Fluorene derivatives, methods for producing the same, and their uses

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] This disclosure relates to novel di(meth)acrylate compounds having a fluorene skeleton, as well as methods for producing the same and their applications. [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 are known to have such a 9,9-bisarylfluorene skeleton, such as (meth)acrylate compounds. Patent documents 1 and 2 describe (meth)acrylate compounds having a 9,9-bis-condensed polycyclic arylfluorene skeleton and curable compositions containing these (meth)acrylate compounds, which exhibit particularly high refractive indices.

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

[0004] [Patent Document 1] Japanese Patent Publication No. 2009-173648 [Patent Document 2] Japanese Patent Publication No. 2018-059059 [Patent Document 3] U.S. Patent Application Publication No. 2003 / 0049173 [Overview of the project] [Problems that the invention aims to solve]

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

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

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

[0008] Therefore, the object of this disclosure is to provide novel di(meth)acrylate compounds exhibiting a high refractive index, as well as methods for producing the same and their applications. [Means for solving the problem]

[0009] As a result of diligent research to achieve the above objectives, the present inventors discovered that a di(meth)acrylate compound having a specific chemical structure in which aryl groups are bonded to the 1st to 8th positions of the fluorene skeleton, surprisingly exhibits the remarkably high refractive index despite not having a 9,9-bisarylfluorene skeleton, thus completing the present invention.

[0010] In other words, the di(meth)acrylate compounds of this disclosure are 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 from 0 to 4, and at least one of m1 and m2 is 1 or more, R 2a and R 2b each independently represents a substituent, n1 and n2 each independently represent an integer from 0 to 4, m1 + n1 and m2 + n2 are each 4 or less, 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 more, R 3a and R 3b each independently represents a hydrogen atom or a methyl group). [[ID= twenty-nine]]

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

[0014] Also, in the above 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 a linear or branched C 1-4 alkylene group, p1 and p2 may be 0.

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

[0016] This disclosure includes a method for producing a compound represented by formula (2) below by reacting it with compounds represented by formulas (3a) and (3b) below.

[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 equation (1) above).

[0019] [ka]

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

[0021] Furthermore, this disclosure includes a curable composition comprising a compound represented by formula (1). The curable composition may further comprise a compound represented by the following formula (7).

[0022] [ka]

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

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

[0025] Furthermore, the ratio of the compound represented by formula (1) to the compound represented by formula (7) may be approximately 10 / 90 to 90 / 10 in terms of mass ratio.

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

[0027] (In the formula, Ar represents an arene ring, R 8 represents a substituent, and u represents a non-negative integer. A 5 represents a linear or branched alkylene group, and v represents an integer greater than or equal to 0. R 9 (This indicates a hydrogen atom or a methyl group).

[0028] In equation (8) above, Ar is C 6-12 It is an allene ring, R 8 is a hydrocarbon group, and u is an integer between 0 and 2. A 5 C is linear or branched. 2-4 It is an alkylene group, and v can be an integer between 1 and 4.

[0029] Furthermore, the ratio of the compound represented by formula (1) to the compound represented by formula (8) may be approximately 10 / 90 to 95 / 5 in terms of mass ratio.

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

[0031] Furthermore, this disclosure includes optical members containing the cured product.

[0032] Furthermore, this disclosure may address the following issues as a secondary objective. That is, another objective of this 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 method for producing the same and its applications.

[0033] Another object of this disclosure is to provide di(meth)acrylate compounds capable of forming cured products with excellent flexibility (or toughness) even if they have a rigid chemical structure such as an aromatic ring skeleton (and thus have high refractive index and heat resistance), as well as a method for producing the same and its applications.

[0034] Another object of this disclosure is to provide di(meth)acrylate compounds that have excellent solubility even when having many aromatic ring skeletons, as well as methods for producing the same and their applications.

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

[0036] The novel di(meth)acrylate compounds of this disclosure 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 that exhibit relatively high heat resistance (high 5% mass loss temperature). Compounds with such high refractive index and heat resistance generally have rigid chemical structures such as aromatic ring skeletons (benzene ring skeletons), and often result in hard and brittle cured products with high glass transition temperatures. However, contrary to expectations, the di(meth)acrylate compounds of the present invention, despite having high refractive index and 5% mass loss temperature, tend to form cured products with surprisingly low glass transition temperatures and relatively flexible properties (or toughness). In addition, while the solubility of a compound usually tends to decrease when it contains many aromatic ring skeletons in its chemical structure, the aforementioned di(meth)acrylate compounds tend to exhibit surprisingly high solubility. [Modes for carrying out the invention]

[0037] [Di(meth)acrylate compounds] The novel di(meth)acrylate compounds of this disclosure are 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 of these independently represents a substituent, and k1 and k2 each independently represent an integer greater than or equal to 0. m1 and m2 each independently represent integers between 0 and 4, and at least one of m1 and m2 is 1 or greater. R 2a and R 2b Each of these independently represents a substituent, and n1 and n2 independently represent integers from 0 to 4. m1+n1 and m2+n2 are each less than or equal to 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, and p1 and p2 independently represent integers greater than or equal to 0. R 3a and R 3b (Each of these independently represents a hydrogen atom or a methyl group.)

[0040] In equation (1) above, Z 1a and Z 1b Examples of arene rings (aromatic hydrocarbon rings) represented by this formula include monocyclic arene rings such as benzene rings, and polycyclic arene rings. Examples of polycyclic arene rings include condensed polycyclic arene rings (condensed polycyclic aromatic hydrocarbon rings) and ring-aggregated arene rings (ring-aggregated polycyclic aromatic hydrocarbon rings).

[0041] Examples of the condensed polycyclic arene ring include condensed polycyclic arene rings having two to four condensed rings such as a condensed bicyclic arene ring and a condensed tricyclic arene ring. Examples of the condensed bicyclic arene ring include condensed bicyclic C 10-16 arene rings such as a naphthalene ring and an indene ring. Examples of the condensed tricyclic arene ring include condensed tricyclic C 14-20 arene rings such as an anthracene ring and a phenanthrene ring. A preferred condensed polycyclic arene ring is a condensed polycyclic C 10-14 arene ring such as a naphthalene ring.

[0042] Examples of the ring assembly arene ring include biarene rings such as a biphenyl ring, a phenylnaphthalene ring, and a binaphthyl ring; and terarenene rings such as a terphenyl ring. A preferred ring assembly arene ring is a C 12-18 biarene ring such as a biphenyl ring.

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

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

[0045] Rings Z 1a and Z 1bThe types may be different from each other, but are preferably the same. Further, when m1 is 2 or more, two or more rings Z 1a may be the same as or different from each other in type. The same applies to m2 and Z 1b .

[0046] Also, the rings Z 1a and Z 1b may each be substituted at any position of the 1st to the 4th positions or the 5th to the 8th positions of the fluorene skeleton, but the 2nd, 3rd and / or 7th positions are preferred. When m1 and m2 are 1, the preferred substitution positions (or bonding positions) are positions that are symmetric with respect to the left and right on the paper surface in the above formula (1), such as the 1,8 positions, 2,7 positions, 3,6 positions, 4,5 positions, etc., and particularly the 2,7 positions are preferred.

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

[0048] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

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

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

[0051] Examples of cycloalkyl groups include cyclopentyl groups, cyclohexyl groups, and other C groups. 5-10 Examples include cycloalkyl groups.

[0052] Examples of aryl groups include phenyl groups, alkylphenyl groups, biphenylyl groups, naphthyl groups, etc. 6-12 Examples include aryl groups. Alkylphenyl groups include mono- or tri-C groups such as methylphenyl (or tolyl) and dimethylphenyl (or xylyl) groups. 1-4 Alkylphenyl groups are one example.

[0053] Examples of aralkyl groups include benzyl groups, phenethyl groups, and other C groups. 6-10 Aryl-C 1-4 Alkyl groups are examples.

[0054] The group [-OR h Examples of these groups include alkoxy groups, cycloalkyloxy groups, aryloxy groups, and aralkyloxy groups, and specifically, the hydrocarbon group R h Examples of corresponding groups include linear or branched C groups such as methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, and t-butoxy groups. 1-10 Examples include alkoxy groups. Cycloalkyloxy groups include, for example, cyclohexyloxy groups and other C groups. 5-10 Examples include cycloalkyloxy groups. Examples of aryloxy groups include phenoxy groups and other C groups. 6-10 Examples include aryloxy groups. Examples of aralkyloxy groups include the benzyloxy group and other C groups. 6-10 Aryl-C 1-4 Alkyloxy groups are one example.

[0055] The aforementioned base [-SR hExamples of these groups include alkylthio groups, cycloalkylthio groups, arylthio groups, and aralkylthio groups, and specifically, the hydrocarbon group R h Examples of groups corresponding to the above include C13 1-10 Examples include alkylthio groups. Cycloalkylthio groups include, for example, cyclohexylthio groups and other C groups. 5-10 Examples include cycloalkylthio groups. Examples of arylthio groups include thiophenoxy groups (phenylthio groups) and other C groups. 6-10 Examples of arylthio groups include the benzylthio group. 6-10 Aryl-C 1-4 Alkylthio groups are one example.

