Curable composition and cured product thereof

Abstract

The present invention prepares a curable composition containing a (meth) acrylate having a 9, 9-bisarylfluorene skeleton, and a naphthyl methyl (meth) acrylate. The (meth) acrylate having a 9, 9-bisarylfluorene skeleton may include a (meth) acrylate represented by formula (1). (In formula (1), R1 represents a substituent, m1 represents an integer of 0-8, Z1a and Z1b independently represent an aromatic hydrocarbon ring, R2a and R2b independently represent a substituent, m2a and m2b independently represent an integer of 0 or more, A1a and A1b independently represent an alkylene group, n1a and n1b independently represent a number of 0 or more, and R3a and R3b independently represent a hydrogen atom or a methyl group. . The curable composition has an excellent balance between a high refractive index and a low viscosity, and also has excellent storage stability.

Description

Technical Field

[0001] This disclosure relates to (meth)acrylate compounds having a 9,9-bisarylfluorene backbone, curable compositions containing naphthyl methyl methacrylate and cured products thereof, as well as methods of manufacturing and uses thereof. Background Technology

[0002] Fluorene-based (meth)acrylate compounds [fluorene-based (meth)acrylates] exhibit excellent optical properties, including high refractive index, and are therefore effectively used as optical plastics (or optical resins) in various optical components. However, despite their high refractive index, fluorene-based (meth)acrylates often suffer from insufficient workability. Therefore, efforts have been made to reduce viscosity by adding solvents or reactive diluents, for example, reactive diluents that are less restrictive in their use as curable compositions compared to solvents.

[0003] Japanese Patent Application Publication No. 2013-53310 (Patent Document 1) discloses a curable composition containing a curable component, which is composed of a specific polyfunctional (meth)acrylate containing a 9,9-bisphenylfluorene skeleton and phenoxybenzyl (meth)acrylate as a reactive diluent.

[0004] In addition, International Publication No. 2021 / 131942 (Patent Document 2) discloses a specific di(meth)acrylate having an aryl fluorene skeleton [e.g., 2,7-di(2-naphthyl)fluorene skeleton, etc.] bonded at positions 1 to 8 (instead of 9,9-position).

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2013-53310

[0008] Patent Document 2: International Publication No. 2021 / 131942 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] Generally, while the viscosity of high-refractive-index (meth)acrylates can be reduced by adding reactive diluents, the refractive index tends to decrease with each addition. A trade-off often exists between high refractive index and low viscosity. Patent Document 1 describes a curable composition that exhibits a high refractive index and improves workability (by reducing viscosity) without compromising curability. However, in recent years, there has been a demand for further increases in refractive index, which the curable composition described in Patent Document 1 sometimes cannot adequately address. There is room for improvement in achieving a balance between high refractive index and low viscosity at a higher level.

[0011] Furthermore, the embodiments in Patent Document 2 describe 9,9-bis(3-hydroxypropyl)-2,7-bis(2-naphthyl)fluorene as a solid exhibiting an extremely high refractive index, and the curable composition containing this compound can achieve a good balance between high refractive index and low viscosity. However, Patent Document 2 does not describe the storage stability of the curable composition.

[0012] Therefore, the purpose of this disclosure is to provide a curable composition and its cured product that have an excellent balance between high refractive index and low viscosity and excellent storage stability, as well as a method for manufacturing the composition and its use.

[0013] Methods for solving problems

[0014] In order to achieve a better balance between high refractive index and low viscosity at a higher level, as described in the reference examples below, the inventors attempted to prepare curable compositions by combining di(meth)acrylates having a diarylfluorene skeleton with aryl groups bonded at positions 1 to 8 as described in Patent Document 2 with a specific reactive diluent. However, they found that the curable compositions exhibited low storage stability. Based on this finding, the inventors conducted further in-depth research to achieve the aforementioned problem. They discovered that when a specific di(meth)acrylate having a 9,9-bisarylfluorene skeleton (with aryl groups bonded at positions 9,9- instead of 1 to 8) is combined with a specific reactive diluent, the resulting curable compositions not only achieve an excellent balance between high refractive index and low viscosity but also exhibit good storage stability, thus completing the present invention (or this disclosure). That is, this disclosure may include the following embodiments, etc.

[0015] Scheme [1]: A curable composition comprising (meth)acrylate having a 9,9-bisarylfluorene backbone and naphthyl methyl methacrylate.

[0016] Scheme [2]: The curable composition according to Scheme [1], wherein the (meth)acrylate having a 9,9-bisarylfluorene backbone comprises the (meth)acrylate represented by the following formula (1).

[0017] [Chemistry 1]

[0018]

[0019] (where R) 1 Indicates a substituent, m1 represents an integer from 0 to 8.

[0020] Z 1a and Z 1b Independently representing aromatic rings,

[0021] R 2a and R 2b The substituents are represented independently, and m2a and m2b independently represent integers greater than 0.

[0022] A 1a and A 1b Independently representing alkylene groups, n1a and n1b independently represent numbers greater than 0.

[0023] R 3a and R 3b (Independently represents a hydrogen atom or a methyl group.)

[0024] Scheme [3]: The curable composition according to Scheme [2], wherein, in the formula (1), R 1 This represents a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, or a substituted amino group; m1 represents an integer from 0 to 2.

[0025] Z 1a and Z 1b Independently represent C 6-18 Aromatic rings (e.g., C) 6-14 Aromatic ring, preferably C 6-12 (aromatic ring)

[0026] R 2a and R 2b Each group independently represents a halogen atom, hydrocarbon group, alkoxy group, acyl group, nitro group, cyano group, or substituted amino group; m2a and m2b independently represent integers from 0 to 2.

[0027] A 1a and A 1b Independently represent C 2-4 Alkylenes, n1a and n1b independently represent 0~10.

[0028] Scheme [4]: ​​The curable composition according to Scheme [2] or [3], wherein, in formula (1), R 1 This represents a hydrocarbon group, and m1 represents an integer from 0 to 2.

[0029] Z 1a and Z 1b Independently represent C 6-12 Aromatic rings (e.g., C) 6-10 (aromatic ring)

[0030] R 2a and R 2b Each group independently represents a hydrocarbon group, and m2a and m2b independently represent integers from 0 to 2.

[0031] A 1a and A 1b Independently represent C 2-3 Alkylenes, n1a and n1b independently represent 0~8.

