Fluorene-containing epoxy (METH)acrylate and use thereof

Abstract

To provide an epoxy (meth)acrylate and a curable composition that exhibit a high refractive index.SOLUTION: A fluorene-containing epoxy (meth)acrylate is represented by the following formula (1). (In the formula, ring Z1a, ring Z1b, ring Z2a, and ring Z2b independently denote an arene ring; A1a and A1b independently denote an alkylene group; n1 and n2 independently denote an integer of 0 or more; R1a and R1b independently denote a hydrogen atom or a methyl group; R2a, R2b, R3a, R3b, R4a, and R4b independently denote a substituent; m1, m2, k1, and k2 independently denote an integer of 0 or more; and s1 and s2 independently denote an integer of 0 to 3.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to an epoxy (meth)acrylate having a bisarylfluorene skeleton and uses thereof. [Background technology]

[0002] Fluorene compounds having a 9,9-bis(aryl)fluorene skeleton have a high refractive index and excellent heat resistance, and are widely used in various materials, such as ink materials, light-emitting materials, organic semiconductors, coating agents, lenses, liquid crystal displays, etc. Among such fluorene compounds, fluorene compounds having a (meth)acryloyl group are disclosed in JP 2009-173648 A (Patent Document 1), such as 9,9-bis[6-(2-acryloylethoxy)-2-naphthyl]fluorene, and in JP 2012-206968 A (Patent Document 2), such as 9,9-bis[5-(3-(meth)acryloyloxy-2-hydroxypropyloxy)-1-naphthyl]fluorene. Fluorene compounds such as fluorene, 9,9-bis[6-(3-(meth)acryloyloxy-2-hydroxypropyloxy)-2-naphthyl]fluorene, 9,9-bis[5-{2-(3-(meth)acryloyloxy-2-hydroxypropyloxy)ethoxy}-1-naphthyl]fluorene, and 9,9-bis[6-{2-(3-(meth)acryloyloxy-2-hydroxypropyloxy)ethoxy}-2-naphthyl]fluorene are disclosed. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-173648 [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-206968 Summary of the Invention [Problem to be solved by the invention]

[0004] However, in recent years, advanced optical properties have been required in the optical field, and even the epoxy (meth)acrylates having a fluorene skeleton described in Patent Documents 1 and 2 do not have sufficient refractive indexes.

[0005] Therefore, an object of the present disclosure is to provide a fluorene-containing epoxy (meth)acrylate having a high refractive index and uses thereof. [Means for solving the problem]

[0006] As a result of intensive research to achieve the above object, the present inventors have found that an epoxy (meth)acrylate having a skeleton in which each benzene ring constituting a 9,9-bis(aryl)fluorene ring is further substituted with an aryl group has a high refractive index, and have completed the present invention (or the present disclosure).

[0007] That is, the present disclosure includes the following aspects.

[0008] Aspect [1]: The following formula (1)

[0009] [ka]

[0010] (In the formula, Ring Z 1a , ring Z 1b , ring Z 2a and ring Z 2b each independently represents an arene ring, A 1a and A 1b each independently represents an alkylene group; n1 and n2 each independently represent an integer of 0 or more; R 1a and R 1b each independently represents a hydrogen atom or a methyl group, R 2a , R 2b , R 3a , R 3b , R 4a and R4b each independently represents a substituent, m1, m2, k1, and k2 independently represent an integer of 0 or more, s1 and s2 independently represent an integer of 0 to 3.

[0011] Fluorene-containing epoxy (meth)acrylate represented by the formula:

[0012] Aspect [2]: In the formula (1), ring Z 1a and ring Z 1b represents a naphthalene ring, and ring Z 2a and ring Z 2b The fluorene-containing epoxy (meth)acrylate according to the above aspect [1], wherein represents a benzene ring or a naphthalene ring.

[0013] Aspect [3]: In the formula (1), ring Z 1a , ring Z 1b , ring Z 2a and ring Z 2b The fluorene-containing epoxy (meth)acrylate according to the above embodiment [1] or [2], wherein represents a naphthalene ring.

[0014] Aspect [4]: ​​A fluorene-containing epoxy (meth)acrylate according to any one of Aspects [1] to [3], wherein n1 and n2 represent 0 or 1 in the formula (1).

[0015] Aspect [5]: In the formula (1), R 1a and R 1b The fluorene-containing epoxy (meth)acrylate according to any one of the above aspects [1] to [4], wherein represents a hydrogen atom.

[0016] Aspect [6]: A curable resin composition comprising the fluorene-containing epoxy (meth)acrylate according to any one of Aspects [1] to [5].

[0017] Aspect [7]: Further, the following formula (2)

[0018] [ka]

[0019] (In the formula, Ring Z 3a and ring Z 3b each independently represents an arene ring, A 2a and A 2b each independently represents an alkylene group; t1 and t2 each independently represent an integer of 0 or more; R 5a and R 5b each independently represents a hydrogen atom or a methyl group, R 6a , R 6b and R 7 each independently represents a substituent, u1 and u2 independently represent integers of 0 or greater, v is an integer between 0 and 8

[0020] and a fluorene-containing (meth)acrylate represented by the following formula (3):

[0021] [ka]

[0022] [In the formula, X is a direct bond or a group represented by the following formula (4):

[0023] [ka]

[0024] (In the formula, R 10a and R 10b each independently represents a hydrogen atom, an alkyl group, or an aryl group; R 10a and R 10b may be bonded to form a hydrocarbon ring, (y is an integer of 2 or greater)

[0025] represents a linking group selected from the group A 3a and A3b each independently represents an alkylene group; w1 and w2 each independently represent an integer of 0 or more; R 8a and R 8b each independently represents a hydrogen atom or a methyl group, R 9a and R 9b each independently represents a substituent, x1 and x2 independently represent an integer of 0 to 4.

[0026] The curable resin composition of the above aspect [6], comprising at least one selected from the group consisting of bisphenol-containing (meth)acrylates represented by the following formula:

[0027] Aspect [8]: A fluorene-containing (meth)acrylate represented by the formula (2), wherein in the formula (2), the ring Z 3a and ring Z 3b represents a benzene ring, and A 2a and A 2b represents an ethylene group, the sum of t1 and t2 is 6 to 16, and the mass ratio of the fluorene-containing epoxy (meth)acrylate represented by formula (1) to the fluorene-containing (meth)acrylate represented by formula (2) is 70 / 30 to 30 / 70.

[0028] Aspect [9]: A bisphenol-containing (meth)acrylate represented by the formula (3), wherein A 3a and A 3b represents an ethylene group, the sum of w1 and w2 is 2 to 6, and the mass ratio of the fluorene-containing epoxy (meth)acrylate represented by formula (1) to the bisphenol-containing (meth)acrylate represented by formula (3) is 70 / 30 to 30 / 70.

[0029] Aspect

[10] : The curable resin composition according to any one of Aspects [6] to [9], which is a photocurable resin composition further comprising a photopolymerization initiator.

[0030] Aspect

[11] : A cured product of the curable resin composition according to any one of Aspects [6] to

[10] .

[0031] Aspect

[12] : The cured product of aspect

[11] , having a refractive index of 1.63 or more.

[0032] Aspect

[13] : A molded article formed from the cured product of aspect

[11] or

[12] .

[0033] Aspect

[14] : The molded article of aspect

[13] , which is an optical element.

[0034] In addition, fluorene compounds have a condensed polycyclic structure, and when further substituted with an aromatic ring, an improvement in refractive index can be expected, but on the other hand, since the structure becomes more bulky, handling properties such as solvent solubility tend to be reduced. Therefore, it is generally difficult to achieve high levels of both handling properties and optical properties in compounds having a polycyclic structure.

[0035] Therefore, the present disclosure may achieve the following secondary objectives (solve the problems):

[0036] An object of the present disclosure is to provide a fluorene-containing epoxy (meth)acrylate that can achieve both a high refractive index and high solvent solubility, and uses thereof.

[0037] Another object of the present disclosure is to provide a curable resin composition that can improve the refractive index and flexibility of a cured product.

[0038] Still another object of the present disclosure is to provide a curable resin composition that is flexible and gives a cured product having high pencil hardness and heat resistance.

[0039] In this specification and claims, the number of carbon atoms in a substituent or the like is expressed as C1, C6, C 10 For example, "C1 alkyl group" means an alkyl group with 1 carbon atom, and "C 6-10 The term "aryl group" refers to an aryl group having 6 to 10 carbon atoms.

[0040] In the present specification and claims, the term "independently" means that two components are independent of each other, for example, an alkylene group A 1a and A 1b In this case, A 1a and A 1b and do not necessarily have to be the same alkylene group, but may be different alkylene groups.