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

[0057] Examples of mono- or disubstituted amino groups include dialkylamino groups and bis(alkylcarbonyl)amino groups. Examples of dialkylamino groups include diC such as dimethylamino groups. 1-4 Examples include alkylamino groups. Bis(alkylcarbonyl)amino groups include, for example, diacetylamino groups and other bis(C) groups. 1-4 Examples include alkyl-carbonyl amino groups.

[0058] These base R 1a and R 1b Typical examples include hydrocarbon groups, alkoxy groups, acyl groups, nitro groups, cyano groups, and substituted amino groups. When k1 is 1 or greater, the preferred group R 1a Examples include alkyl groups and alkoxy groups, specifically linear or branched C groups such as methyl groups. 1-6 Linear or branched C such as alkyl groups and methoxy groups 1-4Examples include alkoxy groups, and among them alkyl groups, particularly linear or branched C groups such as methyl groups. 1-4 Alkyl alkyl groups are preferred. k2 and R 1b The same applies to the base R. 1a When the group R is an aryl group, 1a is ring Z 1a They may form the aforementioned ring-assembled arene ring together. 1b and Z 1b The same applies to this matter.

[0059] The number of substitutions k1 and k2 are given by ring Z. 1a and Z 1b The type can be selected according to the type, for example, an integer from 0 to 7 can be selected, and preferred ranges are, in order, integers from 0 to 6, integers from 0 to 5, integers from 0 to 4, integers from 0 to 3, integers from 0 to 2, and more preferably 0 or 1, and especially 0.

[0060] base R 1a and R 1b The number of substitutions k1 and k2 may be different from each other, but it is preferable that they be the same. Note that if the number of substitutions k1 is 2 or more, the same ring Z 1a Substituting two or more groups R 1a The types may be the same or different from each other. k2 and R 1b The same applies to the base R. 1a and R 1b The types may be different from each other, but it is preferable that they be the same. Base R 1a and R 1b The substitution position is not particularly restricted, ring Z 1a and Z 1b You may choose depending on the type.

[0061] group [-Z 1a -(R 1a ) k1 ] and base[-Z 1b -(R 1b ) k2 ](The following are Z 1The number of substitutions m1 and m2 of the containing group are, for example, integers of about 1 to 3, preferably 1 or 2, and more preferably 1. m1 and m2 may be different from each other, but it is preferable that they be the same. Of m1 and m2, at least one is an integer of 1 or more, preferably both are integers of 1 or more such as 1 to 2, and more preferably both are 1.

[0062] Furthermore, if m1 is 2 or more, then 2 or more bases [-Z 1a -(R 1a ) k1 The types of ] may be the same or different from each other. m2 and base [-Z 1b -(R 1b ) k2 The same applies to ]. Also, if both m1 and m2 are 1 or greater, then base [-Z 1a -(R 1a ) k1 ] and base[-Z 1b -(R 1b ) k2 These two elements may be identical or different from each other, but it is preferable that they be identical.

[0063] R 2a and R 2b The substituents represented by (non-reactive substituents or non-polymerizable substituents) are the Z 1 Any substituent other than the constituent group is acceptable, and typical examples include hydrocarbon groups such as alkyl groups (excluding aryl groups), halogen atoms such as fluorine, chlorine, and bromine atoms, and cyano groups. Examples of alkyl groups include linear or branched C groups such as methyl, ethyl, and t-butyl groups. 1-6 Examples include alkyl groups. When the number of substitutions n1 is 1 or more, preferred R 2a C is linear or branched C 1-4 It is an alkyl group, and more preferably a linear or branched C 1-3 Alkyl groups, particularly C groups such as methyl groups. 1-2 Alkyl alkyl groups are preferred. n2 and R 2b The same applies to this matter.

[0064] R2a and R 2b The number of substitutions n1 and n2 are, for example, integers of about 0 to 3, preferably integers of 0 to 2, more preferably 0 or 1, and especially 0. n1 and n2 may be different from each other, but it is preferable that they be the same. Note that if n1 is 2 or more, multiple R 2a The types may be the same or different from each other. n2 and R 2b The same applies to n1. Also, if both n1 and n2 are 1 or greater, R 2a and R 2b The types may be the same or different from each other, but it is preferable that they be the same. Also, R 2a and R 2b The substitution position of Z is not particularly restricted, 1 It is sufficient if the substitution occurs at a position other than the substitution site of the constituent group.

[0065] m1+n1 and m2+n2 are, for example, integers between 0 and 4, preferably between 1 and 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 linear or branched alkylene groups represented by include linear or branched C groups such as methylene group, ethylene group, trimethylene group, propylene group, 1,2-butanediyl group, and 2-methylpropane-1,3-diyl group. 1-12 Examples include alkylene groups. 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. 1-6 Examples include alkylene groups, more preferably linear or branched C 1-5 Alkylene group, more preferably linear or branched C 1-4 Alkylene groups, particularly linear or branched C groups. 2-4Alkylene groups are preferred, and trimethylene groups are particularly preferred. Group A 1a and A 1b The types may be different from each other, but it is preferable that they be the same.

[0067] A 2a and A 2b Examples of linear or branched alkylene groups represented by include linear or branched C groups such as ethylene, propylene, trimethylene, 1,2-butanediyl, 1,3-butanediyl, and tetramethylene. 2-6 Examples include alkylene groups. Preferred alkylene groups are linear or branched C 2-4 The alkylene group, more preferably linear or branched C 2-3 The alkylene group is preferred, and among these, the ethylene group and the propylene group are preferred, with the ethylene group being particularly preferred. Also, A 2a and A 2b The types may be different from each other, but it is preferable that they be the same.

[0068] Oxyalkylene group (OA) 2a ) and (OA 2b The number of repetitions p1 and p2 can be selected from a range of approximately 0 to 20, for example, and preferred ranges are 0 to 15, 0 to 10, 0 to 8, 0 to 5, 0 to 3, 0 to 2, 0 to 1, and especially 0. When p1 is 2 or more, the (poly)oxyalkylene group [-(OA 2a ) p1 -] 2 or more A 2a The types may be different from each other, but it is preferable that they be the same. p2 and A 2b The same applies to this matter.

[0069] Furthermore, p1 and p2 may be the same or different from each other. Note that the number of repetitions p1 and p2 may be the mean value (or arithmetic mean), i.e., the average number of moles added, and their range is the same as the range of integers mentioned above, including in preferred embodiments.

[0070] Furthermore, the total number of repeats p1 and p2 is the number of oxyalkylene groups (OA) in one molecule of the di(meth)acrylate compound represented by formula (1). 2a ) and (OA 2b This refers to the total number (or the average value of the total number of added moles), and is sometimes simply referred to as p1+p2. p1+p2 can be selected from a range of approximately 0 to 30, and preferred ranges are, in order, 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, especially 0. In addition, p1+p2 may be an integer as described above, but it may also be the average value of the total number of added moles, and its range is the same as the range of integers, including the preferred embodiment.

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

[0072] Furthermore, p1+p2 can be measured by conventional methods. For example, in the preparation of the compound represented by formula (2), which is a raw material for the di(meth)acrylate compound represented by formula (1), later described later, an alkylene oxide (alkylene carbonate or haloalkanol) is added to the compound represented by formula (4), later described later, to form a (poly)alkylene oxy group [-(OA] 2a ) p1 -] and [-(OA) 2b ) p2 When forming the -, the hydroxyl value can be calculated as an arithmetic mean or 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 Japanese Patent Publication No. 2013-53310.

[0073] R 3a and R 3b R may be either a hydrogen atom or a methyl group, but a hydrogen atom is preferred because it can improve reactivity (or curability) and refractive index. 3a and R 3bThe types may be the same or different from each other, but it is preferable that they be the same.

[0074] Examples of typical di(meth)acrylate compounds represented by formula (1) include 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 and 9,9-bis[(meth)acryloyloxyalkyl]-dinaphthylfluorene.

[0075] Examples of 9,9-bis[(meth)acryloyloxyalkyl]-diphenylfluorene include 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, 9,9-bis[3-(meth)acryloyloxypropyl]-4,5-diphenylfluorene, and other 9,9-bis[(meth)acryloyloxypropyl]-diphenylfluorene. 1-6 Examples include alkyl-diphenylfluorene.

[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, 9,9-bis[3-(meth)acryloyloxypropyl]-2,7-di(1-naphthyl)fluorene, and other 9,9-bis[(meth)acryloyloxypropyl]-dinaphthylfluorenes. 1-6 Examples include alkyl-dinaphthylfluorene.