[0032] Scheme [5]: A curable composition according to any one of Schemes [1] to [4], wherein the ratio of the (meth)acrylate having a 9,9-bisarylfluorene skeleton to the (meth)acrylate naphthylmethyl ester is the former / the latter (mass ratio) = 20 / 80 to 85 / 15.

[0033] Scheme [6]: A curable composition according to any one of Schemes [1] to [5], wherein the ratio of the (meth)acrylate having a 9,9-bisarylfluorene skeleton to the (meth)acrylate naphthylmethyl ester is the former / the latter (mass ratio) = 40 / 60 to 80 / 20.

[0034] Scheme [7]: A cured product, which is formed by curing the curable composition of any one of Schemes [1] to [6].

[0035] Scheme [8]: A method for manufacturing a cured material, comprising a step of curing the curable composition described in any one of Schemes [1] to [6].

[0036] Solution [9]: An optical component comprising the cured material described in Solution [7].

[0037] It should be noted that this disclosure may also achieve the following secondary objective (solving secondary issues).

[0038] That is, another object of this disclosure is to provide a curable composition and its cured product that have a balance of high refractive index and low viscosity, excellent storage stability and excellent curability, as well as a method of manufacturing the same and its uses.

[0039] Another object of this disclosure is to provide a curable composition and its cured product that have a balance between high refractive index and low viscosity, excellent storage stability, and excellent heat resistance (or heat decomposition resistance), as well as a method of manufacturing the composition and its use.

[0040] Another object of this disclosure is to provide a curable composition and its cured product that have a balance between high refractive index and low viscosity, excellent storage stability, and excellent flexibility (or toughness, especially flexural durability) even with rigid chemical structures such as aromatic ring skeletons, as well as a method of manufacturing the composition and its use.

[0041] It should be noted that in this specification and claims, the number of carbon atoms of substituents is sometimes expressed as C1, C6, C7, C8, C9 ... 10 The designation is as follows. For example, alkyl groups with 1 carbon atom are represented by "C1 alkyl", and aryl groups with 6 to 10 carbon atoms are represented by "C1 alkyl". 6-10 "Aromatic" and other terms.

[0042] To clarify, in this specification and claims, "independently" means that each of the multiple constituent elements is an independent constituent element. For example, in Z... 1a and Z 1b In this case, it means that they can be the same aromatic ring or different aromatic rings.

[0043] In addition, in this specification and claims, the numerical range represented by "X~Y" can include the numerical values ​​X and Y.

[0044] Invention Effects

[0045] According to this disclosure, a curable composition and its cured product with an excellent balance of high refractive index and low viscosity, as well as excellent storage stability, can be provided, along with a method for manufacturing the composition and its use. Attached Figure Description

[0046] [ Figure 1 ] Figure 1 This is a schematic diagram illustrating the bending method of a cured film (thin film) in a bending durability test. Detailed Implementation

[0047] The curable compositions disclosed herein comprise at least (A) a (meth)acrylate having a 9,9-bisarylfluorene backbone and (B) naphthyl methyl methacrylate.

[0048] [(A) (Meth)acrylates having a 9,9-bisarylfluorene backbone]

[0049] Examples of 9,9-bis(arylfluorene) skeletons in (meth)acrylates (A) having a 9,9-bisarylfluorene skeleton include, for example, 9,9-bisphenylfluorene skeletons, 9,9-bis(biphenyl)fluorene skeletons, 9,9-bisnaphthylfluorene skeletons, etc. 6-18 Aryl)fluorene skeleton [e.g., 9,9-bis(C 6-14 Aryl)fluorene skeleton, etc., preferably 9,9-bis(C 6-10 Aryl)fluorene skeleton, etc. 9,9-bis(C 6-12 The aryl)fluorene skeleton, more preferably the 9,9-bisphenylfluorene skeleton or the 9,9-bis(biphenyl)fluorene skeleton.

[0050] The (meth)acrylate (A) having a 9,9-bisarylfluorene skeleton preferably comprises a (meth)acrylate compound represented by the following formula (F) (also simply referred to as compound (F)).

[0051] [Chemistry 2]

[0052]

[0053] (where R) 1Indicates a substituent, m1 represents an integer from 0 to 8.

[0054] Z 1a and Z 1b Independently representing aromatic rings,

[0055] R 2a and R 2b The substituents are represented independently, and m2a and m2b independently represent integers greater than 0.

[0056] A 1a and A 1b n1a and n1b independently represent alkylene groups, and n1a and n1b independently represent numbers greater than 0 (e.g., integers).

[0057] X 1a and X 1b Independently representing a hydrogen atom or a (meth)acryloyl group,

[0058] X 1a and X 1b At least one of them represents (meth)acryloyl.

[0059] In the above equation (F), as a result of R 1 The substituent can be a non-reactive group or a non-polymerizable group. As R 1 Examples include: halogen atoms, hydrocarbon groups (or groups [-R]). h ]), group [-OR h (where R is the formula) h (representing hydrocarbon group), group [-SR] h (where R is the formula) h It can represent hydrocarbon groups, acyl groups, nitro groups, cyano groups, substituted amino groups (mono- or disubstituted amino groups), etc.

[0060] It is noted that, in this specification and claims, R... h The hydrocarbon groups represented can be independent of each other and may be the same or different.

[0061] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0062] hydrocarbon group (or group [-R]) h The group can be a saturated or unsaturated hydrocarbon group, an aliphatic (including alicyclic) or aromatic hydrocarbon group, and can be a chain (straight-chain or branched-chain) or cyclic, or a combination of chain and cyclic structures. A representative hydrocarbon group R... h Examples include alkyl, cycloalkyl, aryl, and aralkyl groups.

[0063] Examples of alkyl groups (straight-chain or branched alkyl groups) include: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc. 1-10 Alkyl, preferably C 1-6 Alkyl, more preferably C 1-4 alkyl.

[0064] Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, etc. 5-10 Cycloalkyl.

[0065] Examples of aryl groups include: phenyl, alkylphenyl, biphenyl, naphthyl, etc. 6-12 Aryl. Examples of alkylphenyl groups include: methylphenyl (or tolyl), dimethylphenyl (or xylyl), etc., with one to three carbon atoms. 1-4 Alkyl-phenyl.

[0066] Examples of aralkyl groups include benzyl, phenethyl, etc. 6-10 Aryl-C 1-4 alkyl.

[0067] In the above group [-OR h ] and [-SR h In ], as a result of R h The hydrocarbon group represented can be exemplified by R as described above. 1 Examples of hydrocarbon groups that are the same as those in the exemplified hydrocarbon groups (including those in the preferred embodiments) include, for example, alkyl, cycloalkyl, aryl, aralkyl, etc.