[0041] Furthermore, in this specification and claims, when a numerical range is indicated using "X to Y", the extreme numerical values ​​X and Y may be included. [Effects of the Invention]

[0042] According to the present disclosure, the refractive index of a fluorene-containing epoxy (meth)acrylate can be improved. [Brief explanation of the drawings]

[0043] [Figure 1] FIG. 1 is the LC-MS spectrum of 9,9-bis[6-(3-acryloyloxy-2-hydroxypropyloxy)-2-naphthyl]-2,7-di(2-naphthyl)fluorene obtained in Example 1. [Figure 2] FIG. 2 is the FD-MS spectrum of 9,9-bis[6-(3-acryloyloxy-2-hydroxypropyloxy)-2-naphthyl]-2,7-di(2-naphthyl)fluorene obtained in Example 1. [Figure 3] FIG. 3 is the LC-MS spectrum of 9,9-bis[6-(3-acryloyloxy-2-hydroxypropyloxy)-2-naphthyl]-2,7-diphenylfluorene obtained in Example 2. DETAILED DESCRIPTION OF THE INVENTION

[0044] [Fluorene-containing epoxy (meth)acrylate represented by formula (1)] The fluorene-containing epoxy (meth)acrylate represented by the formula (1) (hereinafter also referred to as "fluorene-containing epoxy (meth)acrylate (1)") has a structure in which arene rings are substituted at both the benzene ring and the 9,9-position of the fluorene ring, and therefore has a high refractive index. Furthermore, despite its bulky structure, it also has excellent solvent solubility. It also has high curability, heat resistance, and pencil hardness.

[0045] In the formula (1), ring Z 1a and ring Z 1b Examples of the arene ring (aromatic hydrocarbon ring) represented by the formula (I) include monocyclic arene rings such as a benzene ring, polycyclic arene rings, etc. Examples of the polycyclic arene ring include fused polycyclic arene rings (fused polycyclic aromatic hydrocarbon rings), and ring-assembled arene rings (ring-assembled polycyclic aromatic hydrocarbon rings).

[0046] The fused polycyclic arene ring includes fused bicyclic arene rings, fused tricyclic arene rings, and other fused bicyclic to tetracyclic arene rings. The fused bicyclic arene ring includes fused bicyclic C rings such as naphthalene rings and indene rings. 10-16 The fused tricyclic arene ring includes fused tricyclic C arenes such as anthracene ring and phenanthrene ring. 14-20 Preferred fused polycyclic arene rings include fused polycyclic C arene rings such as naphthalene rings. 10-14 It is an arene ring.

[0047] Examples of the ring-assembled arene ring include biarene rings such as biphenyl ring, phenylnaphthalene ring, and binaphthyl ring; and terarene rings such as terphenyl ring. Preferred ring-assembled arene rings include C 12-18 It is a biarene ring.

[0048] In this specification and claims, the term "ring assembly arene ring" refers to two or more ring systems (arene ring systems) directly linked by single bonds or double bonds, and the number of bonds directly linking the rings is one less than the number of ring systems. For example, as described above, phenylnaphthalene rings and binaphthyl rings are classified as ring assembly arene rings even though they have a fused polycyclic arene ring skeleton, and are clearly distinguished from "fused polycyclic arene rings" such as naphthalene rings (non-ring assembly arene rings).

[0049] Ring Z 1a is the ring Z 1b Among these arene rings, ring Z may be different from ring Z, but is preferably the same. 1a and ring Z 1b As for C 6-12 An arene ring is preferred, and a benzene ring or a fused polycyclic C 10-12 An arene ring is more preferred, a benzene ring and a naphthalene ring are even more preferred, and a naphthalene ring is even more preferred from the viewpoint of achieving both a high refractive index and high solvent solubility.

[0050] Ring Z to the 9-position of the fluorene ring 1a and ring Z 1b The bonding position of is not particularly limited, and for example, 1a and ring Z 1b When is a naphthalene ring, it is at the 1- or 2-position, preferably the 2-position.

[0051] A 1a and A 1b Examples of the alkylene group (linear or branched alkylene group) represented by the formula (I) include C alkylene groups such as ethylene group, propylene group (1,2-propanediyl group), trimethylene group, 1,2-butanediyl group, tetramethylene group, and 2-methylpropane-1,3-diyl group. 2-6 These alkylene groups can be used alone or in combination of two or more. 1a is an alkylene group A 1b Among these, C groups such as ethylene group and propylene group are preferred. 2-3Alkylene groups are preferred, with ethylene groups being particularly preferred.

[0052] The repeating numbers n1 and n2 are each 0 or more and can be selected, for example, from the range of integers from 0 to 15, preferably 0 to 10, 0 to 8, 0 to 6, 0 to 4, 0 to 2, and 0 to 1 in the following stepwise order, with 0 being the most preferred in terms of achieving both a high refractive index and high solvent solubility. Furthermore, n1 and n2 may be the same or different. When n1 and n2 are each an integer of 2 or more, two or more alkylene groups A 1a and A 1b The types may be the same or different.

[0053] In this specification and claims, the "repeating number (number of moles added)" may be an average value (arithmetic mean value, additive mean value) or an average number of moles added, and preferred embodiments may be the same as the above-mentioned preferred range of integers.

[0054] R 1a is R 1b may be different from, but are preferably the same as, 1a and R 1b is a hydrogen atom, since it is possible to achieve both a high refractive index and high solvent solubility.

[0055] Ring Z 1a and ring Z 1b The substitution position of the (meth)acryloyl-containing group on ring Z is not particularly limited. 1a and ring Z 1b is a naphthalene ring, the 1st or 2nd position of the naphthalene ring is bonded to the 9th position of the fluorene ring (bonded in a 1-naphthyl or 2-naphthyl relationship), and substitution is preferably performed in a 1,5-position or 2,6-position relationship, particularly in a 2,6-position relationship, relative to this bonding position.

[0056] R 2a and R 2bExamples of the substituent represented by the formula (non-reactive substituent or non-polymerizable substituent) include a halogen atom, a hydrocarbon group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, an acyl group, a nitro group, and a cyano group.

[0057] Representative examples of these substituents include halogen atoms, hydrocarbon groups such as alkyl groups, cycloalkyl groups, and aralkyl groups, alkoxy groups, acyl groups, nitro groups, cyano groups, and substituted amino groups. 2a and R 2b Examples of the alkyl group include an alkyl group, a cycloalkyl group, an aryl group, and an alkoxy group. Examples of the alkyl group (linear or branched alkyl group) include C 1-6 Examples of the cycloalkyl group include C alkyl groups such as cyclohexyl groups. 5-8 Examples of the aryl group include C aryl groups such as phenyl and naphthyl groups. 6-14 Examples of the alkoxy group (linear or branched chain alkoxy group) include C alkoxy groups such as methoxy groups. 1-4 Alkoxy groups and the like are examples of the substituent R 2a is the substituent R 2b Among these, alkyl groups are preferred, and C groups such as methyl groups are preferred. 1-4 Alkyl groups are particularly preferred.

[0058] R 2a and R 2b The numbers of substitutions m1 and m2 may be integers of 0 or more, and the ring Z 1a and ring Z 1b Each of m1 and m2 may be an integer of 0 to 8, preferably an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2, more preferably 0 or 1, and most preferably 0. The number of substitutions m1 may be different from the number of substitutions m2, but preferably they are the same number of substitutions. When the numbers of substitutions m1 and m2 are 2 or more, the number of substitutions m1 and m2 is 2 or more. 2aand R 2b The types may be the same or different from each other, but are preferably the same.

[0059] Ring Z 2a and ring Z 2b The arene ring represented by the formula: 1a and ring Z 1b Ring Z 2a is the ring Z 2b Among the arene rings, ring Z may be different from ring Z, but is preferably the same. 2a and ring Z 2b As for C 6-12 An arene ring is preferred, a benzene ring and a naphthalene ring are more preferred, and a fused polycyclic C 10-12 An arene ring is more preferred, and a naphthalene ring is most preferred because it can achieve both a high refractive index and high solvent solubility.

[0060] Ring Z 2a and ring Z 2b may be substituted at any of the 1- to 4-positions or the 5- to 8-positions of the fluorene skeleton, but preferred substitution positions (or bonding positions) are positions that are symmetrical on the paper in the formula (1) such as the 1,8-positions, 2,7-positions, 3,6-positions, and 4,5-positions of the fluorene ring, with the 2,7-positions being particularly preferred.

[0061] R 3a and R 3b Examples of the substituent represented by the formula (non-reactive substituent or non-polymerizable substituent) include R 2a and R 2b The substituent R 3a is the substituent R 3b Among the above substituents, alkyl groups (linear or branched alkyl groups) are preferred, and C groups such as methyl groups are also preferred. 1-4 Alkyl groups are particularly preferred.