[0077] Among these di(meth)acrylate compounds represented by formula (1) above, 9,9-bis[3-(meth)acryloyloxypropyl]-2,7-diphenylfluorene and other 9,9-bis[(meth)acryloyloxypropyl] 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 Alkyl]-2,7-di(2-naphthyl)fluorene is more preferred, and among these, 9,9-bis[(meth)acryloyloxypropyl]-2,7-di(2-naphthyl)fluorene and other 9,9-bis[(meth)acryloyloxypropyl] 2-3 Alkyl]-2,7-di(2-naphthyl)fluorene is particularly preferred.

[0078] The di(meth)acrylate compound represented by 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, around 1.6 to 1.8, and preferred ranges are, in order, 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 formula (1) may be, for example, around 50 to 200°C, and preferably, in stages, 80 to 160°C, 100 to 140°C, 110 to 130°C, and 115 to 125°C.

[0080] The di(meth)acrylate compound represented by formula (1) tends to have excellent solubility even when it contains many aromatic ring skeletons (benzene ring skeletons) in its chemical structure, 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)acrylate described in Japanese Patent Publication No. 2018-059059), it dissolves easily in many types of solvents even at relatively high concentrations of about 20-50% by mass, preferably 25-40% by mass, and more preferably 30-35% by mass. Therefore, it is possible to achieve both high refractive index and / or high heat resistance and high solubility, and even if the compound represented by formula (1) is a solid that does not exhibit fluidity at room temperature of about 25°C, its handling properties tend to be effectively improved.

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

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

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

[0084] [ka]

[0085] (In the formula, X 1a and X 1b Each of these independently represents a hydroxyl group, an alkoxy group, or a halogen atom. R 4a and R4b Each of these 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 either 0 or 1. X 2a and X 2b Each of these groups independently exhibits a reactive group capable of forming a carbon-carbon bond (or direct bond) through a coupling reaction; X 3a The reactive group X 2a And, X 3b The reactive group X 2b Furthermore, each exhibits a reactive group capable of forming a carbon-carbon bond through 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 (This is the same as formula (1) above, including preferred embodiments).

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

[0087] The coupling reaction is not particularly limited and includes conventional coupling reactions such as the Suzuki-Miyaura coupling reaction, the Migita-Kosugi-Stille coupling reaction, the Negishi coupling reaction, and the Hiyama coupling reaction, which use palladium catalysts (or palladium(0) catalysts), as well as the Kumada-Tamao-Corriu coupling reaction, which use nickel catalysts (or nickel(0) catalysts). 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 The group can be appropriately selected depending on the type of coupling reaction. When synthesized by the Suzuki-Miyaura coupling reaction, one of the reactive groups (or the first reactive group), for example, group X 2a and X 2b Examples include halogen atoms or fluorinated alkanesulfonyloxy groups. Examples of halogen atoms include iodine, bromine, and chlorine atoms. Examples of fluorinated alkanesulfonyloxy groups include trifluoromethanesulfonyloxy groups (or groups [-OTf]) and other fluorinated C 1-4 Examples include alkanesulfonyloxy groups.

[0089] These reactive groups may be used alone or in combination of two or more. Of these reactive groups, halogen atoms are preferred, iodine atoms and bromine atoms are more preferred, and bromine atoms are particularly preferred.

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

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

[0092] Note that base X 2a and X 2b And, base X 3a and X 3b This means that any pair of reactive groups that can be coupled with each other can be used, and group X 2a and X 2b The second reactive group is a boronic acid group, and group X 3a and X 3b The first reactive group may be a halogen atom or the group X 2a and X 2b The first reactive group is a halogen atom, and group X 3a and X 3b It is preferable that the second reactive group is a boronic acid group or the like.

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

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

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

[0096] R 4a and R 4b q1 may be either a hydrogen atom or an alkyl group, but it is preferably an alkyl group. Also, if both q1 and q2 are 1, R 4a and R 4b The types may be different from each other, but it is preferable that they be the same.

[0097] In the above formula (6) [and formula (5)], base [-A 3a -C(=O)-OR 4a ] and [-A3b -C(=O)-O-R 4b The coefficients q1 and q2 of ] may each be either 0 or 1, but are preferably 1. Also, q1 and q2 may be different from each other, but are preferably the same.

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

[0099] Examples of dihalo-9H-fluorene include 2,7-dibromo-9H-fluorene and the like. Commercially available products may be used for dihalo-9H-fluorene.

[0100] Examples of 9,9-bis(alkoxycarbonylalkyl)dihalofluorene include 9,9-bis(2-methoxycarbonylethyl)-2,7-dibromofluorene, 9,9-bis(2-ethoxycarbonylethyl)-2,7-dibromofluorene, 9,9-bis(2-methoxycarbonylpropyl)-2,7-dibromofluorene, and the like, namely 9,9-bis(C 1-4 alkoxy-carbonyl-C 2-6 alkyl)-dihalofluorene and the like. 9,9-bis(alkoxycarbonylalkyl)dihalofluorene may be prepared, for example, according to the method described in JP-A-2005-89422. Specifically, it may be prepared by reacting 9H-fluorenes unsubstituted at the 9-position such as 2,7-dibromofluorene with acrylic acid esters such as methyl acrylate or haloacetic acid esters such as methyl bromoacetate in the presence of a base catalyst such as trimethylbenzylammonium hydroxide.

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

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

[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, about 1 / 2 to 1 / 10 in molar ratio, and preferred ranges are, in order, 1 / 2.2 to 1 / 8, 1 / 2.5 to 1 / 5, and 1 / 2.7 to 1 / 3.3.

[0104] When synthesized by the Suzuki-Miyaura coupling reaction, the reaction is carried out in the presence of a palladium catalyst. Examples of palladium catalysts include conventional coupling catalysts, such as palladium(O) catalysts and palladium(II) catalysts.

[0105] Examples of palladium(O) catalysts include palladium(O)-phosphine complexes such as tetrakis(triphenylphosphine)palladium(O) [or Pd(PPh3)4] and bis(tri-t-butylphosphine)palladium(O) [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 PdCl2(dppe)], [1,3-bis(diphenylphosphino)propane]palladium(II) dichloride [or PdCl2(dppp)], [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride [or PdCl2(dppf)], bis(triphenylphosphine)palladium(II) dichloride [or PdCl2(PPh3)2], and bis(tri-o-tolylphosphine)palladium(II) dichloride [or PdCl2(P(o-Tol)3)2]. When using a palladium(II) catalyst, the reaction is initiated by reduction to a zero-valent complex by reducing compounds in the reaction system, such as phosphine, amine, or organometallic reagents.

[0107] The palladium catalyst may also be prepared in the reaction system by adding a catalyst precursor such as tris(dibenzylideneacetone)dipalladium(0)chloroform complex [or Pd2(dba)3·CHCl3] and ligands such as phosphines and carbenes.

[0108] These catalysts can be used individually 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 may be, for example, about 0.01 to 0.1 moles in terms of metal, and 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. Examples of bases include metal carbonates or bicarbonates, metal hydroxides, metal fluorides, metal phosphates, metal organic acid salts, and metal alkoxides.

[0110] Examples of metal carbonates or bicarbonates include alkali metal carbonates or bicarbonates such as sodium carbonate, potassium carbonate, cesium carbonate, and sodium bicarbonate, as well as 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 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 individually 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 moles, and preferably 1 to 25 moles, per mole of the compound represented by formula (6).

[0117] The coupling reaction may be carried out with or without a phase transfer catalyst. Examples of phase transfer catalysts include tetrabutylammonium bromide (TBAB) and tetraalkylammonium halides such as trioctylmethylammonium chloride. These phase transfer catalysts can be used individually or in combination of two or more. Of these phase transfer catalysts, TBAB is preferred.

[0118] The coupling reaction may be carried out in the absence or presence of a solvent inert to the reaction. Examples of the solvent include 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 the cyclic ether include dioxane and tetrahydrofuran. Examples of the chain ether include dialkyl ethers such as diethyl ether and diisopropyl ether, and glycol ethers. Examples of the 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 the aliphatic hydrocarbon include hexane and dodecane. Examples of the alicyclic hydrocarbon include cyclohexane. Examples of the aromatic hydrocarbon 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 chain ethers such as dimethoxyethane is preferred.

[0122] The coupling reaction may be carried out in an inert gas atmosphere, for example, in an atmosphere of nitrogen gas; noble gases such as helium and 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 the reaction is complete, the reaction mixture may be separated and purified as needed by conventional separation and purification methods, such as washing, extraction, filtration, dehydration, concentration, decantation, recrystallization, reprecipitation, chromatography, or a combination thereof.

[0124] (The 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 a compound in which q1 and q2 are 1 as the starting material, the compound represented by formula (6). Alternatively, if at least one of q1 and q2 in formula (5) is 0, and in particular q1 and q2 are 0, the compound represented by formula (5A) may be prepared by reacting this compound with, for example, a (meth)acrylic acid ester or an alkyl haloacetate in accordance with the method described in Japanese Patent Application Publication No. 2005-89422.

