanium oxide, glass, or quartz; an organic material or plastic such as a cyclic olefin resin or polycarbonate resin; or a porous body such as wood, to form a film-like coating (or thin film), followed by a curing treatment.

[0242] The cured product of the present disclosure exhibits a high refractive index because it is formed from the di(meth)acrylate compound represented by formula (1). Therefore, the refractive index nD of the cured product at a temperature of 25°C and a wavelength of 589 nm may be, for example, about 1.6 to 1.8, and preferred ranges are the following stepwise ranges: 1.63 to 1.77, 1.65 to 1.75, 1.66 to 1.74, 1.67 to 1.73, 1.68 to 1.72, 1.685 to 1.715, 1.69 to 1.71, and 1.695 to 1.705.

[0243] The refractive index nD before curing (refractive index of the curable composition at a temperature of 25°C and a wavelength of 589 nm) may be, for example, about 1.59 to 1.8, and preferred ranges are the following stepwise ranges: 1.6 to 1.77, 1.63 to 1.75, 1.65 to 1.72, 1.66 to 1.7, 1.665 to 1.695, 1.67 to 1.69, and 1.675 to 1.685.

[0244] The cured product also has high heat resistance, and the 5% mass loss temperature may be, for example, about 200 to 500°C, with preferred ranges being the following stepwise ranges: 300 to 450°C, 330 to 430°C, 340 to 420°C, 350 to 410°C, 360 to 400°C, 365 to 395°C, 370 to 390°C, and 375 to 385°C.

[0245] The cured product has a high refractive index and a high 5% mass loss temperature, yet unexpectedly exhibits a low glass transition temperature Tg, and appears to have relatively flexible properties (or toughness). Therefore, the glass transition temperature Tg of the cured product may be, for example, about -30 to 100°C, and preferred ranges are -10 to 70°C, 0 to 50°C, 5 to 40°C, 10 to 35°C, 15 to 30°C, and 20 to 25°C, in the following stepwise order.

[0246] The viscosity of the curable composition at 25°C may be, for example, about 10 to 1,000,000 mPa·s, preferably 30 to 100,000 mPa·s, and more preferably 50 to 60,000 mPa·s.

[0247] Furthermore, as described above, the di(meth)acrylate compound represented by formula (1) exhibits excellent solubility, and therefore the viscosity of the curable composition can be adjusted depending on the application, etc., using a solvent, and a highly uniform coating film or cured product can be formed. Therefore, a cured product (or cured film) having a two-dimensional structure such as a film can be easily formed by a conventional coating method, and even a thin cured product having a film thickness of, for example, about 50 nm to 300 μm, for example, about 1 μm or less, preferably 80 to 200 nm, and more preferably 100 to 150 nm, can be efficiently and easily formed.

[0248] In this specification and claims, the refractive index, 5% mass loss temperature, glass transition temperature, viscosity of the curable composition, and film thickness of the cured product (cured film) can be measured by the methods described in the examples below. [Example]

[0249] The present disclosure will be described in more detail below based on examples, but the present disclosure is not limited to these examples. Details of raw materials, evaluation methods, etc. are shown below.

[0250] [Raw materials] DNPOA: 9,9-bis(3-acryloyloxypropyl)-2,7-di(2-naphthyl)fluorene, prepared in Example 1 below. BNEFA: 9,9-bis[6-(2-acryloyloxyethoxy)-2-naphthyl]fluorene, prepared in Comparative Example 1 below. BPEFA: 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, manufactured by Osaka Gas Chemicals Co., Ltd. (Comparative Example 2 described later) BPEF-9EOA: a diacrylate adduct in which an average of 9 moles of ethylene oxide (EO) is added to 1 mole of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (or BPEF), prepared in accordance with Reference Example 4 of JP-A 2013-053310. POA: 2-phenoxyethyl acrylate, "Light Acrylate PO-A" manufactured by Kyoeisha Chemical Co., Ltd. OPPEOA: o-phenylphenoxyethyl acrylate, manufactured by Nippon Kayaku Co., Ltd.

[0251] [Evaluation method] (HPLC) The HPLC purity [area %] of the sample was calculated by high performance (or high speed) liquid chromatography (HPLC) using the following measuring equipment and conditions.