[0062] R 3a and R 3b The substitution numbers k1 and k2 of the ring Z2a and ring Z 2b The number of substitutions k1 and k2 may be different from each other, but are preferably the same. When the number of substitutions k1 and k2 is 2 or more, the number of substitutions k1 and k2 is 2 or more. When the number of substitutions k1 and k2 is 2 or more, the number of substitutions k1 and k2 is 2 or more. When the number of substitutions k1 and k2 is 2 or more, the number of substitutions k1 and k2 is 2 or more. When the number of substitutions k1 and k2 is 2 or more, the number of substitutions k2 is 2 or more. When the number of substitutions k1 and k2 is 2 or more, the number of substitutions k2 is 0 or 1. 3a and R 3b The types may be the same or different from each other, but are preferably the same.

[0063] R 4a and R 4b Examples of the substituent represented by the formula (non-reactive substituent or non-polymerizable substituent) include R 2a and R 2b The substituent R 4a is the substituent R 4b Among the above substituents, alkyl groups (linear or branched alkyl groups) are preferred, and C groups such as methyl groups are also preferred. 1-4 Alkyl groups are particularly preferred.

[0064] R 4a and R 4b The numbers of substitutions s1 and s2 may be integers of 0 to 3, preferably integers of 0 to 2, more preferably 0 or 1, and most preferably 0. The number of substitutions s1 may be different from the number of substitutions s2, but is preferably the same. In addition, when the numbers of substitutions s1 and s2 are 2 or more, 2 or more R 4a or R 4b The types may be the same or different from each other, but are preferably the same.

[0065] Preferred fluorene-containing epoxy (meth)acrylates (1) include 9,9-bis[5-(3-(meth)acryloyloxy-2-hydroxypropyloxy)-1-naphthyl]-2,7-diphenylfluorene, 9,9-bis[6-(3-(meth)acryloyloxy-2-hydroxypropyloxy)-2-naphthyl]-2,7-diphenylfluorene, 9,9-bis[5-(3-(meth)acryloyloxy-2-hydroxypropyloxy)-1-naphthyl]-2,7-di(2-naphthyl)fluorene, 9,9-bis[6-(3-(meth)acryloyloxy-2-hydroxypropyloxy)- 9,9-bis[(3-(meth)acryloyloxy-hydroxypropyloxy)-C] such as 9,9-bis[6-(3-(meth)acryloyloxy-2-hydroxypropyloxy)-2-naphthyl]-2-naphthyl]-3,6-di(2-naphthyl)fluorene, 9,9-bis[6-(3-(meth)acryloyloxy-2-hydroxypropyloxy)-2-naphthyl]-4,5-di(2-naphthyl)fluorene, and 9,9-bis[6-(3-(meth)acryloyloxy-2-hydroxypropyloxy)-2-naphthyl]-2,7-di(1-naphthyl)fluorene. 6-12 Aryl]-diC 6-12Arylfluorene; 9,9-bis[5-{2-(3-(meth)acryloyloxy-2-hydroxypropyloxy)ethoxy}-1-naphthyl]-2,7-diphenylfluorene, 9,9-bis[6-{2-(3-(meth)acryloyloxy-2-hydroxypropyloxy)ethoxy}-2-naphthyl]-2,7-diphenylfluorene, 9,9-bis[5-{2-(3-(meth)acryloyloxy-2-hydroxypropyloxy)ethoxy}-1-naphthyl] -2,7-di(2-naphthyl)fluorene, 9,9-bis[6-{2-(3-(meth)acryloyloxy-2-hydroxypropyloxy)ethoxy}-2-naphthyl]-2,7-di(2-naphthyl)fluorene, 9,9-bis[6-{2-(3-(meth)acryloyloxy-2-hydroxypropyloxy)ethoxy}-2-naphthyl]-2,7-di(1-naphthyl)fluorene, etc. 2-4 Alkoxy-C 6-12 Aryl]-diC 6-12 Arylfluorene and the like.

[0066] The fluorene-containing epoxy(meth)acrylate of the present disclosure has a structure in which arene rings are substituted on both the benzene rings constituting the fluorene ring and the 9,9-position of the fluorene ring, and therefore has a high refractive index. The refractive index of the fluorene-containing epoxy(meth)acrylate of the present disclosure may be, for example, about 1.6 to 1.75 at a temperature of 25°C and a wavelength of 589 nm, and preferably ranges in the following stepwise order: 1.62 to 1.75, 1.63 to 1.74, 1.64 to 1.73, 1.65 to 1.69, 1.65 to 1.68, 1.655 to 1.67, and 1.655 to 1.665.

[0067] In this specification and claims, the refractive index of the fluorene-containing epoxy (meth)acrylate can be measured by the method described in the examples below.

[0068] [Method for producing fluorene-containing epoxy (meth)acrylate (1)] The fluorene-containing epoxy (meth)acrylate (1) can be produced by a conventional method, for example, by reacting a compound represented by the following formula (1a):

[0069] [ka]

[0070] (In the formula, ring Z 1a , ring Z 1b , ring Z 2a , ring Z 2b , A 1a , A 1b , n1, n2, R 2a , R 2b , R 3a , R 3b , R 4a , R 4b , m1, m2, k1, k2, s1 and s2 are the same as above, including preferred embodiments.

[0071] with (meth)acrylic acid or a derivative thereof (for example, an alkali metal salt such as sodium).

[0072] The epoxy compound represented by the formula (1a) can be prepared by a conventional method, for example, the method described in JP-A Nos. 2009-155256 and 2022-42002.

[0073] The reaction may be carried out in a solvent or without a solvent, such as aliphatic hydrocarbons like hexane and heptane, aromatic hydrocarbons like benzene and toluene, alcohols like methanol, ethanol, n-propanol, and benzyl alcohol, dialkyl ethers like diethyl ether, cyclic ethers like tetrahydrofuran (THF) and 1,4-dioxane, aromatic ethers like anisole, glycol ethers like ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether (PGME), ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol diethyl ether (DEDG). Examples of suitable ketones include chain ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK); cyclic ketones such as cyclohexanone; acetate esters such as ethyl acetate; lactate esters such as methyl lactate, ethyl lactate, and butyl lactate; lactones or cyclic esters such as γ-butyrolactone; ether esters such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA), and alkoxycarboxylic acid esters such as ethyl 3-ethoxypropionate; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; and sulfoxides such as dimethyl sulfoxide.

[0074] These solvents can be used alone or in combination of two or more. Among these, ether esters are preferred, and alkylene glycol monoalkyl ether acetates such as PGMEA are particularly preferred.

[0075] The proportion of the solvent is, for example, 1 to 100 parts by mass, preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, and even more preferably 12 to 20 parts by mass, relative to 100 parts by mass of the epoxy compound represented by the formula (1a).

[0076] The reaction may be carried out in the presence of a catalyst. The catalyst is preferably a base catalyst. The base catalyst may be an inorganic base or an organic base.

[0077] Examples of inorganic bases include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; and alkaline earth metal hydroxides such as calcium hydroxide.

[0078] Examples of organic bases include amines, quaternary ammonium salts, phosphines, and phosphonium salts. Examples of amines include aliphatic tertiary amines such as triethylamine and tributylamine; aromatic tertiary amines such as N,N-dimethylaniline; and heterocyclic amines such as pyridine, imidazole, 2-methylimidazole, and 2-ethyl-4-methylimidazole. Examples of quaternary ammonium salts include tetramethylammonium chloride, tetramethylammonium bromide, and benzyltrimethylammonium bromide. Examples of phosphines include triphenylphosphine and tributylphosphine. Examples of phosphonium salts include n-butyltriphenylphosphonium bromide.

[0079] These catalysts can be used alone or in combination. Among these catalysts, quaternary ammonium salts are preferred, and tetra C such as tetramethylammonium bromide is preferred. 1-20 Alkylammonium halides are more preferred.

[0080] The proportion of the catalyst is, for example, 0.01 to 10 mol, preferably 0.1 to 5 mol, further preferably 0.3 to 5 mol, even more preferably 0.5 to 3 mol, and most preferably 0.7 to 2 mol, relative to 100 mol of the epoxy compound represented by the formula (1a).

[0081] The reaction may be carried out in the presence of a polymerization inhibitor, if necessary. Examples of the polymerization inhibitor include hydroquinone; hydroquinone monoalkyl ethers such as hydroquinone monomethyl ether (4-methoxyphenol); and alkyl catechols such as t-butylcatechol. These polymerization inhibitors can be used alone or in combination of two or more. Among these, hydroquinone monomethyl ethers such as 4-methoxyphenol are preferred. 1-3 Alkyl ethers are preferred.