[0125] (Preparation of the compound represented by formula (4)) The compound represented by formula (4) can be prepared by reducing the compound represented by formula (5A). Conventional reducing agents may be used for the reduction. Examples of reducing agents include metal hydrides such as boron hydride, aluminum hydride, boranes, aluminum hydride, organosilicon compounds, and organotin compounds.

[0126] Examples of boron hydride metals include alkali metal boron hydride and zinc boron hydride compounds such as zinc borohydride (Zn(BH4)2). Examples of alkali metal borohydride include lithium borohydride compounds such as lithium borohydride (LiBH4), triethyllithium borohydride (LiBH(C2H5)3), tri-s-butyllithium borohydride (LiBH(s-C4H9)3), and bis(2,4,6-trimethylphenyl)lithium borohydride (LiBH(Mes)2); sodium borohydride compounds such as sodium borohydride (NaBH4), cyanosodium borohydride (NaBH3CN), trimethoxysodium borohydride (NaBH(OCH3)3), triacetoxysodium borohydride (NaBH(OCOCH3)3), and sodium borohydride sulfide (NaBH2S3); and potassium borohydride compounds such as tri-s-butylpotassium borohydride (KBH(s-C4H9)3).

[0127] Examples of aluminum hydride metals include aluminum alkali metals. Examples of aluminum alkali metals include lithium aluminum hydride (LiAlH4), trimethoxyaluminum lithium hydride (LiAlH(OCH3)3), tri-t-butoxyaluminum lithium hydride (LiAlH(Ot-C4H9)3), etc.; and sodium aluminum hydride (NaAlH4), bis(2-methoxyethoxy)aluminum sodium hydride ([(CH3OCH2CH2O)2AlH2]Na), etc.

[0128] Examples of boranes include diborane; borane complexes such as borane-tetrahydrofuran complexes and borane-dimethyl sulfide complexes; 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 organosilicon compounds include trialkylsilanes such as triethylsilane, diarylsilanes such as diphenylsilane, and aryldialkylsilanes such as phenyldimethylsilane.

[0131] Examples of organotin compounds include trialkyl stannanes such as tri-n-butyl stannane, dialkyl stannanes such as di-n-butyl stannane, and diaryl stannanes such as diphenyl stannane.

[0132] These reducing agents can be used individually or in combination of two or more. Preferred reducing agents are metal borohydrides such as alkali metal borohydrides, and more preferably sodium borohydrides such as sodium borohydride (NaBH4).

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

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

[0135] The reaction may be carried out in the absence or presence of an inert solvent. Examples of solvents include 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 methanol, ethanol, isopropanol, etc. 1-6 Alcohol is one example.

[0137] Examples of cyclic ethers include dioxane and tetrahydrofuran (THF). Examples of linear 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 solvent can be used alone or in combination of two or more. Preferred solvents are ethers, and cyclic ethers such as THF are even more preferred.

[0140] The reaction may be carried out under an inert gas atmosphere, such as nitrogen gas or a noble 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, 1 to 48 hours.

[0141] After the reaction is complete, the reaction mixture may be separated and purified as needed by conventional separation and purification methods, such as washing, extraction, filtration, dehydration, drying, concentration, decantation, recrystallization, reprecipitation, chromatography, or a combination thereof.

[0142] (The compound represented by formula (2)) The compound represented by formula (2) is A when p1 and p2 are 1 or greater. 2a and A 2bThe compound can be prepared by adding an alkylene oxide (alkylene carbonate or haloalkanol) corresponding to a linear or branched alkylene group represented by formula (4) to the compound represented by formula (4). The addition reaction of the alkylene oxide (alkylene carbonate or haloalkanol) may be carried out by conventional methods, for example, by a method similar to the method described in International Publication No. 2013 / 022065, specifically, in the presence of a base catalyst such as potassium hydroxide, and A such as ethylene oxide. 2a and A 2b Methods include reacting with the corresponding alkylene oxide.

[0143] Furthermore, if p1 and p2 are 0, that is, if the above addition reaction is not performed, the compound represented by formula (4) may be used as 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 compounds represented by formula (1)) The di(meth)acrylate compound represented by formula (1) can be prepared by reacting the compound represented by formula (2) (or the compound represented by formula (4) if p1 and p2 are 0) with the compounds represented by formulas (3a) and (3b) ((meth)acrylic acid or its ester-forming derivative). Unless otherwise specified in this specification and the claims, "ester-forming derivative" refers to alkyl esters (or lower alkyl esters), specifically C13 esters such as methyl esters and ethyl esters. 1-4 This refers to alkyl esters, acid halides such as acid chlorides, and acid anhydrides.

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

[0146] In equations (3a) and (3b) above, X 1a and X 1bExamples of halogen atoms represented by include chlorine atoms, bromine atoms, and iodine atoms, with chlorine atoms being preferred, bromine atoms being preferred, and chlorine atoms being even more preferred. 1a and X 1b The alkoxy group represented by is a lower alkoxy group, such as a linear or branched C group including a methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, and t-butoxy group. 1-4 Examples include alkoxy groups, preferably C such as a methoxy group. 1-2 It is an alkoxy group. 1a and X 1b It is preferable that it is a hydroxyl group.

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

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

[0149] In equations (3a) and (3b) above, X 1a and X 1bIf the halogen atom is present [for example, if the compounds represented by formulas (3a) and (3b) are (meth)acrylate halides], the reaction may be carried out in the presence of a base in order to trap the hydrogen halides produced in the reaction. Bases can be broadly classified into inorganic bases and organic bases, for example.

[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 bicarbonates, specifically alkali metal or alkaline earth metal bicarbonates such as sodium bicarbonate.

[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 types. Among these bases, amines, such as trialkylamines like triethylamine, are preferred. The amount of base used is not particularly limited, but for example, it is 1 to 2 moles, preferably 1.05 to 1.5 moles, and more preferably 1.1 to 1.2 moles per mole of (meth)acrylate halide.

[0153] Furthermore, in equations (3a) and (3b) above, X 1a and X 1b When 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 alkyl (meth)acrylic acid esters], the reaction may be carried out using a conventional esterification catalyst. Examples of catalysts 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 can be preferably used.

[0154] The acid catalyst is not particularly limited and includes 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 individually or in combination of two or more. Furthermore, these acid catalysts may be hydrates.

[0155] Examples of the inorganic acids include strong acids, specifically sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid; and homo- or heteropoly acids, specifically tungstric acid, molybdric acid, tungstosilicate, and molybdosilicic acid.

[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. As the acid catalyst, arenesulfonic acids such as p-toluenesulfonic acid monohydrate are preferred.

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

[0158] The reaction may be carried out in the presence of a polymerization inhibitor. Alternatively, a polymerization inhibitor may be added after the reaction is complete. Examples of polymerization inhibitors include benzoquinone; hydroquinone, hydroquinone monomethyl ether (MEHQ), t-butylhydroquinone, p-benzoquinone and other hydroquinones; pt-butylcatechol and 2-methoxyphenol and other catechols; amines such as N,N-diethylhydroxylamine; 1,1-diphenyl-2-picrylhydrazyl; tri-p-nitrophenylmethyl; and phenothiazines. Polymerization inhibitors 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 per 100 parts by mass of the total amount of the compounds represented by formulas (3a) and (3b), or it may be, for example, about 0.0001 to 0.1 parts by mass per 100 parts by mass of the di(meth)acrylate compound represented by 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 of two or more. Among these solvents, aromatic hydrocarbons such as toluene are preferred. The proportion of the solvent is not particularly limited and may be, for example, 10 to 1000 parts by mass, 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 type of raw materials used. When the compounds represented by formulas (3a) and (3b) are (meth)acrylic acid halides, the reaction temperature is, for example, -10°C 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 alkyl (meth)acrylic acid 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 also be carried out at reflux temperature. The reaction time is not particularly limited and may be, for example, 1 to 24 hours.

[0162] The reaction can be carried out in air or in an inert atmosphere such as nitrogen gas or a noble gas, with stirring, and may be carried out under atmospheric pressure, pressurized pressure, or reduced pressure. In addition, to effectively prevent unexpected polymerization during the reaction, air may be blown into the reaction solution.

[0163] After the reaction is complete, the di(meth)acrylate compound represented by formula (1) that is produced may be separated and purified by conventional methods, such as neutralization, washing, dehydration, filtration, adsorption, concentration, extraction, crystallization, recrystallization, reprecipitation, centrifugation, column chromatography, or a combination thereof.

[0164] [Curable composition and its cured product] This disclosure includes curable compositions and cured products thereof, comprising a di(meth)acrylate compound represented by formula (1) (also referred to as a first polyfunctional (meth)acrylate). The curable composition may contain at least the first polyfunctional (meth)acrylate, and may or may not contain other polymerization components, such as a second polyfunctional (meth)acrylate different from formula (1); monofunctional polymerization components such as monofunctional (meth)acrylate (or reactive diluents).