[0252] Equipment: Hitachi High-Technologies Corporation "L-2000" Column: Imtakt "Cadenza CL-C18 (3 μm) 3.0 × 250 mm" Guard column: Imtakt GCCD0S Detector: L-2420 UV-VIS detector (D2 lamp, 254 nm) Mobile phase: acetonitrile / distilled water (volume ratio) = 90 / 10 (Kanto Chemical Co., Ltd., LC grade) Flow rate: 0.5mL / min

[0253] (FD-MS) Mass spectrometry (MS) was performed using the following measuring equipment and conditions.

[0254] Equipment used: “JMS-T200GC” manufactured by JEOL Ltd. Ionization method: FD (field desorption) Emitter: Carbon Emitter current: 0~50mA (25mA / min).

[0255] ( 1 H-NMR) The sample was dissolved in a heavy solvent (CDCl3 or DMSO-d6) containing tetramethylsilane as an internal standard, and the NMR spectra were analyzed using a nuclear magnetic resonance spectrometer (BRUKER "AVANCE III HD"). 1 H-NMR spectrum was measured.

[0256] (Melting Point) Measurements were carried out using a differential scanning calorimeter (SII Nanotechnology Inc., "EXSTAR DSC6200") under a nitrogen atmosphere at a temperature range of 30 to 220°C with a heating rate of 10°C / min.

[0257] (5% mass reduction temperature) Using a thermogravimetry-differential thermal analyzer (TG-DTA) (TG / DTA6200 manufactured by SII NanoTechnology Inc.), the temperature at which the sample lost 5% by mass was measured under a nitrogen atmosphere at a heating rate of 10°C / min. The sample (cured product) was prepared as follows.

[0258] That is, 3 parts by mass of Irgacure 184 (manufactured by BASF Japan Ltd.) as a photopolymerization initiator was added to 100 parts by mass of the acrylate compound (polymerizable component) shown in Table 1 or 3 collected in a brown bottle, and the mixture was heated to 120°C to dissolve, thereby obtaining a curable composition. The obtained curable composition was irradiated with UV (500 mJ / cm 2 ) was repeated four times to prepare a cured product.

[0259] (glass transition temperature Tg) Measurement was performed using a differential scanning calorimeter ("EXSTAR6000 DSC6220 ASD-2" manufactured by SII NanoTechnology Inc.) in a nitrogen gas atmosphere at a temperature increase rate of 10°C / min. The sample (cured product) used was prepared in the same manner as the sample (cured product) used to measure the 5% mass loss temperature.

[0260] (Refractive index nD before curing) The refractive index before curing was measured at a temperature of 25° C. and a wavelength of 589 nm (D-line). In Example 1 and Comparative Examples 1 to 4, a multi-wavelength Abbe refractometer (DR-M2 (circulating constant temperature water bath 60-C3) manufactured by Atago Co., Ltd.) was used as the refractometer, and in Examples 2 to 10, a digital refractometer (RX-7000i manufactured by Atago Co., Ltd.) was used.

[0261] The refractive index of DNFDP-m obtained in Example 1 was calculated by dissolving the sample in chloroform to prepare solutions with concentrations of 7.67% by mass and 16.8% by mass, and then measuring the refractive index of the resulting solutions to create a calibration curve (approximate straight line), and extrapolating the concentration to 100% by mass.

[0262] The refractive index of the DNPOA obtained in Example 1 was calculated by dissolving the sample in toluene to prepare solutions with concentrations of 25.0% by mass and 48.7% by mass, and then measuring the refractive index of the resulting solutions to create a calibration curve (approximate straight line), and extrapolating the concentration to 100% by mass.

[0263] The refractive index of the BNEFA obtained in Comparative Example 1 was also calculated by extrapolating the concentration to 100% by mass based on a calibration curve (an approximate straight line using the least squares method) created by measuring the refractive index of multiple toluene solutions with different concentrations.

[0264] (Refractive index nD of the cured product (cured film) and film thickness) The refractive index of the cured product was measured for the cured film obtained by photocuring the sample at a temperature of 25°C and a wavelength of 589 nm (D-line). The method for preparing the sample (cured film) and the measuring device are described below.