[0082] The proportion of the polymerization inhibitor is, for example, 0.01 to 10 mol, preferably 0.1 to 7 mol, further preferably 0.3 to 6 mol, even more preferably 0.5 to 5 mol, and most preferably 1 to 3 mol, relative to 100 mol of the epoxy compound represented by the formula (1a).

[0083] The reaction temperature is, for example, 50 to 150°C, preferably 70 to 140°C, further preferably 90 to 130°C, and even more preferably 100 to 120°C. The reaction time is not particularly limited and is, for example, 30 minutes to 100 hours, preferably 1 to 50 hours. The reaction is usually carried out in air or an inert gas atmosphere under normal pressure or pressure.

[0084] The reaction product may be separated and purified by a conventional method, for example, a separation means such as filtration, concentration, extraction, or crystallization.

[0085] [Curable composition and cured product thereof] The curable composition of the present disclosure includes the fluorene-containing epoxy (meth)acrylate (1). The curable composition may or may not include other polymerization components, such as a second multifunctional (meth)acrylate different from the formula (1) or a monofunctional polymerization component (or reactive diluent) such as a monofunctional (meth)acrylate.

[0086] The second polyfunctional (meth)acrylate is not particularly limited as long as it is a compound having a plurality (two or more) of (meth)acryloyl groups. The number of (meth)acryloyl groups per molecule is, for example, 2 to 10, preferably 2 to 6, more preferably 2 to 4, particularly preferably 2 to 3, and particularly preferably 2.

[0087] Examples of the second polyfunctional (meth)acrylate include epoxy (meth)acrylates (vinyl ester resins) such as aliphatic epoxy (meth)acrylates, alicyclic epoxy (meth)acrylates, aromatic epoxy (meth)acrylates, and poly(meth)acrylates of novolac epoxy resins; urethane (meth)acrylates; polyester (meth)acrylates (poly(meth)acrylates of polyester polyols having two or more hydroxyl groups); alkylene glycol di(meth)acrylates; polyalkylene glycol di(meth)acrylates; di(meth)acrylates of alicyclic diols; di(meth)acrylates of aromatic diols; 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 multifunctional (meth)acrylates may be commercially available products.

[0088] Examples of the aliphatic epoxy (meth)acrylate include di(meth)acrylates of (poly)alkylene glycol diglycidyl ethers such as di(meth)acrylates of 1,6-hexanediol diglycidyl ether and di(meth)acrylates of polypropylene glycol diglycidyl ether.

[0089] Examples of the alicyclic epoxy (meth)acrylate include C 1,4-cyclohexanedimethanol diglycidyl ether di(meth)acrylate. 5-10 Examples include di(meth)acrylates of epoxy compounds having an aliphatic ring.

[0090] Examples of the aromatic epoxy (meth)acrylate include di(meth)acrylates of diglycidyl ethers of bisphenols or biphenols, or their alkylene oxide 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.

[0091] Examples of the alkylene glycol di(meth)acrylate include C alkylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, etc. 2-10 Examples include alkylene glycol di(meth)acrylate.

[0092] Examples of the polyalkylene glycol di(meth)acrylate include di- to hexa-C di(meth)acrylate such as diethylene glycol di(meth)acrylate. 2-10 Examples include alkylene glycol di(meth)acrylate.

[0093] Examples of the di(meth)acrylate of the alicyclic diol include C di(meth)acrylate of 1,4-cyclohexanedimethanol, etc. 5-10 Examples include di(meth)acrylates of diol compounds having an aliphatic ring.

[0094] Examples of the di(meth)acrylate of the aromatic diol include di(meth)acrylate of a diol having a fluorene skeleton, di(meth)acrylate of a bisphenol or biphenol, or di(meth)acrylate of an alkylene oxide adduct thereof.

[0095] Examples of the poly(meth)acrylate of the low molecular weight polyol compound having about 3 to 6 hydroxyl groups or its alkylene oxide (alkylene carbonate or haloalkanol) adduct include glycerin tri(meth)acrylate, diglycerin tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and sorbitol tri- or hexa(meth)acrylate.

[0096] Examples of the monofunctional polymerization component (or reactive diluent) include monofunctional vinyl monomers, monofunctional (meth)acrylic monomers, etc. Examples of the 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 such as methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, methylthio (meth)acrylate, and phenylthio (meth)acrylate.

[0097] These monofunctional polymerization components can be used alone or in combination of two or more. Among these monofunctional polymerization components, monofunctional (meth)acrylic monomers, particularly monofunctional (meth)acrylates, are often used.

[0098] Among these other polymerization components, the curable composition of the present disclosure preferably contains a di(meth)acrylate of an aromatic diol. In particular, the curable composition of the present disclosure preferably contains a combination of the fluorene-containing epoxy(meth)acrylate (1) with the fluorene-containing (meth)acrylate represented by formula (2) and / or the bisphenol-containing (meth)acrylate represented by formula (3), because this combination can achieve both a high refractive index and high flexibility. Furthermore, the curable composition of the present disclosure exhibits excellent flexibility even after curing, as well as high pencil hardness and heat resistance.

[0099] (Fluorene-containing (meth)acrylate represented by formula (2)) The fluorene-containing (meth)acrylate represented by the formula (2) (hereinafter also referred to as "fluorene-containing (meth)acrylate (2)") can improve the flexibility required for films and the like by combining it with the fluorene-containing epoxy (meth)acrylate (1) without significantly reducing the high refractive index of the fluorene-containing epoxy (meth)acrylate (1).

[0100] In the formula (2), ring Z 3a and ring Z 3b The arene ring represented by the formula (1) includes ring Z 1a and ring Z 1b Examples of the arene ring include the arene rings exemplified by the ring Z. 3a is the ring Z 3b Among the arene rings, ring Z may be different from ring Z, but is preferably the same. 3a and ring Z 3b As for C 6-12 An arene ring is preferred, and a benzene ring is more preferred since it can achieve both a high refractive index and high flexibility.

[0101] A 2a and A 2b The alkylene group (linear or branched alkylene group) represented by the formula (1) includes, including preferred embodiments thereof, A 1a and A 1bThe alkylene group can be selected from the alkylene groups exemplified above.

[0102] The repeat numbers t1 and t2 are each an integer of 0 or more, and can be selected from the range of integers from 0 to 20, for example. From the viewpoint of achieving both a high refractive index and high flexibility, they are preferably integers from 1 to 15, 2 to 10, 3 to 8, 4 to 7, and more preferably 5 or 6, in the following stepwise order. The total number of t1 and t2 (t1+t2) is preferably an integer from 1 to 30, 2 to 20, 4 to 18, 6 to 16, 7 to 14, 9 to 13, and more preferably 10 to 12, in the following stepwise order. The total number of t1 and t2 may be an average value. Furthermore, t1 and t2 may be the same or different. When t1 and t2 are each an integer of 2 or more, two or more alkylene groups A 2a and A 2b The types may be the same or different.

[0103] R 5a is R 5b may be different from, but are preferably the same as, 5a and R 5b is a hydrogen atom, since it can achieve both a high refractive index and high flexibility.

[0104] Ring Z 3a and ring Z 3b The substitution position of the (meth)acryloyl-containing group on ring Z is not particularly limited. 3a and ring Z 3b When is a benzene ring, it may be at any of the 2- to 4-positions, but the 4-position is preferred.

[0105] R 6a and R 6b The substituent (non-reactive substituent or non-polymerizable substituent) represented by the formula (1), including preferred embodiments thereof, is 2a and R 2b The substituents can be selected from those exemplified as:

[0106] R 6a and R6b The ranges of the substitution numbers u1 and u2, including the preferred ranges, are the same as those of R 2a and R 2b The number of substitutions m1 and m2 can be selected from the range of

[0107] R 7 The substituent (non-reactive substituent or non-polymerizable substituent) represented by the formula (1), including preferred embodiments thereof, is 4a and R 4b The substituents can be selected from those exemplified as:

[0108] R 7 The number of substitutions v is, for example, an integer of about 0 to 6, preferably an integer of 0 to 4, an integer of 0 to 2, more preferably 0 or 1, and most preferably 0. When v is 2 or more, 2 or more R 7 The types may be the same or different from each other, but are preferably the same.

[0109] Preferred fluorene-containing (meth)acrylates (2) include 9,9-bis[(meth)acryloyloxypolyC] such as 9,9-bis[4-((meth)acryloyloxy-tetra- or heptaethoxyphenyl]fluorene]. 2-4 and alkoxy-phenyl]fluorene.

[0110] (Bisphenol-containing (meth)acrylate represented by formula (3)) The bisphenol-containing (meth)acrylate represented by the formula (3) (hereinafter also referred to as "bisphenol-containing (meth)acrylate (3)") can improve the flexibility required for films and the like by combining it with the fluorene-containing epoxy (meth)acrylate (1) without significantly reducing the high refractive index of the fluorene-containing epoxy (meth)acrylate (1).