[0165] (Second polyfunctional (meth)acrylate) The second polyfunctional (meth)acrylate is not particularly limited and may be any compound having multiple (two or more) (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, most preferably 2 to 3, and especially preferably 2.

[0166] Examples of the second type of 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-type 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 polyfunctional (meth)acrylates may be used alone or in combination of two or more. These second polyfunctional (meth)acrylates may be commercially available.

[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 C1,4-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 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 alkylene glycol di(meth)acrylates include ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, and other C 2-10 Examples include alkylene glycol di(meth)acrylate.

[0171] The polyalkylene glycol di(meth)acrylate mentioned above may include, for example, diethylene glycol di(meth)acrylate and other di to hexa-C 2-10 Examples include alkylene glycol di(meth)acrylate.

[0172] Examples of di(meth)acrylates of alicyclic diols include C1,4-cyclohexanedimethanol di(meth)acrylate. 5-10 Examples include di(meth)acrylates of diol compounds having an aliphatic ring.

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

[0174] Examples of poly(meth)acrylates of low molecular weight polyol compounds having approximately 3 to 6 hydroxyl groups or their alkylene oxide (alkylene carbonate or haloalkanol) adducts 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 or hexa(meth)acrylate.

[0175] Of these second polyfunctional (meth)acrylates, di(meth)acrylates of biphenols or bisphenols or their alkylene oxide (alkylene carbonate or haloalkanol) adducts are preferred, and even more preferred are 9,9-bis[hydroxyaryl]fluorene represented by the following formula (7) or di(meth)acrylates of its alkylene oxide (alkylene carbonate or haloalkanol) adduct.

[0176] [ka]

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

[0178] In equation (7) above, Z 2a and Z 2b The arene ring represented by is Z in formula (1) above. 1a and Z 1b Examples include the arene ring shown as an example. Preferred ring Z 2a and Z 2b C is a benzene ring, naphthalene ring, biphenyl ring, etc. 6-12 C such as an arene ring, more preferably a benzene ring, naphthalene ring, etc. 6-10 This refers to an arene ring, particularly a benzene ring.

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

[0180] If r is 1 or greater, the preferred base R 5This is an alkyl group, a cyano group, or a halogen atom, more preferably an alkyl group, and especially linear or branched C such as a methyl group. 1-4 Alkyl alkyl groups are preferred.

[0181] base R 5 The number of substitutions r is, for example, an integer of about 0 to 7, preferably in the following increments: an integer from 0 to 6, an integer from 0 to 4, an integer from 0 to 3, an integer from 0 to 2, and more preferably 0 or 1, especially 0. If r is 2 or more, then 2 or more base R 5 The types may be the same or different from each other. Also, base R 5 The substitution position is not particularly limited, and is, for example, at the 2nd to 7th positions of the fluorene ring, preferably at the 2nd, 3rd and / or 7th positions, and more preferably at the 2nd or 2,7th positions.

[0182] R 6a and R 6b Examples of substituents represented by (1) include R 1a and R 1b Examples of substituents similar to those exemplified above include the following:

[0183] These base R 6a and R 6b Among these, typical examples include hydrocarbon groups, alkoxy groups, acyl groups, nitro groups, cyano groups, and substituted amino groups. When s1 is 1 or greater, the preferred group R 6a These include alkyl groups, aryl groups, and alkoxy groups, specifically linear or branched C 1-6 Linear or branched C such as alkyl groups and methoxy groups 1-4 Examples include alkoxy groups, with alkyl and aryl groups being preferred, and especially linear or branched C groups such as methyl groups. 1-4 C such as alkyl groups and phenyl groups 6-10 Aryl groups are preferred. s2 and R 6b The same applies to the base R. 6a When the group R is an aryl group, 6a These are each ring Z. 2aThey may form the aforementioned ring-assembled arene ring together. 6b and Z 2b The same applies to this matter.

[0184] base R 6a and R 6b The number of permutations s1 and s2 of the ring Z can be any integers greater than or equal to 0. 2a or Z 2b The appropriate integer can be selected depending on the type, for example, an integer of about 0 to 8, preferably, in order below that, an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2, with 0 or 1 being preferred, and 0 being particularly preferred.

[0185] Note that s1 and s2 may be different from each other, but it is preferable that they be the same. Also, if s1 is 2 or more, then 2 or more R 6a The types may be the same or different from each other. s2 and R 6b The same applies to the base R. 6a and R 6b The types may be the same or different from each other. 6a and R 6b The substitution position is not particularly restricted, ring Z 2a and Z 2b The substitution only needs to occur at positions other than the ether bond (-O-) and the bond position to the 9th position of the fluorene ring, and ring Z 2a and Z 2b In this case, substitution is preferred at the ortho position (the carbon atom adjacent to the ether bond) relative to the ether bond (-O-).

[0186] A 4a and A 4b Examples of linear or branched alkylene groups represented by the above formula (1) include A 2a and A 2b The same applies to the alkylene group exemplified as an example, including preferred embodiments, and the ethylene group is particularly preferred. Also, A 4a and A 4b The types may be different from each other, but it is preferable that they be the same.

[0187] Oxyalkylene group (OA) 4a ) and (OA 4b The repeating numbers t1 and t2 of the polyoxyalkylene group can be selected from a range of approximately 0 to 20, for example. Preferred ranges for applications where high refractive index or heat resistance is important are, in order, 0 to 15, 0 to 10, 0 to 6, 0 to 2, and especially 0 to 1. Preferred ranges for applications where low viscosity or flexibility (toughness) is important are, in order, 1 to 10, 3 to 8, 4 to 7, and especially 5 to 6. When t1 is 2 or more, the polyoxyalkylene group [-(OA 4a ) t1 -] 2 or more A 4a The types may be different from each other, but it is preferable that they be the same. t2 and A 4b The same applies to this matter.

[0188] Furthermore, t1 and t2 may be the same or different from each other. Note that the number of repetitions t1 and t2 may be the mean value (or arithmetic mean), i.e., the average number of moles added, and their range is the same as the range of integers described above, including in preferred embodiments.

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

[0190] If the values ​​of t1, t2, or t1+t2 are too large, it may become difficult to improve the refractive index and heat resistance, and if they are too small, it may become difficult to improve handling and flexibility.

[0191] Base [-O-(A 4a O) t1 -] and [-O-(A 4b O) t2 -] Ring Z 2a and Z 2b The substitution position for is not particularly limited. 4a O) t1 The substitution position is ring Z 2a If the ring is a benzene ring, the phenyl group attached to the 9th position of the fluorene ring is preferably at the 2nd, 3rd, or 4th position, with the 3rd or 4th position being particularly preferred. Also, ring Z 2a If the group is a naphthalene ring, then the group [-O-(A 4a O) t1 The substitution site of -] is preferably one of the positions 5 to 8 of the naphthyl group bonded to the 9th position of the fluorene ring, and in particular, it is preferable that the 9th position of the fluorene ring is substituted at the 1st or 2nd position of the naphthalene ring (substituted in a 1-naphthyl or 2-naphthyl relationship), and that this substitution site is substituted in a relationship such as 1,5- or 2,6-, especially a relationship of 2,6-. Also, ring Z 2a If the ring set is an allene ring, then the base [-O-(A 4a O) t1 The substitution position of -] is not particularly limited; for example, ring Z 2a is a biphenyl ring (or ring Z) 2a is a benzene ring, s1 is 1, R 6a If the group is a phenyl group, the 9th position of the fluorene ring is bonded to the 3rd position of the biphenyl ring, and the group [-O-(A 4a O) t1 It is preferable that the -] is substituted at the 6th or 4' position of the biphenyl ring, particularly at the 6th position.

[0192] R 7a and R 7b R may be either a hydrogen atom or a methyl group, but a hydrogen atom is preferred because it easily improves reactivity (or curability) and refractive index.7a and R 7b The types may be the same or different from each other, but it is preferable that they be the same.

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

[0194] Examples of typical 9,9-bis[hydroxyaryl]fluorenes that constitute 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 9,9-bis(alkyl-hydroxyphenyl)fluorene include 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, and other 9,9-bis[(mono or di)C 1-4 Examples include alkyl-hydroxyphenyl fluorene.

[0197] Examples of 9,9-bis(aryl-hydroxyphenyl)fluorene include 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene and other 9,9-bis(C 6-10 Examples include 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] Typical alkylene oxides (alkylene carbonates or haloalkanols) that may be added to the 9,9-bis[hydroxyaryl]fluorene include ethylene oxide, propylene oxide, and other C3 2-3 Alkylene oxide (C 2-3 Alkylene carbonate or C 2-3 Examples include haloalkanols. Furthermore, the number of moles (or average number of moles) t1+t2 of the alkylene oxide (alkylene carbonate or haloalkanol) added may be, for example, around 0 to 20. In applications where a high refractive index or heat resistance is important, 0 to 2 is preferred, while in applications where low viscosity or flexibility (toughness) is important, 9 to 13 is preferred.