[0265] In Example 1, 3 parts by mass of Irgacure 184 (manufactured by BASF Japan Ltd.) as a photopolymerization initiator was added to 100 parts by mass of DNPOA collected in a brown bottle, and the mixture was diluted with toluene. This diluted solution (curable composition) was dropped onto the surface of a silicon wafer of approximately 3 cm x 3 cm and spin-coated (1000 rpm, 30 seconds) to form a thin film, which was then irradiated with UV (500 mJ / cm). 2 ) to prepare a cured film, and the film thickness and refractive index nD of the obtained cured film were measured using a high-speed spectroscopic ellipsometer ("M-2000" manufactured by JA Woollam).

[0266] In Comparative Examples 2 to 4 and Examples 5 and 8 to 10, 3 parts by mass of Irgacure 184 (manufactured by BASF Japan Ltd.) was added as a photopolymerization initiator to 100 parts by mass of the acrylate compound (polymerizable component) shown in Table 1 or 3 collected in a brown bottle, and the mixture was heated to melt and mix. The obtained curable composition was applied to a TAC (cellulose acetate) film with an applicator to a film thickness of 200 to 400 μm, and the obtained coating film was irradiated with UV (500 mJ / cm 2 ) was performed once to prepare a cured film, and the refractive index nD of the obtained cured film was measured using a multi-wavelength Abbe refractometer ("DR-M2 (circulating constant temperature water bath 60-C3)" manufactured by Atago Co., Ltd.), and the film thickness was measured using "MDQ-30" manufactured by Mitutoyo Corporation.

[0267] (viscosity) The viscosity (melt viscosity) of the DNPOA obtained in Example 1 at 150° C. was measured using a CAP2000+ viscometer (manufactured by Brookfield Corporation) with an optional rotor (cone 6) selected according to the viscosity to be measured at a rotation speed of 900 rpm.

[0268] The viscosity at 25°C of Examples 2 to 10 and Comparative Examples 2 to 4 was measured using a TV-22 viscometer (cone-plate type, "TVE-22L" manufactured by Toki Sangyo Co., Ltd.) with an optional rotor (01:1°34' x R24, 07:3° x R7.7) selected according to the viscosity to be measured, at a rotation speed of 0.5 to 20 rpm.

[0269] (Solubility) 0.3 g of sample was weighed into a sample bottle, and 0.7 g (Condition 1: solids concentration 30% by mass) or 1.0 g (Condition 2: solids concentration 23% by mass) of solvent was added. The resulting mixture was stirred at 50°C for 10 minutes using a bioshaker (TAITEC Corporation, "BR-43FH"). The mixture after stirring was evaluated according to the following criteria. The solvents used were methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), ethyl acetate, propylene glycol monomethyl ether acetate (PGMEA), toluene, dimethylformamide (DMF), and cyclohexanone.

[0270] ○…Dissolution △: Some of the liquid dissolves, but it is cloudy ×...Insoluble.

[0271] (curable) Curability was evaluated based on the feel of the surface of the cured product (cured film) prepared to determine the refractive index nD of the cured product, according to the following criteria.

[0272] ○...No tackiness (adhesion) on the cured surface ×: The surface of the cured product is tacky (sticky).

[0273] [Example 1] (Preparation of DBrFDP-m) 9,9-bis(2-methoxycarbonylethyl)-2,7-dibromofluorene (DBrFDP-m) was synthesized in the same manner as in Example 1 of JP 2005-89422 A, except that 37.9 g (0.44 mol) of methyl acrylate was used instead of t-butyl acrylate and 54.7 g (0.17 mol) of 2,7-dibromo-9H-fluorene was used instead of fluorene.