[0111] In the formulas (3) and (4), R of the linking group of X 10a and R 10bExamples of the alkyl group represented by the formula (I) include a linear or branched C alkyl group such as a methyl group, an ethyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group. 1-6 Among these alkyl groups, linear or branched C 1-4 Alkyl groups are preferred, with methyl groups being particularly preferred.

[0112] R 10a and R 10b Examples of the aryl group represented by the formula include C 6-10 Among these aryl groups, a phenyl group is preferred.

[0113] base R 10a is the group R 10b may be different from or the same as the group R 10a and R 10b and may be bonded to each other to form a hydrocarbon ring, such as a cyclopentane ring or a cyclohexane ring. 5-8 The hydrocarbon ring may be a cycloalkane ring or the like. The hydrocarbon ring may be an alkyl group (C such as a methyl group). 1-4 It may have one or more substituents such as alkyl groups.

[0114] The linking group of X is -(CH2) y In -, y may be an integer of 2 or more, preferably 2 to 10, further preferably 2 to 6, even more preferably 2 to 4, and most preferably 2 or 3.

[0115] X is a direct bond, R 10a and R 10b is a linking group that is a methyl group, R 10a and R 10b is a hydrogen atom, -S- group, and -SO2- group are preferred, and R 10a and R 10b is more preferably a methyl group.

[0116] A 3a and A 3bThe alkylene group (linear or branched alkylene group) represented by the formula (1) includes, including preferred embodiments thereof, A 1a and A 1b The alkylene group can be selected from the alkylene groups exemplified above.

[0117] The repeat numbers w1 and w2 are each 0 or more and can be selected, for example, from the range of integers from 0 to 10. From the viewpoint of achieving both a high refractive index and high flexibility, they are preferably integers from 1 to 5, more preferably integers from 2 to 4, and even more preferably 2 or 3. The total number of w1 and w2 (w1+w2) is, for example, an integer from 1 to 10, preferably an integer from 2 to 8, more preferably an integer from 3 to 6, and even more preferably an integer from 3 to 5. The total number of w1 and w2 may be an average value. Furthermore, w1 and w2 may be the same or different. When w1 and w2 are each an integer of 2 or more, two or more alkylene groups A 3a and A 3b The types may be the same or different.

[0118] R 8a is R 8b may be different from, but are preferably the same as, 8a and R 8b is a hydrogen atom, since it can achieve both a high refractive index and high flexibility.

[0119] R 9a and R 9b The substituent (non-reactive substituent or non-polymerizable substituent) represented by the formula (1), including preferred embodiments thereof, is 2a and R 2b The substituents can be selected from those exemplified as:

[0120] R 9a and R 9bThe numbers of substitutions x1 and x2 may be integers of 0 to 4, preferably integers of 0 to 2, more preferably 0 or 1, and most preferably 0. The number of substitutions x1 may be different from the number of substitutions x2, but is preferably the same. When the numbers of substitutions x1 and x2 are 2 or more, the number of substitutions x1 and x2 is 2 or more. 9a or R 9b The types may be the same or different from each other, but are preferably the same.

[0121] Preferred bisphenol-containing (meth)acrylates (3) include di(meth)acrylates of ethylene oxide (EO) 4-mol adducts of biphenol; di(meth)acrylates of EO adducts of bisphenols, such as di(meth)acrylates of EO 2-mol adducts of bisphenol A, di(meth)acrylates of EO 4-mol adducts of bisphenol A, di(meth)acrylates of EO 4-mol adducts of bisphenol F, and di(meth)acrylates of EO 4-mol adducts of bisphenol S.

[0122] (Proportion of polymerized components) When a high refractive index is required for the curable resin composition of the present disclosure, the proportion of the fluorene-containing (meth)epoxy acrylate (1) can be, for example, 10% by mass or more, specifically, selected from a range of about 30 to 100% by mass, based on the total amount of polymerization components, preferably 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, and particularly preferably substantially 100% by mass, i.e., the polymerization component is solely the fluorene-containing epoxy (meth)acrylate (1). When the proportion of the fluorene-containing epoxy (meth)acrylate (1) is above the lower limit, the refractive index and heat resistance tend to be improved.

[0123] When the curable resin composition of the present disclosure is required to have high flexibility in addition to a high refractive index, it is preferable to combine the fluorene-containing epoxy(meth)acrylate (1) with the fluorene(meth)acrylate (2) and / or bisphenol(meth)acrylate (3). The mass ratio of the fluorene-containing epoxy(meth)acrylate (1) to the total amount of the fluorene(meth)acrylate (2) and bisphenol(meth)acrylate (3) is, for example, [(1)] / [(2)+(3)]=90 / 10 to 10 / 90, preferably 80 / 20 to 20 / 80, more preferably 70 / 30 to 30 / 70, and even more preferably 60 / 40 to 40 / 60.

[0124] In particular, the mass ratio of the fluorene-containing epoxy (meth)acrylate (1) to the fluorene (meth)acrylate (2) is, for example, the former / latter = 90 / 10 to 10 / 90, preferably 80 / 20 to 20 / 80, further preferably 70 / 30 to 30 / 70, and even more preferably 60 / 40 to 40 / 60.

[0125] The mass ratio of the fluorene-containing epoxy (meth)acrylate (1) to the bisphenol (meth)acrylate (2) is, for example, the former / latter = 90 / 10 to 10 / 90, preferably 80 / 20 to 20 / 80, more preferably 70 / 30 to 30 / 70, and even more preferably 60 / 40 to 40 / 60.

[0126] (Other ingredients) The curable composition may further contain a polymerization initiator, a solvent, an additive, and the like in addition to the polymerization component (or the monomer component).

[0127] The polymerization initiator may be a thermal polymerization initiator (thermal radical generator) or a photopolymerization initiator (photoradical generator).

[0128] Examples of thermal polymerization initiators include organic peroxides and azo compounds. Examples of organic peroxides include dialkyl peroxides such as di-t-butyl peroxide; diacyl peroxides such as lauroyl peroxide and benzoyl peroxide; peracids (or peresters) such as t-butyl hydroperoxide, cumene hydroperoxide, and t-butyl peracetate; ketone peroxides; peroxycarbonates; and peroxyketals. Examples of azo compounds include azonitrile compounds such as 2,2'-azobis(isobutyronitrile), azoamide compounds, and azoamidine compounds. These thermal polymerization initiators can be used alone or in combination of two or more.

[0129] Photopolymerization initiators include phosphines such as phenyl-bis(2,4,6-trimethylbenzoyl)-phosphine oxide (BAPO), diphenyl-2,4,6-trimethylbenzoyl-phosphine oxide (MAPO), phenyl-2,4,6-trimethylbenzoyl-ethoxy-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-methyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-ethyl-phosphine oxide, and bis(2,4,6-trimethylbenzoyl)-n-butyl-phosphine oxide; benzoins such as benzoin and benzoin ethyl ether; and acetophenone. Examples of photopolymerization initiators include acetophenones such as 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1-hydroxycyclohexyl phenyl ketone; 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.

[0130] Among these polymerization initiators, photopolymerization initiators are preferred. Furthermore, among the photopolymerization initiators, those containing phosphines are preferred, and photopolymerization initiators containing acylphosphine oxide-based polymerization initiators are more preferred, and diphenyl-tri-C such as MAPO are more preferred. 1-3 Photoinitiators containing alkylbenzoyl-phosphine oxides are particularly preferred.

[0131] From the viewpoint of improving curability, it is preferable to combine a phosphine and an acetophenone as a photopolymerization initiator. The proportion of the acetophenone is, for example, 1 to 1,000 parts by mass, preferably 10 to 500 parts by mass, more preferably 50 to 300 parts by mass, and even more preferably 100 to 200 parts by mass, relative to 100 parts by mass of the phosphines.

[0132] The proportion of the polymerization initiator (thermal and / or photopolymerization initiator) is, for example, 0.1 to 15 parts by mass, preferably 0.5 to 10 parts by mass, more preferably 1 to 8 parts by mass, and even more preferably 2 to 7 parts by mass, relative to 100 parts by mass of the total amount of the polymerization components.

[0133] The photopolymerization initiator may be combined with a photosensitizer. Typical examples of the photosensitizer include tertiary amines, such as trialkylamines; trialkanolamines such as triethanolamine; dialkylaminobenzoic acid alkyl esters, specifically, N,N-dimethylaminobenzoic acid ethyl esters such as p-(dimethylamino)benzoic acid ethyl esters, N,N-dimethylaminobenzoic acid amyl esters such as p-(dimethylamino)benzoic acid amyl esters; bis(dialkylamino)benzophenones such as 4,4-bis(diethylamino)benzophenone; and dialkylaminobenzophenones such as 4-(dimethylamino)benzophenone. These photosensitizers may be used alone or in combination of two or more.