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

[0201] When the curable composition contains a second polyfunctional (meth)acrylate, the proportion of the di(meth)acrylate compound represented by formula (7) can be selected from a range of, for example, 30 to 100% by mass relative to the total second polyfunctional (meth)acrylate. Preferred ranges are, in stages, 50% by mass or more, 70% by mass or more, 90% by mass or more, and more preferably substantially 100% by mass, i.e., it is preferable that the second polyfunctional (meth)acrylate contains only the di(meth)acrylate compound represented by formula (7).

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

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

[0204] (Monofunctional polymerization components) The monofunctional polymerization component (or reactive diluent) can be any 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. Specifically, 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 individually 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 monofunctional (meth)acrylates include aliphatic monofunctional (meth)acrylates; alicyclic monofunctional (meth)acrylates; aromatic monofunctional (meth)acrylates; and monofunctional (meth)acrylates containing sulfur atoms. These monofunctional (meth)acrylates can be used individually or in combination of two or more types.

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

[0208] Examples of alicyclic monofunctional (meth)acrylates include C636 5-10 Examples of cross-linked cyclic (meth)acrylates include cycloalkyl (meth)acrylates, dicyclopentenyl (meth)acrylates, and isobornyl (meth)acrylates.

[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 C2-phenoxyethyl (meth)acrylate, 2-(2-naphthoxy)ethyl (meth)acrylate, and 2-(o-phenylphenoxy)ethyl (meth)acrylate. 6-12 Aryloxy C 2-4 Examples include alkyl (meth)acrylates; mono(meth)acrylates of bisphenols or biphenols (or their alkylene oxide adducts), such as mono(meth)acrylates of ethylene oxide adducts of bisphenol A; and (meth)acrylates having a fluorene skeleton, such as 9-(meth)acryloyloxymethylfluorene.

[0210] Examples of monofunctional (meth)acrylates containing sulfur atoms include alkylthio(meth)acrylates, arylthio(meth)acrylates, aralkylthio(meth)acrylates, and arylthioalkyl(meth)acrylates. Examples of alkylthio(meth)acrylates include methylthio(meth)acrylates. 1-6 Examples include alkylthio(meth)acrylates. Examples of arylthio(meth)acrylates include phenylthio(meth)acrylate and other C3 6-10 Examples include arylthio(meth)acrylates. Examples of arylthio(meth)acrylates include benzylthio(meth)acrylate. 6-10 Aryl C 1-6 Examples include alkylthio(meth)acrylates. Examples of arylthioalkyl(meth)acrylates include 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 maintain a high refractive index while being easily reduced in viscosity, and among these, compounds represented by the following formula (8) are preferred.

[0212] [ka]

[0213] (In the formula, Ar represents an arene ring, R 8 represents a substituent, and u represents a non-negative integer. A 5 represents a linear or branched alkylene group, and v represents an integer greater than or equal to 0. R 9 (This indicates a hydrogen atom or a methyl group).

[0214] In formula (8), the arene ring represented by Ar is Z in formula (1). 1aand Z 1b Examples include the arene ring shown as an example. Preferred rings Ar include benzene rings, naphthalene rings, biphenyl rings, etc. 6-12 An arene ring, more preferably a benzene ring or a biphenyl ring, with the biphenyl ring being particularly preferred due to its high refractive index and excellent curability when combined with the (meth)acrylate represented by formula (1).

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

[0216] base R 8 The number of substitutions u can be 0 or an integer greater than or equal to 1, and can be selected depending on the type of ring Ar, for example, an integer of about 0 to 4, preferably an integer of about 0 to 2, more preferably 0 or 1, and especially 0. Note that if u is 2 or more, then there are 2 or more bases R 8 The types may be the same or different from each other. Also, base R 8 The substitution position is not particularly restricted.

[0217] A 5 Examples of linear or branched alkylene groups represented by the above formula (1) include A 2a and A 2b The same applies to the alkylene group exemplified and other preferred embodiments, with the ethylene group being particularly preferred.

[0218] Oxyalkylene group (OA) 5The number of repetitions v of the polyoxyalkylene group can be selected from a range of approximately 0 to 10, preferably in the following increments: 0 to 4, 1 to 3, 1 to 2, and especially 1. If v is too large, it may be difficult to improve the refractive index and heat resistance, and if it is too small, it may be difficult to improve the handling properties. When v is 2 or more, the polyoxyalkylene group [-(OA 5 ) v -] 2 or more A 5 The types may be different from each other, but it is preferable that they be the same.

[0219] R 9 This can be either a hydrogen atom or a methyl group, but a hydrogen atom is preferred because it easily improves reactivity (or curability) and refractive index.

[0220] Group [-O-(A] for ring Ar 5 O) v -CO-CR 9 The bond position of the =CH2] is not particularly restricted, and if the ring Ar is a biphenyl ring, the group [-O-(A] is attached at position 2 of the biphenyl ring. 5 O) v -CO-CR 9 It is preferable that [=CH2] is bonded.

[0221] Typical compounds represented by formula (8) include those in which Ar is replaced by C such as a benzene ring, naphthalene ring, or biphenyl ring. 6-12 It is an arene ring, R 8 is a hydrocarbon group such as an alkyl group, u is an integer from 0 to 2, A 5 is linear or branched C 2-4 Examples include compounds with an alkylene group where v is an integer from 1 to 4. Specific examples include compounds where Ar is a benzene ring and A 5 is linear or branched C 2-3 Compounds that are alkylene groups and where v is an integer between 1 and 2, such as phenoxy C2- 2-3 Alkyl (meth)acrylates, etc.; Ar is a biphenyl ring, A 5 is linear or branched C 2-3Compounds that are alkylene groups and where v is an integer between 1 and 2, such as biphenylyloxy C2-(o-phenylphenoxy)ethyl (meth)acrylate. 2-3 Alkyl (meth)acrylates, etc.; Ar is a naphthalene ring, A 5 is linear or branched C 2-3 Compounds with an alkylene group where v is an integer between 1 and 2, such as naphthoxy C in 2-(2-naphthoxy)ethyl (meth)acrylate. 2-3 Examples include alkyl (meth)acrylates.

[0222] These compounds represented by formula (8) can be used individually or in combination of two or more. In particular, biphenylyloxy C is suitable 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 approximately 10 / 90 to 95 / 5 (mass ratio), for example, 30 / 70 to 90 / 10, and preferably in stages as follows: 50 / 50 to 85 / 15, 60 / 40 to 80 / 20, and 65 / 35 to 75 / 25. If the proportion of the compound represented by formula (8) is too high, the refractive index and curability may decrease, and if it is too low, the handling properties may not be sufficiently improved.

[0224] Furthermore, when the curable composition contains the compound represented by formula (8), the proportion of the compound represented by formula (8) can be selected from a range of approximately 30 to 100% by mass relative to the total monofunctional (meth)acrylate, and preferred ranges are, in stages, 50% or more by mass, 70% or more by mass, 90% or more by mass, and more preferably substantially 100% by mass, that is, it is preferable that the monofunctional (meth)acrylate consists only of the compound represented by formula (8). Also, when the curable composition contains monofunctional (meth)acrylate, the proportion of monofunctional (meth)acrylate can be selected from a range of approximately 30 to 100% by mass relative to the total monofunctional polymerization components, and preferred ranges are, in stages, 50% or more by mass, 70% or more by mass, 90% or more by mass, and more preferably substantially 100% by mass.

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

[0226] (Ingredients other than polymerization components) The curable composition may further contain polymerization initiators, solvents, additives, etc., in addition to polymerization components (or monomer components).

[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 peracid esters) 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 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, per 100 parts by mass of the total amount of polymerization components.

[0231] Furthermore, the photopolymerization initiator may be combined with a photosensitizer. Typical photosensitizers include tertiary amines, such as trialkylamines; trialcanolamines such as triethanolamine; alkyl dialkylaminobenzoates, specifically N,N-dimethylaminobenzoate ethyl such as p-(dimethylamino)benzoate ethyl, N,N-dimethylaminobenzoate amyl such as p-(dimethylamino)benzoate amyl; bis(dialkylamino)benzophenone such as 4,4-bis(diethylamino)benzophenone; and dialkylaminobenzophenone 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, per 100 parts by mass of the polymerization initiator.