[0274] (Preparation of DNFDP-m) A reactor was charged with 192.3 g (0.39 mol) of DBrFDP-m, 200 g (1.2 mol) of 2-naphthylboronic acid, 4.3 L of dimethoxyethane, and 1 L of 2 M aqueous sodium carbonate. Under a nitrogen stream, 22.4 g (19.4 mmol) of tetrakis(triphenylphosphine)palladium(0) [or Pd(PPh3)4] was added and the mixture was heated to reflux at an internal temperature of 71–78°C for 5 hours. After cooling to room temperature, 2.0 L of toluene and 500 mL of ion-exchanged water were added, followed by five separate extractions and washings. The organic layer changed color from deep orange to brown. The insoluble matter was filtered and concentrated to yield 305 g of brown crude crystals. The resulting crude crystals were dissolved in a mixture of 1.5 kg of ethyl acetate and 300 g of isopropyl alcohol (IPA) by heating, cooled to below 10°C with ice water, and stirred for 1 hour to precipitate crystals. The precipitated crystals were filtered and dried under reduced pressure to obtain 130 g of gray-brown crystals. The obtained gray-brown crystals were purified by column chromatography (silica gel carrier, developing solvent chloroform:ethyl acetate (volume ratio) = 4:1), then recrystallized from methanol and dried under reduced pressure to obtain 116 g of 9,9-bis(2-methoxycarbonylethyl)-2,7-di(2-naphthyl)fluorene (DNFDP-m) represented by the following formula (white crystals, yield 54.9%, HPLC purity 99.4% area%). 1 The results of H-NMR and FD-MS are shown below.

[0275] [ka]

[0276] 1 H-NMR (CDCl3, 300MHz): δ(ppm)1.7(t,4H),2.6(t,4H),3.4(s,6H),7.5(m,4H),7.7-8.0(m,14H),8.1(s,2H)

[0277] FD-MS: m / z 590 (M+).

[0278] The refractive index nD of DNFDP-m was 1.845, the melting point was 191°C, and the 5% mass loss temperature was 390°C.

[0279] (Preparation of 2,7-dinaphthylfluorene-9,9-dipropanol) A 3 L reactor equipped with a stirrer, dropping funnel, and three-way stopcock was charged with 201 g (0.340 mol) of DNFDP-m and purged with nitrogen. Then, 1.7 L of tetrahydrofuran (THF) was added to dissolve the product and the mixture was cooled with water. Under water cooling, 52.4 g (1.38 mol) of sodium borohydride was added in portions over 5 minutes, followed by 174 mL (1.38 mol) of boron trifluoride diethyl etherate over 1 hour. The mixture was then stirred at room temperature for 22 hours. The reaction progress was monitored by HPLC. After the reaction, the THF was removed from the reaction mixture by distillation under heating and reduced pressure (external temperature 45°C, diaphragm pump). 2.5 L of dichloromethane was added and the mixture was stirred for 1 hour to dissolve the product. The mixture was washed three times with 1.5 L of purified water and dried over sodium sulfate. After filtering off the sodium sulfate, the mixture was concentrated to dryness by heating under reduced pressure (external temperature 60°C, oil rotary pump) to obtain 176 g of 2,7-dinaphthylfluorene-9,9-dipropanol [or 9,9-bis(3-hydroxypropyl)-2,7-di(2-naphthyl)fluorene] represented by the following formula as a white solid in a yield of 96.9%. 1 The results of H-NMR are shown below.

[0280] [ka]

[0281] 1 H-NMR (DMSO-d6, 300MHz): δ (ppm) 0.9 (m, 4H), 2.2 (m, 4H), 3.2 (t, 4H), 4.2 (t, 2H), 7.5-8.4 (m, 20H).

[0282] (Preparation of DNPOA) A 500 mL three-neck flask equipped with a Dean-Stark cap was charged with 30.0 g (0.06 mol) of 2,7-dinaphthylfluorene-9,9-dipropanol, 10.5 g (0.15 mol) of acrylic acid, 55 g of toluene, and 0.12 g (1.0 mmol) of 2-methoxyphenol. The system was purged with nitrogen and heated to 95°C. After homogenizing the components, 1.33 g (7.0 mmol) of p-toluenesulfonic acid monohydrate was added. After purging with nitrogen again, the system was refluxed for 4 hours. The reaction temperature was 110-115°C.