[0134] The proportion of the photosensitizer is, for example, 1 to 200 parts by mass, preferably 5 to 150 parts by mass, and more preferably 10 to 100 parts by mass, relative to 100 parts by mass of the polymerization initiator.

[0135] The curable composition may not contain a solvent. However, since the fluorene-containing epoxy (meth)acrylate (1) has unexpectedly high solubility, the curable composition may contain a solvent as needed to adjust the handling properties.

[0136] Examples of solvents include alcohols such as methanol, ethanol, n-propanol, and benzyl alcohol; dialkyl ethers such as diethyl ether; cyclic ethers such as tetrahydrofuran (THF) and 1,4-dioxane; aromatic ethers such as anisole; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether (PGME), ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol diethyl ether (DEDG); acetone, methyl ethyl ketone (M chain ketones such as methyl isobutyl ketone (MIBK) and methyl isobutyl ketone (MIBK); cyclic ketones such as cyclohexanone; lactones or cyclic esters such as γ-butyrolactone; alkylene glycol monoalkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate (PGMEA); alkoxycarboxylic acid esters such as ethyl 3-ethoxypropionate; amides such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide, and N-methyl-2-pyrrolidone (NMP); and sulfoxides such as dimethyl sulfoxide (DMSO).

[0137] These solvents can be used alone or in combination of two or more. Among these solvents, aromatic alcohols such as benzyl alcohol, aromatic ethers such as anisole, glycol ethers such as PGME, chain ketones such as acetone, cyclic ketones such as cyclohexane, lactones such as γ-butyrolactone, amides such as DMF and NMP, and sulfoxides such as DMSO are preferred because they have excellent solubility for the fluorene-containing epoxy (meth)acrylate (1).

[0138] The proportion of the solvent is not particularly limited, and the concentration of the solid content (components other than the solvent) relative to the entire curable composition is, for example, 0.1 to 90 mass%, preferably 1 to 80 mass%, further preferably 3 to 70 mass%, even more preferably 5 to 60 mass%, and most preferably 10 to 50 mass%.

[0139] Examples of additives include conventional additives such as colorants, stabilizers, fillers, antistatic agents, flame retardants, surfactants, plasticizers, curing agents, and polymerization inhibitors. Examples of stabilizers include heat stabilizers, antioxidants, and ultraviolet absorbers. These additives can be used alone or in combination of two or more.

[0140] The proportion of the additive is, for example, about 30% by mass or less, preferably 20% by mass or less, 10% by mass or less, and 5% by mass or less in stages relative to the total curable composition. The proportion may be 0.001 to 15% by mass, specifically 0.01 to 3% by mass.

[0141] [Cured product] The curable composition of the present disclosure can be easily cured by applying active energy (or active energy rays) to produce a cured product. The active energy can be thermal energy and / or light energy, such as ultraviolet light or X-rays.

[0142] When heat treatment is carried out using thermal energy, the heating temperature is, for example, 50 to 200°C, preferably 60 to 150°C, and more preferably 70 to 120°C.

[0143] When light energy such as ultraviolet light is used for light irradiation, the amount of light irradiation energy can be appropriately selected depending on the application, for example, 50 to 10,000 mJ / cm 2 , preferably 70 to 8000 mJ / cm 2 , and more preferably 100 to 5000 mJ / cm 2 , more preferably 200 to 3000 mJ / cm 2 , and most preferably 300 to 1000 mJ / cm2 is.

[0144] The shape of the cured product is not particularly limited, and may be a three-dimensional cured product such as a lens or tube; a two-dimensional cured product (or cured film) such as a film, sheet, or plate; or a one-dimensional cured product such as a line, fiber, or rod.

[0145] The method for producing the cured product is not particularly limited, and for example, the curable composition may be molded or poured (injected) into a predetermined mold depending on the shape of the cured product, followed by a curing treatment (heating and / or light irradiation). Furthermore, in the case of a two-dimensional cured product, the curable composition may be applied to a substrate or base, for example, a metal such as aluminum; an inorganic material or ceramic such as titanium oxide, glass, or quartz; an organic material or plastic such as a cyclic olefin resin or polycarbonate resin; or a porous body such as wood, to form a film-like coating (or thin film), followed by a curing treatment.

[0146] The cured product of the present disclosure exhibits a high refractive index because it is formed from the fluorene-containing epoxy (meth)acrylate compound (1). Therefore, the refractive index nD of the cured product at a temperature of 25°C and a wavelength of 589 nm may be, for example, about 1.6 to 1.8, and preferably ranges in the following stepwise order: 1.63 or more, 1.63 to 1.77, 1.65 to 1.75, 1.655 to 1.74, 1.66 to 1.73, 1.665 to 1.71, 1.67 to 1.7, 1.675 to 1.695, and 1.68 to 1.69.

[0147] The cured product of the present disclosure also has high heat resistance, and the glass transition temperature Tg of the cured product may be, for example, about 150 to 300°C, and preferably the following stepwise temperatures: 180 to 270°C, 200 to 250°C, 210 to 245°C, 220 to 240°C, and 230 to 235°C.

[0148] The 5% weight loss temperature of the cured product may be, for example, about 300 to 450°C, and preferably ranges in the following stepwise order: 330 to 440°C, 340 to 430°C, 350 to 420°C, 355 to 410°C, 360 to 400°C, 365 to 395°C, and 370 to 390°C.

[0149] The pencil hardness of the cured product (particularly the cured film) is, for example, HB or higher, preferably F or higher, further preferably H or higher, and even more preferably 2H or higher.

[0150] In this specification and claims, the refractive index, 5% weight loss temperature, glass transition temperature and pencil hardness of the cured product can be measured by the methods described in the examples below. [Example]

[0151] 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 evaluation items and raw materials are shown below.

[0152] (LC-MS) The HPLC (high performance or high performance liquid chromatograph) was performed using a Shimadzu Corporation "Nexera XR" device, an "LCMS-2020" MS unit, and a Phenomenex "Kinetex C-18" column. The sample was dissolved in a mixed solvent of acetonitrile and THF (acetonitrile / THF = 90 / 10 (mass ratio)) and measured.

[0153] (FD-MS) Mass spectrometry (MS) was performed using the following measuring equipment and conditions.

[0154] Equipment used: “JMS-T200GC” manufactured by JEOL Ltd. Ionization method: FD (field desorption) Emitter: Carbon Emitter current: 0 to 50mA (25mA / min)

[0155] ( 1 H-NMR) The sample was dissolved in a heavy solvent (DMSO-d6) containing tetramethylsilane as an internal standard, and the NMR spectra were analyzed using a nuclear magnetic resonance spectrometer (BRUKER "AVANCE III HD"). 1 H-NMR spectrum was measured.

[0156] (Solubility) Each of the solvents described below was added to 100 mg of sample to adjust the concentration to 30% by mass, and the sample was stirred for 1 hour at room temperature (25°C) to check its solubility in each solvent. If the sample did not dissolve at room temperature (25°C), it was gradually heated to 50°C or 80°C, and after reaching 80°C, it was stirred for 1 hour, and the solubility was checked according to the following evaluation criteria.

[0157] ◎: Dissolved at 25℃ ○: Dissolved at 50℃ △: Dissolved at 80℃ ×: No dissolution even after stirring for 1 hour after reaching 80°C

[0158] (Refractive index nD) The refractive index was measured using a refractometer at a temperature of 25°C and a wavelength of 589 nm (D-line). The refractive index before curing (refractive index of fluorene-containing epoxy (meth)acrylate) was measured using an "RX-7000i" refractometer manufactured by Atago Co., Ltd., and the refractive index of the cured product was measured using a "DR-M2 / 1410" refractometer manufactured by Atago Co., Ltd. Furthermore, the refractive index before curing was calculated by dissolving the sample in PGMEA to prepare solutions with concentrations of 10, 30, and 50% by mass, measuring the refractive index of the resulting solutions and a solution with a concentration of 0% by mass (PGMEA only), and extrapolating the concentration to 100% by mass on a calibration curve (approximate straight line).

[0159] (curable) The sample (curable resin composition) coated on a TAC (cellulose acetate) film was heated on a hot plate at 100°C for 5 minutes, and then irradiated with UV light (500 mJ / cm) using a high-pressure mercury lamp. 2 The curability under the conditions was evaluated according to the following criteria.

[0160] ○: Hardened without stickiness ×: Sticky and not cured sufficiently

[0161] (Flexibility) The cured film formed on the TAC film was evaluated according to the following criteria.