[0068] As the above-mentioned group [-OR h For example, examples can be given related to the aforementioned hydrocarbon group R. h Examples of corresponding groups include: alkoxy, cycloalkoxy, aryloxy, arylalkoxy, etc. Examples of alkoxy groups (straight-chain or branched-chain alkoxy groups) include: methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, tert-butoxy, etc. 1-10 Alkyl groups. Examples of cycloalkoxy groups include cyclohexyloxy, etc. (C) 5-10 Cycloalkoxy. Examples of aryloxy groups include phenoxy groups, etc. 6-10 Aryloxy group. Examples of aryl alkoxy groups include: benzyloxy group, etc. 6-10 Aryl-C 1-4 Alkyl group.

[0069] As the above-mentioned group [-SR h For example, examples can be given related to the aforementioned hydrocarbon group R. h Examples of corresponding groups include: alkylthio, cycloalkylthio, arylthio, arylalkylthio, etc. Examples of alkylthio groups include: methylthio, ethylthio, propylthio, n-butylthio, tert-butylthio, etc. 1-10Alkylthio group. Examples of cycloalkylthio groups include cyclohexylthio group, etc. 5-10 Cycloalkylthio group. Examples of aryl thio groups include: thiophenoxy (phenylthio), etc. 6-10 Arylthio group. Examples of aryl thio groups include benzyl thio group, etc. 6-10 Aryl-C 1-4 Alkylthio group.

[0070] Examples of acyl groups include: acetyl group, etc. 1-6 Alkyl-carbonyl, etc.

[0071] Examples of mono- or disubstituted amino groups include dialkylamino and bis(alkylcarbonyl)amino. Examples of dialkylamino groups include dimethylamino and other dicarbonylamino compounds. 1-4 Alkylamino. Examples of bis(alkylcarbonyl)amino groups include diacetylamino and other bis(C)amino groups. 1-4 Alkyl-carbonyl)amino.

[0072] In these R 1 Representative examples include: halogen atoms, hydrocarbon groups, alkoxy groups, acyl groups, nitro groups, cyano groups, and substituted amino groups. R is a preferred choice. 1 The atom is a halogen atom, a hydrocarbon group, or a cyano group, more preferably an alkyl group, an aryl group, or other hydrocarbon group. Examples of alkyl groups (straight-chain or branched alkyl groups) include methyl, ethyl, tert-butyl, etc. 1-6 Alkyl groups, preferably methyl groups, etc. 1-4 Alkyl groups are preferred from the viewpoint of easily increasing the refractive index, and C4 groups are more preferred. 6-12 Aryl (e.g., phenyl, naphthyl, etc. C 6-10 (Aromatics, etc.)

[0073] As R 1 The substitution number m1 is, for example, an integer from 0 to 6, preferably an integer from 0 to 4, an integer from 0 to 2, more preferably 0 or 1, or 0 or 2, especially 0 or 2. It should be noted that when m1 is 2 or more, two or more R... 1 The types can be the same or different from each other. Furthermore, in the two benzene rings forming the fluorene framework, when both benzene rings have R... 1 During substitution, the R on a benzene ring 1 Types and R on another benzene ring 1 The species can be the same or different from each other, but the same is preferred. Additionally, R... 1 The replacement position is not particularly limited as long as it is position 1 to 8 of the fluorene skeleton. For example, it can be position 2, position 3, position 2, 7, etc., with position 2, 7 being preferred.

[0074] As a product of Z 1a or Z 1bThe aromatic rings represented include, for example, monocyclic aromatic rings such as benzene rings and polycyclic aromatic rings. Examples of polycyclic aromatic rings include fused polycyclic aromatic rings and cyclic aromatic rings.

[0075] Examples of fused polycyclic aromatic rings include fused bicyclic aromatic rings, fused tricyclic aromatic rings, and fused bicyclic to tetracyclic aromatic rings. Examples of fused bicyclic aromatic rings include naphthalene rings and indene rings. 10-16 Aromatic rings, etc. Examples of fused tricyclic aromatic rings include anthracene rings, phenanthrene rings, and other fused tricyclic C4 rings. 14-20 Aromatic rings, etc. Preferred fused polycyclic aromatic rings are fused polycyclic C-rings such as naphthalene rings. 10-14 Aromatic rings.

[0076] Examples of cyclic aromatic rings include: biphenyl rings, phenylnaphthalene rings, binaphthalene rings, and other biaromatic rings; terphenyl rings and other teraromatic rings, etc. Preferred cyclic aromatic rings are biphenyl rings, etc. 12-18 Biaromatic ring.

[0077] It should be noted that in this specification and claims, "cyclic aromatic ring" refers to a compound in which two or more ring systems (aromatic ring systems) are directly connected by single or double bonds, and the number of bonds in the connecting rings is only one less than the number of ring systems. For example, as mentioned above, phenylnaphthalene rings, binaphthalene rings, etc., even if they have a fused polycyclic aromatic ring skeleton, are classified as cyclic aromatic rings, and are clearly distinguished from "fused polycyclic aromatic rings" such as naphthalene rings (acyclic aromatic rings).

[0078] Preferred Z 1a and Z 1b C 6-14 Aromatic rings and other C 6-18 Aromatic rings, more preferably benzene rings, naphthalene rings, biphenyl rings, etc. 6-12 Aromatic rings, preferably benzene rings, naphthalene rings, etc. 6-10 Aromatic rings, especially considering excellent storage stability, are preferred, with benzene rings being preferred; and biphenyl rings, etc., are preferred from the perspective of easily increasing the refractive index. 10-12 Aromatic ring. Additionally, Z 1a and Z 1b The types can be the same or different from each other, but the same is preferred.

[0079] To clarify, the Z-axis bonded to the 9th bit of the fluorene ring... 1a and Z 1b The substitution position (connection position) in Z is not particularly limited; for example, when Z... 1a Z 1b When it is a benzene ring, the substitution position can be arbitrary, when Z 1a Z1b When it is a naphthalene ring, it can be at any position, either 1-naphthyl or 2-naphthyl, preferably at position 2. 1a Z 1b When it is a biphenyl ring, it can be any position among the 2, 3, and 4 positions, with the 3 position being preferred.