[0233] The curable composition does not need to contain a solvent, but because the di(meth)acrylate compound represented by formula (1) has surprisingly high solubility, a solvent may be included as needed to adjust handling. The solvent is not particularly limited and may include, for example, hydrocarbons, specifically aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons, specifically methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, etc.; ethers, specifically linear ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and 1,4-dioxane, etc.; ketones, specifically dialkyl ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexano Examples of solvents include cyclic ketones such as methyl acetate, ethyl acetate, and butyl acetate; glycol ether acetates, specifically (poly)alkylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) and diethylene glycol monobutyl ether acetate; sulfoxides, specifically dimethyl sulfoxide; amides, specifically dimethylformamide (DMF), dimethylacetamide, and N-methyl-2-pyrrolidone; and nitriles, specifically acetonitrile. These solvents can be used individually or as mixed solvents in combination of two or more. Of 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 concentration of the solid content (components other than the solvent) may be such that it is, for example, about 0.1 to 50% by mass, specifically about 20 to 50% by mass, preferably 25 to 40% by mass, and more preferably 30 to 35% by 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, polymerization inhibitors, etc. Examples of stabilizers include heat stabilizers, antioxidants, and ultraviolet absorbers. These additives can be used individually or in combination of two or more.

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

[0237] (cured product) The curable compositions of this disclosure readily harden upon application of active energy (or active energy rays), producing a cured product. The active energy can be thermal energy and / or light energy, such as ultraviolet rays or X-rays.

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

[0239] Furthermore, when using light energy such as ultraviolet light for irradiation, the amount of light irradiation energy can be appropriately selected depending on the application, for example, 50 to 10,000 mJ / cm². 2 Preferably 70-8000 mJ / cm² 2 More preferably 100-5000 mJ / cm² 2 In particular, 500-3000 mJ / cm² 2 That is the case.

[0240] The shape of the cured product is not particularly limited and may be a three-dimensional structure such as a lens-shaped or tubular cured product, a two-dimensional structure such as a film-shaped, sheet-shaped, or plate-shaped cured product (or cured film), or a one-dimensional structure such as a linear or fibrous or rod-shaped cured product.

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

[0242] The cured product of this disclosure is formed from a di(meth)acrylate compound represented by formula (1) and therefore exhibits a high refractive index. For this reason, the refractive index nD of the cured product at a temperature of 25°C and a wavelength of 589 nm may be, for example, around 1.6 to 1.8, and preferred ranges are, in order, 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 nD at a temperature of 25°C and a wavelength of 589 nm for the curable composition) may be, for example, around 1.59 to 1.8, and preferred ranges are, in order, 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] Furthermore, the cured product also possesses high heat resistance, and the 5% mass loss temperature may be, for example, around 200 to 500°C. Preferred ranges are, in stages, 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 surprisingly exhibits a low glass transition temperature Tg, suggesting it possesses relatively flexible properties (or toughness). Therefore, the glass transition temperature Tg of the cured product may be, for example, around -30 to 100°C, and preferred ranges are, in order, -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.

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

[0247] Furthermore, as mentioned above, the di(meth)acrylate compound represented by formula (1) exhibits excellent solubility, so the curable composition can be adjusted to a viscosity suitable for the application using a solvent, and a highly uniform coating film or cured product can be formed. Therefore, the two-dimensional cured product (or cured film) in the form of a film can be easily formed by conventional coating methods, and the film thickness may be, for example, about 50 nm to 300 μm, and even a thin film cured product with a thickness of, for example, about 1 μm or less, preferably 80 to 200 nm, and more preferably 100 to 150 nm can be formed efficiently or easily.

[0248] In this specification and within the 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. [Examples]

[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 described below. BNEFA: 9,9-Bis[6-(2-acryloyloxyethoxy)-2-naphthyl]fluorene, prepared in Comparative Example 1 described later. BPEFA: 9,9-Bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, manufactured by Osaka Gas Chemical Co., Ltd. (Comparative Example 2, described later) BPEF-9EOA: A diacrylate adduct obtained by adding an average of 9 moles of ethylene oxide (EO) to 1 mole of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (or BPEF), prepared according to Reference Example 4 described in Japanese Patent Publication No. 2013-053310. POA: 2-Phenoxyethyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd. ("Light Acrylate PO-A") OPPEOA: o-phenylphenoxyethyl acrylate, manufactured by Nippon Kayaku Co., Ltd.

[0251] [Evaluation Method] (HPLC) Based on the following measuring equipment and conditions, the HPLC purity [area %] of the sample was calculated by high-performance (or high-speed) liquid chromatography (HPLC).

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

[0253] (FD-MS) Mass spectrometry (MS) was performed based on 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 is dissolved in a deuterated solvent (CDCl3 or DMSO-d6) containing tetramethylsilane as an internal standard, and then analyzed using a nuclear magnetic resonance spectrometer (BRUKER AVANCE III HD). 1 The 1H-NMR spectrum was measured.

[0256] (Melting point) A differential scanning calorimeter (EXSTAR DSC6200, manufactured by SII Nanotechnology Co., Ltd.) was used to perform measurements under a nitrogen atmosphere, with a measurement temperature of 30-220°C and a heating rate of 10°C / min.

[0257] (5% mass reduction temperature) Thermogravimetric analysis was performed using a differential thermal analyzer (TG-DTA) (TG / DTA6200, manufactured by SII Nanotechnology Co., Ltd.) to measure the temperature at which the mass of the sample decreased by 5% by mass under a nitrogen atmosphere and a heating rate of 10°C / min. The sample (cured material) was prepared as follows.

[0258] Specifically, 3 parts by mass of Irgacure 184 (manufactured by BASF Japan Ltd.) was added to 100 parts by mass of the acrylate compound (polymerizable component) listed in Table 1 or 3, which was collected in a brown bottle, as a photopolymerization initiator, and the mixture was heated to 120°C to dissolve and obtain a curable composition. The obtained curable composition was then subjected to UV irradiation (500 mJ / cm²). 2 The process was repeated four times to produce a hardened product.

[0259] (Glass transition temperature Tg) The measurement was performed using a differential scanning calorimeter (EXSTAR6000 DSC6220 ASD-2, manufactured by SII Nanotechnology Co., Ltd.) under a nitrogen gas atmosphere at a heating rate of 10°C / min. The sample (cured material) used was prepared in the same manner as the sample (cured material) used for the measurement of the 5% mass loss temperature.

[0260] (Refractive index nD before hardening) The refractive index before curing was measured at a temperature of 25°C and a wavelength of 589 nm (D line). For Examples 1 and Comparative Examples 1-4, a multi-wavelength Abbe refractometer (DR-M2 (60-C3 circulating constant temperature water bath) manufactured by Atago Co., Ltd.) was used as the refractometer, while for Examples 2-10, 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, measuring the refractive index of the resulting solutions, and then extrapolating the concentration to 100% by mass in a calibration curve (approximate straight line).

[0262] Furthermore, the refractive index of 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 measuring the refractive index of the resulting solutions. The refractive index of the resulting calibration curve (approximate straight line) was then extrapolated to 100% by mass.

[0263] The refractive index of 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 of different concentrations.

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

[0265] In Example 1, 100 parts by mass of DNPOA collected in a brown bottle were mixed with 3 parts by mass of Irgacure 184 (manufactured by BASF Japan Ltd.) as a photopolymerization initiator, and then diluted with toluene. This diluted solution (curable composition) was dropped onto the surface of a silicon wafer approximately 3 cm x 3 cm and spin-coated (1000 rpm, 30 seconds) to form a thin film, which was then irradiated with UV light (500 mJ / cm²). 2 A cured film was prepared by ) and the film thickness and refractive index nD of the obtained cured film were measured using a high-speed spectroscopic ellipsometer (JAWoollam "M-2000").

[0266] In Comparative Examples 2-4 and Examples 5 and 8-10, 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 compounds (polymerizable components) listed in Table 1 or 3, collected in a brown bottle, and the mixture was heated, melted, and mixed. The resulting curable composition was applied to a TAC (cellulose acetate) film to a thickness of 200-400 μm using an applicator, and the resulting coating was irradiated with UV light (500 mJ / cm²). 2 A cured film was prepared by performing the following procedure once. The refractive index nD of the obtained cured film was measured using a multi-wavelength Abbe refractometer (DR-M2 (60-C3 circulating constant temperature water bath) manufactured by Atago Corporation), and the film thickness was measured using an MDQ-30 manufactured by Mitutoyo Corporation.

[0267] (viscosity) The viscosity (melt viscosity) of DNPOA obtained in Example 1 at 150°C was measured using a CAP2000+ viscometer (BROOKFIELD), 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 for Examples 2-10 and Comparative Examples 2-4 was measured using a TV-22 viscometer (cone plate type, "TVE-22L" manufactured by Toki Sangyo Co., Ltd.). The optional rotor (01: 1°34′ × R24, 07: 3° × R7.7) was selected according to the viscosity to be measured, and the measurement was performed at a rotation speed of 0.5 to 20 rpm.

[0269] (Solubility) 0.3 g of the sample was weighed into a sample bottle, and 0.7 g of solvent (Condition 1: solid content concentration 30% by mass) or 1.0 g (Condition 2: solid content concentration 23% by mass) was added. The resulting mixture was stirred for 0 minutes at 50°C using a bio-shaker (BR-43FH, manufactured by Taitec Co., Ltd.). The stirred mixture 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 △...Partially dissolves, but remains cloudy. ×...Insoluble.