[0283] The resulting solution was washed with 195 g of toluene and 20 g of 20% by mass brine (internal temperature 60-70°C), then neutralized with 20 g of 10% caustic soda water (10% by mass sodium hydroxide aqueous solution) and 20 g of 20% by mass brine (internal temperature 60-70°C), and the aqueous layer was confirmed to have a pH of 10 or higher. 500 ppm by mass of 2-methoxyphenol was added to the entire organic layer, and the solution was homogenized. The solution was washed twice with 20 g of 20% by mass brine and twice with 20 g of ion-exchanged water (internal temperature 60-70°C), and the aqueous layer was confirmed to have a pH of 7. Subsequently, 6 g of activated carbon (FP-6 manufactured by Mizusawa Chemical Industries, Ltd.) was added to the organic layer, and the mixture was stirred at room temperature for 1 hour. After filtration through Celite, the mixture was concentrated and dried under reduced pressure at 100°C overnight to obtain 2,7-dinaphthylfluorene-9,9-dipropyl diacrylate [or 9,9-bis(3-acryloyloxypropyl)-2,7-di(2-naphthyl)fluorene] (DNPOA) represented by the following formula as a pale yellow solid (HPLC purity 93.2%). 1 The results of H-NMR are shown below. The obtained DNPOA was also evaluated in various ways.

[0284] [ka]

[0285] 1 H-NMR (CDCl3, 300MHz): δ (ppm) 1.1 (m, 4H), 2.3 (m, 4H), 3.9 (t, 4H), 5.7 (dd, 2H), 6.0 (dd, 2H), 6.3 (dd, 2H), 7.5-8.1 (m, 20H).

[0286] [Comparative Example 1] BNEFA represented by the following formula was prepared in accordance with Synthesis Example 1 described in JP 2018-059059 A (Patent Document 2), and various evaluations were carried out. [ka]

[0287] Comparative Example 2 Each evaluation was carried out using BPEFA (manufactured by Osaka Gas Chemicals Co., Ltd.) represented by the following formula. [ka]

[0288] The evaluation results are shown in Table 1.

[0289] [Table 1]

[0290] As is clear from Table 1, the DNPOA obtained in Example 1 exhibited a significantly high refractive index nD. As shown by the conventional acrylate compounds in Comparative Examples 1 and 2, the refractive index tends to improve with an increase in the aromatic ring structure (benzene ring structure) in the molecular structure. However, the DNPOA of Example 1 and the BNEFA of Comparative Example 1 have the same number of aromatic ring structures, and the refractive index surprisingly improved by 0.03 simply by changing the bonding position of the naphthalene ring. Note that even an increase in refractive index of about 0.01 is considered to be advantageous, and therefore can be said to have a significant effect.

[0291] Furthermore, the 5% mass loss temperature of the cured product was also high for the DNPOA obtained in Example 1. Thus, despite exhibiting a high refractive index and heat resistance, the glass transition temperature was unexpectedly low.

[0292] Furthermore, Table 2 shows the evaluation results of the solubility in various solvents of Example 1 (DNPOA) and Comparative Example 1 (BNEFA).

[0293] [Table 2]

[0294] As is clear from Table 2, Comparative Example 1 (BNEFA) had many ratings of × or △, indicating low solubility. This indicates that while the aromatic ring structure in the molecular structure tends to improve the refractive index, it also tends to reduce solubility, i.e., it is difficult to achieve both a high refractive index and high solubility (ease of handling). In contrast, DNPOA obtained in Example 1, despite having the same number of aromatic ring structures as BNEFA, exhibited high solubility in various solvents and exhibited an excellent balance between refractive index and solubility.

[0295] [Examples 2 to 10, Comparative Examples 3 to 4] Acrylate compounds were mixed in the mass ratios shown in Table 3 below, and the curable compositions containing the resulting mixtures were evaluated. Note that the numbers in parentheses in the acrylate compound column in Table 3 indicate parts by mass.

[0296] [Table 3]

[0297] As is clear from Table 3, the curable compositions of Examples 2 to 10, which contained the DNPOA of Example 1, also exhibited significantly high refractive indices nD. On the other hand, the curable compositions of Comparative Examples 3 and 4, which contained the BNEFA of Comparative Example 1 instead of DNPOA, had lower refractive indices than the corresponding Examples 2 and 5. Furthermore, Examples 3 and 6, which showed refractive indices close to those of Comparative Examples 3 and 4, had significantly lower viscosities and were excellent in handleability. Therefore, the Examples achieved a good balance between high refractive indices and low viscosities.