[0080] By R 2a or R 2b The substituent can be a non-reactive group or a non-polymerizable group. As R 2a R 2b Examples of R mentioned above can be cited. 1 Examples include groups that are the same as those in the exemplified group (including those in the preferred embodiment). R is a representative example. 2a R 2b Examples include: halogen atoms, hydrocarbon groups, alkoxy groups, acyl groups, nitro groups, cyano groups, substituted amino groups, etc., preferably alkyl (straight-chain or branched-chain alkyl), cycloalkyl, aryl, aralkyl and other hydrocarbon groups, alkoxy (straight-chain or branched-chain alkoxy) groups, etc. [-OR h More preferably, C such as methyl 1-6 Alkyl, cyclohexyl, and other C 5-8 Cycloalkyl, phenyl, and other C 6-14 Aryl, benzyl, etc. C 6-12 Aryl-C 1-6 Alkyl, methoxy, and other C 1-4 Alkoxy. Preferably, alkyl, aryl (phenyl, etc. C60) groups are used. 6-10 aryl, etc.), arylalkyl and other hydrocarbon groups (e.g., C 1-12 Hydrocarbon group), particularly preferred alkyl group (methyl, etc. C 1-4 Alkyl groups, etc.), aralkyl groups, with aralkyl groups (benzyl groups, etc., C16) being particularly preferred. 6-10 Aryl-C 1-4 Alkyl group). Additionally, R 2a and R 2b The types can be the same or different from each other. It should be noted that when R... 2a When it is aryl, R 2a Can be with Z 1a Together they form a ring aggregate of aromatic rings; when R 2b When it is aryl, R 2b Can be with Z 1b Together they form a ring aggregate of aromatic hydrocarbon rings.

[0081] R 2a or R 2b The substitution number m2a or m2b can be determined according to Z. 1a or Z 1bThe types are appropriately selected, and each can be an integer from approximately 0 to 6, preferably an integer from 0 to 4, more preferably an integer from 0 to 2, and even more preferably 0 or 1, especially 0. m2a and m2b can be different from each other, but are preferably the same. In addition, when m2a is 2 or more, there are two or more R... 2a The types can be the same or different; when m2b is 2 or more, there are 2 or more R 2b The types can be the same or different from each other.

[0082] R 2a and R 2b There are no particular restrictions on the replacement position, in Z 1a and Z 1b In the middle, as long as it is at position 9 of the fluorene ring and with the group [-O-(A 1a O) n1a -X 1a ] and [-O-(A 1b O) n1b -X 1b (abbreviated as containing X) 1 The substitution can be performed at a position other than the bonding site of the group (e.g., at Z). 1a and Z 1b In the above containing X 1 ortho position of the group (with X) 1 Substitution of carbon atoms adjacent to the bonding position of the group.

[0083] As a result of A 1a Or A 1b Examples of alkylene compounds (straight-chain or branched-chain) include: ethylene, propylene (1,2-propyl), trimethylene, 1,2-butadiene, tetramethylene, etc. 2-6 Alkylenes, etc., preferably C 2-4 Alkylene, more preferably ethylene, propylene, etc. 2-3 Alkylene, particularly ethylene. Additionally, A 1a and A 1b The types can be the same or different from each other, but the same is preferred.

[0084] alkeneoxy[-(A 1a O)-] or [-(A 1bThe number of repetitions (additional moles) n1a or n1b of O)-] can each be selected from, for example, a range of about 0 to 20, preferably in the following ranges: 0 to 15, 0 to 10, 0 to 8, 0 to 7, 0 to 6; depending on the application, for example, where high refractive index is particularly important, more preferably in the following ranges: 0 to 10, 0 to 6, 0 to 3, 0 to 2, 0 to 1.5 (e.g., 0.5 to 1.5), and further preferably 0 to 1 (e.g., 1); where low viscosity and / or flexibility (toughness or flexural durability) is particularly important, more preferably in the following ranges: 0 to 15, 1 to 10, 3 to 8, 4 to 7, 4.5 to 6.5, and further preferably 5 to 6. It should be noted that in this specification and claims, the "number of repetitions (additional moles)" can be an integer, or an average value (arithmetic mean, summative average) or average addition of moles. Therefore, n1a and n1b can be integers (e.g., integers in the range described above) or averages (average number of added moles).

[0085] Additionally, the sum of the repetitions n1a and n1b, i.e., the number of alkoxides [-(A] in one molecule, represents the total number of repetitions. 1a O)-] and [-(A 1b The total number (or the total number of moles added together) of O)-] is sometimes simply referred to as n1a+n1b. In this disclosure, n1a+n1b can be used instead of n1a and n1b in the above formula (F) [or the above formula (1) described later].

[0086] n1a+n1b can be selected from a range of approximately 0 to 40, preferably in the following ranges: 0 to 30, 0 to 20, 0 to 16, 0 to 14, 0 to 12; depending on the application, for example, where high refractive index is particularly important, more preferably in the following ranges: 0 to 20, 0 to 12, 0 to 6, 0 to 4, 0 to 3 (e.g., 1 to 3), and further preferably 0 to 2 (e.g., 2); where low viscosity and / or flexibility (toughness or flexural durability) is particularly important, more preferably in the following ranges: 0 to 30, 2 to 20, 5 to 17, 6 to 16, 8 to 14, 9 to 13, and further preferably 10 to 12. Furthermore, n1a+n1b can be an integer (e.g., an integer within the range described above) or an average value (average number of added moles). Note that n1a+n1b can be measured according to the method described in Japanese Patent Application Publication No. 2013-053310, etc.

[0087] When n1a, n1b and / or n1a+n1b are within a moderate range that is not too large, there is a tendency to suppress the decrease in refractive index. When the moderate range is not too small, there is a tendency to suppress the increase in viscosity (decrease in operability) and the decrease in flexibility (toughness or flexural durability).

[0088] Furthermore, n1a and n1b can be the same as or different from each other. When n1a is 2 or more, there are 2 or more alkeneoxy groups [-(A 1a The types of [O)-] can be different from each other, but are preferably the same; when n1b is 2 or more, there are 2 or more alkeneoxy groups [-(A 1b The types of O)-] can be different from each other, but it is preferred that they are the same.