[0162] ○: The cured film can be peeled cleanly from the TAC film △: Can be peeled off from the TAC film, but not cleanly ×: Cannot be peeled off from TAC film

[0163] (5% weight loss temperature) Using a thermogravimetry-differential thermal analyzer (TG-DTA) (Rigaku Corporation, "TG-DTA8122"), the temperature at which the sample lost 5% by mass was measured under conditions of a nitrogen atmosphere and a heating rate of 10°C / min.

[0164] (glass transition temperature Tg) The glass transition temperature of the sample was measured using a differential scanning calorimeter (DSC) (TA Instruments "Discovery DSC25") at a measurement temperature of 30 to 350°C and a temperature rise rate of 10°C / min.

[0165] (Pencil hardness) In accordance with the pencil hardness method (JIS K-5600-5-4 (1999)), a pencil hardness tester ("HEIDON-14" manufactured by Shinto Scientific Co., Ltd.) was used to measure the hardness of a 10 μm thick cured film formed on a polyethylene terephthalate plate by pressing it at an angle of 45° with a load of 750 g and moving it at a speed of 1 mm / sec.

[0166] (Raw materials and reagents) BNFGA: 9,9-bis[6-(3-acryloyloxy-2-hydroxypropoxy)-2-naphthyl]fluorene represented by the following formula, synthesized in accordance with Example 1 of JP-A 2001-354735

[0167] [ka]

[0168] DNBNF: 9,9-bis(6-hydroxy-2-naphthyl)-2,7-di(2-naphthyl)fluorene represented by the following formula, synthesized in accordance with Synthesis Example 1 and Example 1A described in JP-A 2022-42002

[0169] [ka]

[0170] DNBNFG: 9,9-bis(6-glycidyloxy-2-naphthyl)-2,7-di(2-naphthyl)fluorene represented by the following formula, synthesized in accordance with Example 3A of JP-A 2022-42002

[0171] [ka]

[0172] DPBNF: 9,9-bis(6-hydroxy-2-naphthyl)-2,7-diphenylfluorene represented by the following formula, synthesized in accordance with Synthesis Example 1 and Example 1A described in JP-A 2022-42002

[0173] [ka]

[0174] DPBNFG: 9,9-bis(6-glycidyloxy-2-naphthyl)-2,7-diphenylfluorene represented by the following formula, synthesized in accordance with Example 3A of JP-A 2022-42002

[0175] [ka]

[0176] DNFPA: 2,7-dinaphthylfluorene-9,9-dipropyl diacrylate [or 9,9-bis(3-acryloyloxypropyl)-2,7-di(2-naphthyl)fluorene] represented by the following formula, synthesized in accordance with the method described in Example 1 of WO2021 / 131942

[0177] [ka]

[0178] BPEF-9EOA: a diacrylate adduct in which an average of 9 moles of ethylene oxide (EO) is added to 1 mole of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF) represented by the following formula, synthesized according to the method described in Reference Example 4 of JP-A 2013-53310.

[0179] [ka]

[0180] BisA-4EOA: Diacrylate of an adduct in which an average of 4 moles of ethylene oxide are added to 1 mole of bisphenol A represented by the following formula, "FA-324A" manufactured by Hitachi Chemical Co., Ltd.

[0181] [ka]

[0182] Example 1 (Synthesis of DNBNFGA) The reaction was carried out by adding 48.9 g (0.06 mol) of DNBNFG, 10.8 g (0.15 mol) of acrylic acid, 7.5 g of propylene glycol monomethyl acetate, 0.09 g (0.6 mmol) of tetramethylammonium bromide, and 0.13 g (1.0 mmol) of 4-methoxyphenol to a 100 mL flask, followed by stirring at 110°C for 10 hours, thereby carrying out the reaction shown in the following formula, and obtaining 9,9-bis[6-(3-acryloyloxy-2-hydroxypropyloxy)-2-naphthyl]-2,7-di(2-naphthyl)fluorene (DNBNFGA).

[0183] [ka]

[0184] The LC-MS spectrum of the obtained DNBNFGA is shown in Figure 1, and the FD-MS spectrum is shown in Figure 2. In Figure 2, a peak at m / z = 958, which corresponds to DNBNFGA, was confirmed. 1 The results of the H-NMR spectrum are shown below.

[0185] 1 H-NMR (DMSO-d6, 300MHz): δ(ppm)4.04-4.28(m,10H), 5.44(OH,2H), 6.12(dd,4H), 6.12-6.22(m,2H), 7.09(d ,2H), 7.29(s,2H), 7.47-7.57(m,6H), 7.70(d,4H), 7.81(t,4H), 7.89-8.01(m,10H), 8.18(d,2H), 8.23(s,2H)

[0186] The refractive index nD of the obtained DNBNFGA was 1.66. The solubility of the obtained DNBNFGA was evaluated, and the results are shown in Table 1.

[0187] (Preparation of curable composition and production of cured film) To 100 parts by mass (3.00 g) of DNBNFGA, 3 parts by mass of photoinitiator A ("Omnirad 184" manufactured by IGM Reins BV) and 2 parts by mass of photoinitiator B ("Omnirad TPO H" manufactured by IGM Reins BV) were added, diluted with 3.00 g of solvent (PGMEA), and mixed to prepare a curable composition. The resulting curable composition was applied to a TAC (cellulose acetate) film using an applicator, heated on a hot plate at 100°C for 5 minutes, and then irradiated with UV (500 mJ / cm) from a high-pressure mercury lamp. 2 ) to obtain a cured film. The obtained cured product of DNBNFGA had a refractive index of 1.687, a Tg of 231.7°C, a 5% weight loss temperature of 380°C, and a pencil hardness of 2H. The evaluation results are shown in Table 2.

[0188] Example 2 (Synthesis of DPBNFGA) The reaction was carried out by adding 11.6 g (15.5 mmol) of DPBNFG, 2.4 g (34.8 mmol) of acrylic acid, 13.1 g of propylene glycol monomethyl acetate, 0.02 g (0.2 mmol) of tetramethylammonium bromide, and 0.03 g (0.3 mmol) of 4-methoxyphenol to a 100 mL flask, stirring at 110°C for 30 hours, and carrying out the reaction shown in the following formula, to obtain 27.1 g of 9,9-bis[6-(3-acryloyloxy-2-hydroxypropyloxy)-2-naphthyl]-2,7-diphenylfluorene (DPBNFGA) as a propylene glycol monomethyl acetate solution with a solids content of 50 mass%.

[0189] [ka]

[0190] The LC-MS spectrum of the obtained DPBNFGA is shown in Figure 3. In Figure 3, a peak corresponding to DNBNFGA was confirmed at m / z = 859 (= 858 [DPBNFGA] + 1 [e+]). 1 The results of the H-NMR spectrum are shown below.

[0191] 1 H-NMR (DMSO-d6, 300MHz): δ(ppm)4.04-4.28(m,10H), 5.46(OH,2H), 6.14(dd,4H), 6.14-6.23(m,2H), 7.09(d,2) H), 7.29-7.33(m,4H), 7.42(t,4H), 7.50(d,2H), 7.61-7.68(m,8H), 7.76-7.85(m,4H), 7.85(s,2H), 8.10(d,2H)

[0192] The refractive index nD of the obtained DPBNFGA was 1.659. The solubility of the obtained DPBNFGA was evaluated, and the results are shown in Table 1.

[0193] (Preparation of curable composition and production of cured film) To 100 parts by mass (3.00 g) of DPBNFGA, 3 parts by mass of photoinitiator A ("Omnirad 184" manufactured by IGM Reins BV) and 2 parts by mass of photoinitiator B ("Omnirad TPO H" manufactured by IGM Reins BV) were added, diluted with 3.00 g of solvent (PGMEA), and mixed to prepare a curable composition. The resulting curable composition was applied to a TAC (cellulose acetate) film using an applicator, heated on a hot plate at 100°C for 5 minutes, and then irradiated with UV (500 mJ / cm) from a high-pressure mercury lamp. 2 ) to obtain a cured film. The obtained cured DPBNFGA product had a refractive index of 1.682, a Tg of 239.9°C, a 5% weight loss temperature of 280°C, and a pencil hardness of 2H. The evaluation results are shown in Table 2.

[0194] Example 3 (Preparation of curable composition and production of cured film) To 50 parts by mass (1.50 g) of DNBNFGA and 50 parts by mass (1.50 g) of BPEF-9EOA, 3 parts by mass of photoinitiator A ("Omnirad 184" manufactured by IGM Reins BV) and 2 parts by mass of photoinitiator B ("Omnirad TPO H" manufactured by IGM Reins BV) were added, diluted with 3.00 g of solvent (PGMEA), and mixed to prepare a curable composition. The resulting curable composition was applied to a TAC (cellulose acetate) film using an applicator, heated on a hot plate at 100°C for 5 minutes, and then irradiated with UV (500 mJ / cm) using a high-pressure mercury lamp. 2 ) to obtain a cured film. The obtained cured product of DNBNFGA had a refractive index of 1.630, a Tg of 113.3°C, a 5% weight loss temperature of 366°C, and a pencil hardness of 3H. The evaluation results are shown in Table 2.