[0298] Furthermore, the 5% mass loss temperature of the cured products of the examples was also high, and therefore they exhibited high refractive index and heat resistance. [Industrial Applicability]

[0299] The di(meth)acrylate compound (or curable composition or cured product thereof) of the present disclosure exhibits excellent optical properties such as a high refractive index, and high heat resistance, and therefore may be used in a variety of applications, for example, coating agents or coating films, specifically, protective films for paints, inks, electronic devices, liquid crystal components, etc.; adhesives, pressure-sensitive adhesives; resin fillers; electric and electronic materials or electric and electronic components (electrical and electronic devices), specifically, antistatic agents, carrier transport agents, light-emitting bodies, organic photoreceptors, thermosensitive recording materials, photochromic materials, hologram recording materials, charging trays, conductive sheets, optical disks, inkjet printers, digital paper, color filters, organic EL elements, organic semiconductor lasers, dye-sensitized solar cells, sensors, EMI shielding films, etc.; mechanical materials or mechanical parts (devices), specifically, automotive materials or parts, aerospace-related materials or parts, sliding members, etc.

[0300] In particular, it can be effectively used as an optical component (optical element) or optical material, for example, optical adhesives (sealants) or pressure-sensitive adhesives such as OCR (optical clear resin) and OCA (optical clear adhesive) tapes or films, optical films (optical sheets), optical lenses, prisms, holograms, optical fibers, etc.

[0301] Examples of optical films include polarizing films, polarizing elements and polarizer protective films that constitute polarizing films, retardation films, alignment films, viewing angle widening (compensation) films, diffusers, prism sheets, light guide plates, brightness enhancement films, near-infrared absorbing films, reflective films, anti-reflection (AR) films, reflection-reducing (LR) films, anti-glare (AG) films, transparent conductive (ITO) films, anisotropic conductive films (ACF), electromagnetic wave shielding (EMI) films, films for electrode substrates, films for color filter substrates, barrier films, color filter layers, black matrix layers, adhesive layers or release layers between optical films, etc. The optical film may be an optical film for displays such as liquid crystal displays (LCDs), organic light-emitting diode (OLED) displays (OLEDs), plasma displays (PDPs), field emission displays (FEDs), and electronic paper.

[0302] Examples of optical lenses include eyeglass lenses, contact lenses, camera lenses, VTR zoom lenses, pickup lenses, Fresnel lenses, solar condensing lenses, objective lenses, and rod lens arrays.

Claims

1. The following formula (2) 【Chemistry 1】 (In the formula, Z １ａ and Z １ｂ each independently represents a naphthalene ring or a biphenyl ring, R １ａ and R １ｂ are each independently a linear or branched chain C １－４ represents an alkyl group, k1 and k2 each independently represent an integer of 0 to 3, m1 and m2 represent 1; R ２ａ and R ２ｂ are each independently a linear or branched chain C １－４ represents an alkyl group, n1 and n2 each independently represent an integer of 0 to 3, A １ａ and A １ｂ are each independently a linear or branched chain C １－６ represents an alkylene group, A ２ａ and A ２ｂ are each independently a linear or branched chain C ２－４ represents an alkylene group, and p1 and p2 each independently represent an integer of 0 to 3. A compound represented by the formula:

2. In the formula (2), Z １ａ and Z １ｂ is a naphthalene ring, A １ａ and A １ｂ is linear or branched C １－４ is an alkylene group, The compound according to claim 1, wherein p1 and p2 are 0.

3. The following formula (5A) 【Chemistry 2】 (In the formula, R ４ａ and R ４ｂ each independently represents a hydrogen atom or an alkyl group, A ３ａ and A ３ｂ are each independently A in the formula (2). １ａ and A １ｂ represents an alkylene group having one less carbon atom corresponding to Z １ａ and Z １ｂ , R １ａ and R １ｂ , k1 and k2, m1 and m2, R ２ａ and R ２ｂ , and n1 and n2 are the same as in formula (2) above).

3. A method for producing the compound according to claim 1, comprising a reduction step of reducing a compound represented by the formula:

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