[0089] Group [-O-(A 1a O) n1a -X 1a ] and [-O-(A 1b O) n1b -X 1b (i.e., containing X) 1 (Group) phase in ring Z 1a and Z 1b There are no particular restrictions on the substitution positions, as long as they are respectively substituted at Z 1a and Z 1b The appropriate position is sufficient. In Z 1a and / or Z 1b In the case of a benzene ring, containing X 1 Groups in ring Z 1a and Z 1b The substitution position is preferably at any of the 2, 3, or 4 positions of the phenyl group bonded to the 9 position of the fluorene ring, particularly at the 3 or 4 position, and especially preferably at the 4 position. Additionally, in Z... 1a and / or Z 1b In the case of a naphthalene ring, containing X 1 Groups in ring Z 1a and Z 1b The substitution sites on the fluorene ring are mostly at any of the 5-8 positions of the naphthyl group bonded to the 9th position of the fluorene ring. For example, substitution is performed at the 1st or 2nd position of the naphthyl group bonded to the 9th position of the fluorene ring (substitution in a 1-naphthyl or 2-naphthyl relationship). For this substitution site, substitution in a 1,5, 2,6 relationship, especially a 2,6 relationship, is preferred. Additionally, in Z... 1a and / or Z 1b In the case of a ring-based aromatic hydrocarbon ring, containing X 1 The substitution position of the group is not particularly limited; for example, it can be substituted on the aromatic ring bonded to the 9-position of fluorene or on the aromatic ring adjacent to that ring. For example, in Z... 1a and / or Z 1b It is a biphenyl ring (or Z) 1a and / or Z 1b It is a benzene ring, m2a and / or m2b is 1, R 2a and / or R 2bIn the case of phenyl, the 3-position of the biphenyl ring is preferably bonded to the 9-position of fluorene, and the 6-position of the biphenyl ring is preferably bonded to the position containing X. 1 On the group.

[0090] X 1a and X 1b It can be either a hydrogen atom or a (meth)acryloyl group, but at least one of them is (meth)acryloyl, preferably both are (meth)acryloyl. Therefore, the (meth)acrylate (A) having a 9,9-bisarylfluorene skeleton preferably comprises: X in the above formula (F). 1a and X 1b Both are (meth)acrylates with (meth)acryloyl groups, i.e., (meth)acrylates represented by the following formula (1) (also simply referred to as compound (1)).

[0091] [Chemistry 3]

[0092]

[0093] (where R) 1 m1, Z 1a Z 1b R 2a R 2b m2a, m2b, A 1a A 1b n1a and n1b are each (including the preferred embodiment) the same as the above formula (F).

[0094] R 3a and R 3b (Independently represents a hydrogen atom or a methyl group.)

[0095] In the above equation (1), R 3a R 3b It can be either a hydrogen atom or a methyl group, but from the viewpoint of easily improving reactivity (or curability) and refractive index, a hydrogen atom is preferred. 3a and R 3b The types can be the same or different from each other, but the same is preferred.

[0096] Representative compounds (F) [or compound (1)] include: (meth)acrylate compounds as defined in the above formula (F) [or the above formula (1)], etc.

[0097] R 1 This represents a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, or a substituted amino group; m1 represents an integer from 0 to 2.

[0098] Z 1a and Z 1b Independently represent C 6-18Aromatic rings (preferably benzene rings, naphthalene rings, biphenyl rings, etc.) 6-12 (aromatic ring)

[0099] R 2a and R 2b Each group independently represents a halogen atom, hydrocarbon group, alkoxy group, acyl group, nitro group, cyano group, or substituted amino group; m2a and m2b independently represent integers from 0 to 2.

[0100] A 1a and A 1b Independently represent C 2-4 Alkylene groups, n1a and n1b independently represent numbers from 0 to 10, or n1a+n1b represent numbers from 0 to 20.

[0101] (Meth)acrylate compounds, etc.;

[0102] Preferably, (meth)acrylate compounds as defined in the above formula (F) [or the above formula (1)] are preferred:

[0103] R 1 Indicates hydrocarbon groups such as alkyl, aryl, and aralkyl (e.g., C10, C20, C30, C40, C50, C60, C70, C80, C9 ... 1-10 (hydrocarbon group), m1 represents an integer from 0 to 2,

[0104] Z 1a and Z 1b Independently represent C 6-12 Aromatic rings (e.g., benzene rings, naphthalene rings, etc.) 6-10 (aromatic ring)

[0105] R 2a and R 2b Independently representing hydrocarbon groups such as alkyl, aryl, aralkyl, etc. (e.g., C 1-10 (Hydrocarbon group), m2a and m2b independently represent integers from 0 to 2.

[0106] A 1a and A 1b Independently represent C 2-3 Alkylene, n1a and n1b independently represent numbers from 0 to 8 (especially 0 to 3 or 3 to 8), or n1a+n1b represent numbers from 0 to 16 (especially 0 to 6 or 6 to 16), etc.

[0107] More preferably, (meth)acrylate compounds as defined in the above formula (F) [or the above formula (1)], etc.:

[0108] R 1 Indicate C 1-6 Alkyl groups (especially C16, methyl groups, etc.) 1-4 Alkyl), C 6-12 aryl and other aryl or C6-10 Aryl-C 1-4 Alkyl groups and other aryl groups, especially aryl groups, particularly phenyl, naphthyl, and other C-aryl groups. 6-10 Aryl, m1 represents an integer from 0 to 2,

[0109] Z 1a and Z 1b Independently, they are benzene rings, naphthalene rings, etc. (C) 6-10 Aromatic rings (especially benzene rings), or benzene rings or biphenyl rings,

[0110] R 2a and R 2b Independently represent C 1-6 Alkyl groups (especially C16, methyl groups, etc.) 1-4 Alkyl), C 6-12 aryl and other aryl (especially phenyl) or C 6-12 Aryl-C 1-6 Alkyl and other aralkyl groups, especially alkyl or aralkyl groups, particularly aralkyl groups (especially benzyl and other C groups) 6-10 Aryl-C 1-4 Alkyl group), m2a and m2b independently represent integers from 0 to 2.

[0111] A 1a and A 1b Independently representing C(x) such as ethylene, propylene, etc. 2-3 (Meth)acrylate compounds, etc., in which alkylene (especially ethylene), n1a and n1b independently represent numbers from 0 to 7 (especially 0 to 2 or 4 to 7), or n1a+n1b represent numbers from 0 to 14 (especially 0 to 4 or 8 to 14).

[0112] Examples of specific compounds (F) [or compound (1)] include mono- or di(meth)acrylates of 9,9-bis(hydroxyaryl)fluorene or its alkylene oxide (or the corresponding alkylene carbonate or haloalkanol) adducts [especially di(meth)acrylates].