[0195] Example 4 (Preparation of curable composition and production of cured film) To 50 parts by mass (1.50 g) of DNBNFGA and 50 parts by mass (1.50 g) of bisphenol A-4EOA, 3 parts by mass of photoinitiator A ("Omnirad 184" manufactured by IGM Reins BV) and 2 parts by mass of photoinitiator B ("Omnirad TPO H" manufactured by IGM Reins BV) were added, diluted with 3.00 g of solvent (PGMEA), and mixed to prepare a curable composition. The resulting curable composition was applied to a TAC (cellulose acetate) film using an applicator, heated on a hot plate at 100°C for 5 minutes, and then irradiated with UV (500 mJ / cm) from a high-pressure mercury lamp. 2 ) to obtain a cured film. The obtained cured product of DNBNFGA had a refractive index of 1.637, a Tg of 136.1°C, a 5% weight loss temperature of 372°C, and a pencil hardness of 3H. The evaluation results are shown in Table 2.

[0196] Comparative Examples 1 to 3 The solubility results of BNFGA are shown in Table 1 as Comparative Example 1, those of DNBNF are shown in Table 1 as Comparative Example 2, and those of DNFPA are shown in Table 1 as Comparative Example 3.

[0197] Furthermore, curable compositions were prepared from BNFGA of Comparative Example 1 and DNFPA of Comparative Example 3 in the same manner as in Example 1, and the cured products were evaluated. The results are shown in Table 2.

[0198] [Table 1]

[0199] [Table 2]

[0200] The cured products of Examples 1 and 2 exhibited higher refractive indices than those of Comparative Example 1. Furthermore, the cured products of Examples 1 and 2 exhibited higher glass transition temperatures than those of Comparative Example 3. Furthermore, the DNBNFGA of Example 1 and the DPBNFGA of Example 2 exhibited solvent solubility equivalent to that of Comparative Example 1, despite having a structure with more aromatic rings than those of Comparative Examples 1 to 3. Of these, the DNBNFGA of Example 1 exhibited the highest solvent solubility, despite having a structure with the most aromatic rings.

[0201] Furthermore, the cured products of Examples 3 and 4 could be obtained as flexible films without a significant decrease in refractive index, and despite their flexibility, they had high pencil hardness and excellent heat resistance. [Industrial Applicability]

[0202] The fluorene-containing epoxy (meth)acrylate of the present disclosure has excellent properties such as high heat resistance and a high refractive index, and can be used in various heat- or photo-curable (meth)acrylic resin applications, and is preferably suitable for use in photo-curable (meth)acrylic resin applications.

[0203] Specifically, the curable resin composition containing the fluorene-containing epoxy (meth)acrylate of the present disclosure (or a cured product obtained using the curable resin composition containing the fluorene-containing epoxy (meth)acrylate of the present disclosure) can be used in a wide variety of applications, including ink materials; light-emitting materials such as light-emitting materials for organic electroluminescence (EL) applications; organic semiconductors; graphitization precursors; gas separation membranes such as CO gas separation membranes; coating agents, for example, optical overcoats or hard coats such as coating agents for LED (light-emitting diode) elements; lenses, for example, pickup lenses such as pickup lenses for DVDs (digital versatile discs), and microlenses for liquid crystal projectors. The fluorene-containing epoxy (meth)acrylate of the present disclosure can be suitably used for applications such as microlenses, eyeglass lenses, polarizing films such as polarizing films for liquid crystal displays, anti-reflection films such as anti-reflection films for display devices, materials for touch panels, materials for flexible substrates, display materials (filters, films such as protective films, etc.) for PDPs (plasma displays), LCDs (liquid crystal displays), organic electroluminescent displays, VFDs (vacuum fluorescent displays), SEDs (surface-conduction electron-emitting displays), FEDs (field emission displays), NEDs (nano-emissive displays), cathode ray tubes, and electronic paper, etc., membranes for fuel cells, optical fibers, optical waveguides, holograms, etc. In particular, the fluorene-containing epoxy (meth)acrylate of the present disclosure can be suitably used for optical material applications, and the optical materials can be in the form of films, sheets, plates, lenses, tubes, etc., although irregular shapes are also acceptable when used as resist additives for color filters, etc.

Claims

1. The following formula (1) 【Chemical 1】 (In the formula, Ring Z １ａ , ring Z １ｂ , ring Z ２ａ and ring Z ２ｂ each independently represents an arene ring, A １ａ and A １ｂ each independently represents an alkylene group; n1 and n2 each independently represent an integer of 0 or more; R １ａ and R １ｂ each independently represents a hydrogen atom or a methyl group, R ２ａ , R ２ｂ , R ３ａ , R ３ｂ , R ４ａ and R ４ｂ each independently represents a substituent, m1, m2, k1, and k2 each independently represent an integer of 0 or more; s1 and s2 independently represent an integer of 0 to 3. Fluorene-containing epoxy (meth)acrylate represented by the formula:

2. In the formula (1), ring Z １ａ and ring Z １ｂ represents a naphthalene ring, and ring Z ２ａ and ring Z ２ｂ The fluorene-containing epoxy (meth)acrylate according to claim 1, wherein represents a benzene ring or a naphthalene ring.

3. In the formula (1), ring Z １ａ , ring Z １ｂ , ring Z ２ａ and ring Z ２ｂ The fluorene-containing epoxy (meth)acrylate according to claim 1 or 2, wherein represents a naphthalene ring.

4. 3. The fluorene-containing epoxy (meth)acrylate according to claim 1, wherein n1 and n2 each represent 0 or 1 in formula (1).

5. In the formula (1), R １ａ and R １ｂ The fluorene-containing epoxy (meth)acrylate according to claim 1 or 2, wherein represents a hydrogen atom.

6. A curable resin composition comprising the fluorene-containing epoxy (meth)acrylate according to claim 1 or 2.

7. Furthermore, the following formula (2) 【Chemistry 2】 (In the formula, Ring Z ３ａ and ring Z ３ｂ each independently represents an arene ring, A ２ａ and A ２ｂ each independently represents an alkylene group; t1 and t2 each independently represent an integer of 0 or more; R ５ａ and R ５ｂ each independently represents a hydrogen atom or a methyl group, R ６ａ , R ６ｂ and R ７ each independently represents a substituent, u1 and u2 independently represent an integer of 0 or more, and v represents an integer of 0 to 8. and a fluorene-containing (meth)acrylate represented by the following formula (3): 【Chemistry 3】 [In the formula, X is a direct bond or the following formula (4): 【Chemistry 4】 (In the formula, R １０ａ and R １０ｂ each independently represents a hydrogen atom, an alkyl group, or an aryl group; R １０ａ and R １０ｂ may be bonded to form a hydrocarbon ring, and y represents an integer of 2 or more. represents a linking group selected from the group A ３ａ and A ３ｂ each independently represents an alkylene group; w1 and w2 each independently represent an integer of 0 or more; R ８ａ and R ８ｂ each independently represents a hydrogen atom or a methyl group, R ９ａ and R ９ｂ each independently represents a substituent, x1 and x2 independently represent an integer of 0 to 4.

7. The curable resin composition according to claim 6, comprising at least one member selected from the group consisting of bisphenol-containing (meth)acrylates represented by the formula:

8. The compound contains a fluorene-containing (meth)acrylate represented by the formula (2), and in the formula (2), the ring Z ３ａ and ring Z ３ｂ represents a benzene ring, and A ２ａ and A ２ｂ represents an ethylene group, the total number of t1 and t2 is 6 to 16, and the mass ratio of the fluorene-containing epoxy (meth)acrylate represented by formula (1) to the fluorene-containing (meth)acrylate represented by formula (2) is the former / latter = 70 / 30 to 30 / 70.

9. The bisphenol-containing (meth)acrylate represented by the formula (3) is contained, and in the formula (3), A ３ａ and A ３ｂ represents an ethylene group, the total number of w1 and w2 is 2 to 6, and the mass ratio of the fluorene-containing epoxy (meth)acrylate represented by formula (1) to the bisphenol-containing (meth)acrylate represented by formula (3) is the former / latter = 70 / 30 to 30 / 70.

10. The curable resin composition according to claim 6, which is a photocurable resin composition further comprising a photopolymerization initiator.

11. A cured product of the curable resin composition according to claim 6.

12. The cured product according to claim 11, which has a refractive index of 1.63 or more.

13. A molded article formed from the cured product according to claim 11.

14. The molded article according to claim 13, which is an optical element.

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