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

[0272] ○...The surface of the hardened material lacks tackiness (adhesion). ×...The hardened surface has tackiness (adhesion).

[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 described in Japanese Patent Publication No. 2005-89422, 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) 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 solution were charged into a reactor. Under a nitrogen atmosphere, 22.4 g (19.4 mmol) of tetrakis(triphenylphosphine)palladium(0) [or Pd(PPh3)4] was added, and the reaction was carried out by heating under 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 deionized water were added, and the mixture was washed by 5 separatory extractions. The organic layer changed from dark orange to brown. The insoluble matter was filtered and concentrated to obtain 305 g of brown crude crystals. The obtained crude crystals were heated and dissolved in a mixture of 1.5 kg of ethyl acetate and 300 g of isopropyl alcohol (IPA), then cooled to below 10°C in ice water and stirred for 1 hour to precipitate crystals. After filtering the precipitated crystals, they were dried under reduced pressure to obtain 130 g of grayish-brown crystals. The obtained grayish-brown crystals were purified by column chromatography (silica gel support, developing solvent chloroform:ethyl acetate (volume ratio) = 4:1), recrystallized with 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 1H-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] Furthermore, the refractive index nD of DNFDP-m was 1.845, its melting point was 191°C, and its 5% mass loss temperature was 390°C.

[0279] (Preparation of 2,7-dinaphthylfluorene-9,9-dipropanol) 201 g (0.340 mol) of DNFDP-m was charged into a 3 L reactor equipped with a stirrer, dropping funnel, and three-way stopcock. After purging with nitrogen, 1.7 L of tetrahydrofuran (THF) was added and dissolved, and the reactor was cooled with water. Under water cooling, 52.4 g (1.38 mol) of sodium borohydride was added in installments over 5 minutes, followed by the dropwise addition of 174 mL (1.38 mol) of boron trifluoride diethyl ether complex over 1 hour. The mixture was then stirred at room temperature for 22 hours. The reaction progress was confirmed by HPLC. After the reaction, THF was removed from the reaction mixture under heating and reduced pressure (ambient temperature 45°C, diaphragm pump). Then, 2.5 L of dichloromethane was added and stirred for 1 hour to dissolve. 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 under reduced pressure (ambient temperature 60°C, oil rotary pump), yielding 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 the 1H-NMR spectrum 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) 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 were charged into a 500 mL three-necked flask fitted with a Dean-Stark valve. The system was purged with nitrogen, and the temperature was raised to 95°C to homogenize the components. Then, 1.33 g (7.0 mmol) of p-toluenesulfonic acid monohydrate was added, the system was purged with nitrogen again, and the mixture was refluxed for 4 hours. The reaction temperature was 110-115°C.

[0283] The obtained solution was washed with 195 g of toluene and 20 g of 20% by mass saline solution (internal temperature 60-70°C), then neutralized with 20 g of 10% caustic soda solution (10% by mass sodium hydroxide aqueous solution) and 20 g of 20% by mass saline solution (internal temperature 60-70°C), and it was confirmed that the aqueous layer had a pH of 10 or higher. 500 ppm by mass of 2-methoxyphenol was added to the entire organic layer to homogenize the solution, and it was washed twice with 20 g of 20% by mass saline solution and twice with 20 g of deionized water (internal temperature 60-70°C), and it was confirmed that the aqueous layer had a pH of 7. Subsequently, 6 g of activated carbon (FP-6, manufactured by Mizusawa Chemical Co., Ltd.) was added to the organic layer, stirred at room temperature for 1 hour, filtered by Celite, concentrated, and dried under reduced pressure at 100°C overnight to obtain 2,7-dinaphthylfluorene-9,9-dipropyldiacrylate [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 the 1H-NMR spectrum are shown below. Furthermore, various evaluations were performed on the obtained DNPOA.

[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 Japanese Patent Publication No. 2018-059059 (Patent Document 2), and each evaluation was performed. [ka]

[0287] [Comparative Example 2] Each evaluation was performed using BPEFA (manufactured by Osaka Gas Chemical Co., Ltd.), which is 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 showed a remarkably 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 skeleton (benzene ring skeleton) in the molecular structure. However, surprisingly, the refractive index of DNPOA in Example 1 and BNEFA in Comparative Example 1 improved by 0.03 simply because the number of aromatic ring skeletons was the same and only the bonding position of the naphthalene ring differed. It should be noted that even an increase of about 0.01 in refractive index is considered advantageous, so this can be considered a remarkable effect.

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

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

[0293] [Table 2]

[0294] As is clear from Table 2, Comparative Example 1 (BNEFA) received many × and △ ratings, indicating low solubility. This suggests that while aromatic ring skeletons in the molecular structure tend to improve the refractive index, they also tend to decrease solubility, meaning that it is difficult to achieve both a high refractive index and high solubility (handling ease). In contrast, DNPOA obtained in Example 1 showed high solubility in various solvents despite having the same number of aromatic ring skeletons as BNEFA, demonstrating an excellent balance between refractive index and solubility.

[0295] [Examples 2-10, Comparative Examples 3-4] Acrylate compounds were mixed in the mass ratios listed 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 of Table 3 represent parts by mass.

[0296] [Table 3]

[0297] As is clear from Table 3, the curable compositions of Examples 2-10, which included DNPOA from Example 1, also showed a remarkably high refractive index nD. On the other hand, the curable compositions of Comparative Examples 3-4, which included BNEFA from Comparative Example 1 instead of DNPOA, had a lower refractive index compared to the corresponding Examples 2 and 5. Furthermore, Examples 3 and 6, which showed refractive indices close to those of Comparative Examples 3-4, had remarkably low viscosity and excellent handling properties. Therefore, the examples demonstrated a good balance between high refractive index and low viscosity.

[0298] Furthermore, the 5% mass loss temperature of the cured product in the example was also high. Therefore, it exhibited high refractive index and heat resistance. [Industrial applicability]

[0299] The di(meth)acrylate compounds (or curable compositions or cured products thereof) of this disclosure exhibit excellent optical properties such as a high refractive index and high heat resistance, and may therefore be used in a variety of applications, such as coatings or coating films, specifically paints, inks, protective films for electronic equipment and liquid crystal components; adhesives and sealants; resin fillers; electrical and electronic materials or electrical and electronic components (electrical and electronic equipment), specifically antistatic agents, carrier transport agents, light emitters, organic photoreceptors, thermal recording materials, photochromic materials, holographic recording materials, charging trays, conductive sheets, optical discs, inkjet printers, digital paper, color filters, organic EL elements, organic semiconductor lasers, dye-sensitized solar cells, sensors, EMI shielding films, etc.; and mechanical materials or mechanical parts (equipment), 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. Examples include optical adhesives (sealants) or optical adhesives such as OCR (optical clear resin), OCA (optical clear adhesive) tapes or films, optical films (optical sheets), optical lenses, prisms, holograms, and optical fibers.

[0301] Examples of optical films include polarizing films, polarizing element and polarizer protective films constituting polarizing films, phase difference films, alignment films, viewing angle expansion (compensation) films, diffusers (films), prism sheets, light guide plates, brightness enhancement films, near-infrared absorption films, reflective films, anti-reflective (AR) films, anti-reflective (LR) films, anti-glare (AG) films, transparent conductive (ITO) films, anisotropic conductive films (ACF), electromagnetic shielding (EMI) films, films for electrode substrates, films for color filter substrates, barrier films, color filter layers, black matrix layers, and adhesive or release layers between optical films. Optical films may also be optical films for displays such as liquid crystal displays (LCDs), organic light-emitting diodes (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 focusing 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 either a naphthalene ring or a biphenyl ring. R １ａ and R １ｂ Each is independently linear or branched C １－４ It represents an alkyl group, and k1 and k2 each independently represent integers from 0 to 3. m1 and m2 indicate 1. R ２ａ and R ２ｂ Each is independently linear or branched C １－４ It represents an alkyl group, and n1 and n2 each independently represent integers from 0 to 3. A １ａ and A １ｂ each independently represents a linear or branched C １－６ alkylene group, A ２ａ and A ２ｂ Each is independently linear or branched C ２－４ (This indicates an alkylene group, where p1 and p2 independently represent integers from 0 to 3.) A compound represented by the formula.

2. In the above formula (2), Z １ａ and Z １ｂ This is a naphthalene ring, A １ａ and A １ｂ is linear or branched C １－４ It 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 of these independently represents a hydrogen atom or an alkyl group. A ３ａ and A ３ｂ Each of these independently corresponds to A in equation (2) above. １ａ and A １ｂ Correspondingly, it shows an alkylene group with one less carbon atom. 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). A method for producing the compound according to claim 1 or 2, comprising a reduction step of reducing the compound represented by .

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