[0113] Examples of the aforementioned 9,9-bis(hydroxyaryl)fluorene include: 9,9-bis(hydroxyphenyl)fluorene, 9,9-bis(alkyl-hydroxyphenyl)fluorene, 9,9-bis(aryl-hydroxyphenyl)fluorene, 9,9-bis(hydroxynaphthyl)fluorene, and 9,9-bis[(aryl-aralkyl-hydroxy)phenyl]fluorene.

[0114] Examples of 9,9-bis(hydroxyphenyl)fluorene include 9,9-bis(4-hydroxyphenyl)fluorene.

[0115] 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, etc. (Single or di)C 1-4 [alkyl-hydroxyphenyl]fluorene, etc.

[0116] Examples of 9,9-bis(aryl-hydroxyphenyl)fluorene include: 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, etc. 6-10 Aryl-hydroxyphenyl)fluorene, etc.

[0117] 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.

[0118] Examples of 9,9-bis[(aryl-arylalkyl-hydroxy)phenyl]fluorene include: 9,9-bis[(3-benzyl-4-hydroxy-5-phenyl)phenyl]fluorene, etc. 6-10 Aryl-C 6-10 Aryl C 1-4 [alkyl-hydroxy)phenyl]fluorene; 9,9-bis[(3-benzyl-4-hydroxy-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene, etc. 9,9-bis[(C 6-10 Aryl-C 6-10 Aryl C 1-4 [alkyl-hydroxy)phenyl]-di(C 6-10 Aryl)fluorene, etc.

[0119] Representative examples of the aforementioned epoxides (or corresponding alkylene carbonates or haloalkanols) that can be added to the above-mentioned 9,9-bis(hydroxyaryl)fluorene include: ethylene oxide, propylene oxide, etc. 2-3 Epoxides (C6C6) 2-3 alkylene esters or C 2-3 (e.g., haloalkanols). Furthermore, the number of moles added to the above-mentioned alkylene oxides (alkylene carbonates or haloalkanols) (or the average number of moles added) corresponds to the description of n1a+n1b above, including the preferred embodiments.

[0120] As more specific compounds (F) [or compounds (1)], in cases where a high refractive index is particularly important, examples include 9,9-bis[4-(meth)acryloyloxyphenyl]fluorene, 9,9-bis[(meth)acryloyloxyphenyl]fluorene, 9,9-bis[(meth)acryloyloxyalkoxyphenyl]fluorene, 9,9-bis[(aryl-aryl-(meth)acryloyloxy)phenyl]fluorene or 9,9-bis[(aryl-aryl-(meth)acryloyloxyalkoxy)phenyl]fluorene, preferably 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-(meth)acryloyloxypropoxy)phenyl]fluorene, etc. 2-4 [alkoxy-phenyl]fluorene, or 9,9-bis[(3-benzyl-4-(2-(meth)acryloyloxyethoxy)-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene, etc. 9,9-bis[(C 6-10 Aryl-C 6-10 Aryl C 1-4 Alkyl-(meth)acryloyloxy C 2-4 [alkoxy)phenyl]-di(C 6-10 Aryl)fluorene; where low viscosity and / or flexibility (toughness or flexural durability) are particularly important, examples include: 9,9-bis[(meth)acryloyloxypolyalkoxyphenyl]fluorene, preferably: 9,9-bis[4-((meth)acryloyloxy-tetraheptaethoxy)phenyl]fluorene, etc. 9,9-bis[(meth)acryloyloxypolyC 2-4 [Alkoxy-phenyl]fluorene.

[0121] (Meth)acrylates (A) having a 9,9-bisarylfluorene skeleton may contain compound (F) alone [or compound (1)] or may contain two or more compounds (F) [or compound (1)].

[0122] The proportion of compound (F) [or compound (1)] relative to the total amount of (meth)acrylate (A) having a 9,9-bisarylfluorene skeleton is, for example, about 30 to 100% by mass, preferably in the following ranges: more than 50% by mass, more than 70% by mass, more than 90% by mass, and more preferably basically 100% by mass.

[0123] To clarify, compound (F) may contain at least X. 1a and X 1b Both are (meth)acryloyl compounds (1) [di(meth)acrylate], and may also contain X 1a X 1bThe compound [mono(meth)acrylate] is a compound with one side being a hydrogen atom and the other side being a (meth)acryloyl group, or it can be a mixture of the above-mentioned compound (1) [di(meth)acrylate] and the above-mentioned mono(meth)acrylate. The above-mentioned mono(meth)acrylate can be a byproduct generated during the synthesis of compound (1) [di(meth)acrylate]. The mono(meth)acrylate, as the above-mentioned byproduct, can be removed or separated from the corresponding compound (1) [di(meth)acrylate], but from the point of view of productivity, complete removal is often difficult (cumbersome or impractical), so it can be purified without complete removal and contained together with compound (1) [di(meth)acrylate] (coexisting).

[0124] Therefore, in compound (F), as long as compound (1) [di(meth)acrylate] is the main component, it is preferable that the proportion of the above-mentioned mono(meth)acrylate relative to the total amount of compound (1) [di(meth)acrylate] and the above-mentioned mono(meth)acrylate in high performance (or high speed) liquid chromatography (HPLC) is, for example, about 30% or less (e.g., 0 to 20%), preferably 15% or less (e.g., 1 to 12%), more preferably 10% or less (e.g., 2 to 8%), and particularly about 5% or less. It should be noted that in this specification and claims, the above-mentioned area ratio can be calculated by measuring compound (F) [or compound (1)] using HPLC under the conditions of mobile phase: acetonitrile / distilled water (volume ratio) = 90 / 10, flow rate: 0.5 mL / min, and detection wavelength: 254 nm.

[0125] [(B) Naphthyl methyl methacrylate]

[0126] Naphthyl methyl methacrylate (B) can function as a reactive diluent. When combined with (meth)acrylates having a 9,9-bisarylfluorene backbone, rather than with (meth)acrylates having aryl groups only at positions 1-8 of the fluorene backbone, (B) achieves a good balance between high refractive index and low viscosity, while unexpectedly exhibiting excellent storage stability.

[0127] As (B) naphthyl methyl methacrylate, 1-naphthyl methyl methacrylate is preferred, and 1-naphthyl methyl acrylate is more preferred.

[0128] The mass ratio (A / B) of (meth)acrylate (A) having a 9,9-bisarylfluorene skeleton to (meth)acrylate naphthylmethyl methyl ester (B) can be, for example, the former / the latter (mass ratio) = about 10 / 90 to 90 / 10, preferably in the following ranges: 20 / 80 to 85 / 15, 30 / 70 to 82 / 18, 40 / 60 to 80 / 20, 45 / 55 to 75 / 25, and more preferably in the following ranges: 35 / 65 to 65 / 35, 40 / 60 to 60 / 40, 45 / 55 to 55 / 45. In addition, when the (meth)acrylate (A) having a 9,9-bisarylfluorene skeleton contains a compound (F) [or compound (1)] with a large n1a+n1b, from the viewpoint of further improving flexibility (especially bending durability), the above-mentioned mass ratio (A / B) can be, for example, about 53 / 47 to 90 / 10, preferably in the following ranges: 55 / 45 to 85 / 15, 60 / 40 to 80 / 20, 65 / 35 to 75 / 25. Furthermore, when the (meth)acrylate (A) having a 9,9-bisarylfluorene skeleton also has an aryl group (naphthyl, etc.) at the 1 to 8 positions, or a polycyclic aromatic ring (biphenyl ring, etc.) bonded at the 9,9-position, or an aralkyl group (benzyl, etc.) bonded at the 9,9-position, the above-mentioned mass ratio (A / B) can be, for example, about 10 / 90 to 50 / 50, preferably in the following ranges: 15 / 85 to 45 / 55, 20 / 80 to 40 / 60, 25 / 75 to 35 / 65. When the proportion of (meth)acrylate (A) having a 9,9-bisarylfluorene skeleton is within a moderate range that is not too small, there is a tendency to: easily suppress the decrease in refractive index, or easily suppress the decrease in curability, or easily suppress the decrease in flexural durability. When the proportion of (meth)acrylate naphthylmethyl ester (B) is within a moderate range that is not too small, there is a tendency to: easily reduce viscosity without significantly reducing the refractive index, or easily suppress the decrease in storage stability.

[0129] The total proportion of (meth)acrylate (A) and (meth)acrylate naphthyl methyl methacrylate (B) having a 9,9-bisarylfluorene backbone is, for example, about 30 to 100% by mass relative to the total polymerizable components in the curable composition, preferably in the following ranges: 50% or more by mass, 70% or more by mass, 90% or more by mass, and more preferably substantially 100% by mass.

[0130] [Other components in the curing composition]

[0131] The curable composition, as a polymerizable component, only needs to contain at least (meth)acrylate (A) and naphthyl methyl (meth)acrylate (B) having a 9,9-bisarylfluorene backbone, and may include or exclude other components different from this as needed.

[0132] Other components include, for example, multifunctional or monofunctional polymerizable components (polymerizable components or monomeric components), polymerization initiators, solvents, additives, etc., that do not belong to the categories of (meth)acrylates (A) and (meth)acrylate naphthyl methyl methacrylate (B) having a 9,9-bisarylfluorene skeleton.

[0133] (Multifunctional polymeric components)

[0134] There are no particular limitations on other multifunctional polymerizable components that differ from (meth)acrylates (A) having a 9,9-bisarylfluorene backbone; examples include other multifunctional (meth)acrylates (secondary multifunctional (meth)acrylates), etc. The multifunctional (meth)acrylate is any compound having a plurality (more than two) (meth)acryloyl groups, with the number of (meth)acryloyl groups per molecule being, for example, 2 to 10, preferably 2 to 6, more preferably 2 to 4, particularly preferably 2 to 3, and especially preferably 2.

[0135] Examples of second-functional (meth)acrylates include: aliphatic epoxy (meth)acrylates, alicyclic epoxy (meth)acrylates, aromatic epoxy (meth)acrylates, poly(meth)acrylates of phenolic varnish-type epoxy resins, etc.; 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; alicyclic diol di(meth)acrylates; di(meth)acrylates of biphenols or bisphenols or their alkylene oxide (alkylene carbonate or haloalkanol) adducts; 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, etc.

[0136] Examples of the aforementioned aliphatic epoxy (meth)acrylates include, for example, di(meth)acrylates of 1,6-hexanediol diglycidyl ether, di(meth)acrylates of polypropylene glycol diglycidyl ether, and di(meth)acrylates of (poly)alkylene glycol diglycidyl ether.

[0137] Examples of the aforementioned alicyclic epoxy (meth)acrylates include, for instance, di(meth)acrylates of 1,4-cyclohexanediethanol diglycidyl ether, etc., which have a C 5-10 Di(meth)acrylates of aliphatic ring epoxides.

[0138] Examples of the aforementioned aromatic epoxy (meth)acrylates include, for example, di(meth)acrylates of bisphenol A diglycidyl ether, and di(meth)acrylates of diglycidyl ethers of biphenols or bisphenols or their epoxy alkylene carbonate (alkylene carbonate or haloalkanol) adducts. Examples of bisphenols include, for example, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, etc. Examples of biphenols include, for example, p,p'-biphenol, m,m'-biphenol, o,o'-biphenol, etc.

[0139] Examples of alkylene glycol di(meth)acrylates include, for example, ethylene glycol di(meth)acrylate and butanediol di(meth)acrylate. 2-10 Alkyl glycol di(meth)acrylate.

[0140] Examples of the aforementioned polyalkylene glycol di(meth)acrylates include, for example, diethylene glycol di(meth)acrylates and other 2 to 6 C acrylates. 2-10 Alkyl glycol di(meth)acrylate.

[0141] Examples of di(meth)acrylates of the aforementioned alicyclic diols include, for instance, di(meth)acrylates of 1,4-cyclohexanediethanol, etc., which have a C 5-10 Di(meth)acrylate of aliphatic ring diol compounds.

[0142] Among the di(meth)acrylates of biphenols or bisphenols or their alkylene oxide (alkylene carbonate or haloalkanol) adducts, examples of biphenols or bisphenols include those exemplified in the section on aromatic alkylene oxides (meth)acrylates above, such as 9,9-bis[hydroxyaryl]fluorene.

[0143] Examples of poly(meth)acrylates that are low molecular weight polyol compounds having about 3 to 6 hydroxyl groups or their epoxide (alkylene carbonate or haloalkanol) adducts include: glycerol tri(meth)acrylate, diglycerol tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and sorbitol tri- to hexa(meth)acrylates.

[0144] Other polyfunctional polymeric components [or second polyfunctional (meth)acrylates] may be included alone or in combination of two or more. Commercially available second polyfunctional (meth)acrylates may be used.

[0145] It should be noted that in the second polyfunctional (meth)acrylate, low-viscosity polymerizable components, such as alkylene glycol di(meth)acrylate or polyalkylene glycol di(meth)acrylate, can be used as reactive diluents.

[0146] The proportion of other multifunctional polymeric components [or second multifunctional (meth)acrylates] relative to the total polymeric components in the curable composition is, for example, 0 to 50% by mass, preferably in the following ranges: less than 30% by mass, less than 10% by mass, and less than 5% by mass.

[0147] (Monofunctional polymeric component)

[0148] As other monofunctional polymerizable components, there are no particular restrictions as long as they do not belong to the category of (meth)acrylates (A) and naphthyl methyl (meth)acrylate (B) with a 9,9-bisarylfluorene skeleton. They are usually low-viscosity compounds and can function as reactive diluents. As other monofunctional polymerizable components (or reactive diluents), any compound possessing a polymerizable group (or polymerizable unsaturated bond), such as an olefinic unsaturated group, specifically vinyl, allyl, or (meth)acryloyl groups, is acceptable. Examples include monofunctional vinyl monomers and monofunctional (meth)acrylate 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 acid monomers include: (meth)acrylic acid; (meth)acrylamide; N-substituted (meth)acrylamides such as N-hydroxymethyl (meth)acrylamide and N,N-dimethyl (meth)acrylamide; (meth)acrylonitrile; and monofunctional (meth)acrylates.

[0149] These monofunctional polymerizable components can be used alone or in combination of two or more. Among these monofunctional polymerizable components, monofunctional (meth)acrylate monomers are preferred.

[0150] Examples of monofunctional (meth)acrylates include: aliphatic monofunctional (meth)acrylates, alicyclic monofunctional (meth)acrylates, aromatic monofunctional (meth)acrylates, and sulfur-containing monofunctional (meth)acrylates. These monofunctional (meth)acrylates can be used alone or in combination of two or more.

[0151] Examples of aliphatic monofunctional (meth)acrylates include: methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc. (meth)acrylate C 1-20 Alkyl esters.

[0152] Examples of alicyclic monofunctional (meth)acrylates include: cyclohexyl (meth)acrylate, etc. (meth)acrylate C 5-10 Bridged cyclic (meth)acrylates such as cycloalkyl esters, dicyclopentenyl (meth)acrylate, and isobornyl (meth)acrylate.

[0153] 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 2-phenoxyethyl (meth)acrylate, 2-(2-naphthoxy)ethyl (meth)acrylate, and 2-(o-phenylphenoxy)ethyl (meth)acrylate. 6-12 Aryloxy C 2-4 Alkyl esters, etc.; mono(meth)acrylates of bisphenols or biphenols (or their alkyl oxide adducts), etc.; (meth)acrylates with a fluorene skeleton, such as 9-(meth)acryloyloxymethylfluorene, etc.

[0154] Examples of monofunctional (meth)acrylates containing sulfur atoms include: alkyl thioacrylates, aryl thioacrylates, aryl alkyl thioacrylates, and aryl thioalkyl acrylates. Examples of alkyl thioacrylates include: methyl thioacrylate, etc. (Methacrylate C) 1-6 Alkyl thioesters. Examples of aryl thioesters of (meth)acrylate include: phenyl thioesters of (meth)acrylate, etc. (meth)acrylate C 6-10 Aryl thioesters. Examples of aryl thioesters of (meth)acrylate include: benzyl thioester of (meth)acrylate, etc. (meth)acrylate C 6-10 Aryl C 1-6 Alkyl thioesters. Examples of arylthioalkyl esters of (meth)acrylate include: phenylthioethyl (meth)acrylate, etc. (meth)acrylate C 6-10 ArylthioC 2-4 Alkyl esters.

[0155] The proportion of other monofunctional polymerizable components [especially monofunctional (meth)acrylates and other monofunctional (meth)acrylate monomers] relative to the total polymerizable components in the curable composition is, for example, 0 to 50% by mass, preferably in the following ranges: less than 30% by mass, less than 10% by mass, and less than 5% by mass.

[0156] (Polymerization initiator)

[0157] Polymerization initiators can be thermal polymerization initiators (thermal free radical polymerization initiators) or photopolymerization initiators (photofree radical polymerization initiators).

[0158] Examples of thermal polymerization initiators include organic peroxides and azo compounds. Examples of organic peroxides include dialkyl peroxides such as di-tert-butyl peroxide; diacyl peroxides such as lauroyl peroxide and benzoyl peroxide; peroxy acids (or peresters) such as tert-butyl hydroperoxide, cumene hydroperoxide, and tert-butyl peracetate; peroxide ketones; peroxy carbonates; and peroxy ketals. Examples of azo compounds include azonitrile compounds such as 2,2'-azobis(isobutyronitrile), azoamides, and azomides. These thermal polymerization initiators can be used alone or in combination of two or more.

[0159] Examples of photopolymerization initiators include: benzoin derivatives, specifically benzoin alkyl ethers such as benzoin and benzoin ethyl ether; acetophenone derivatives such as acetophenone; α-hydroxyphenone derivatives such as 2-hydroxy-2-methyl-1-phenylprop-1-one and 1-hydroxycyclohexyl-phenyl ketone; aminoacetophenone derivatives such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoaminoprop-1-one; anthraquinone derivatives such as anthraquinone and 2-methylanthraquinone; thioxanthone derivatives such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; and benzophenone derivatives such as benzophenone. Tonones; benzoylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, etc. These photopolymerization initiators can be used alone or in combination of two or more. Preferred photopolymerization initiators include: α-hydroxybenzophenones, benzoylphosphine oxides, and combinations thereof.

[0160] The proportion of the polymerization initiator (thermal and / or photopolymerization initiator) relative to 100 parts by mass of the total amount of polymerizable components in the curable composition 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.

[0161] In addition, photopolymerization initiators can be used in combination with photosensitizers. Representative photosensitizers include the following conventional examples: tertiary amines, such as trialkylamines; trialkylolamines such as triethanolamine; alkyl esters of dialkylaminobenzoates, specifically N,N-dimethylaminobenzoate such as ethyl p-(dimethylamino)benzoate, N,N-dimethylaminobenzoate such as amyl p-(dimethylamino)benzoate, etc.; bis(dialkylamino)benzophenone such as 4,4-bis(diethylamino)benzophenone; dialkylaminobenzophenone such as 4-(dimethylamino)benzophenone, etc. These photosensitizers can be used alone or in combination of two or more.

[0162] The proportion of photosensitizer relative to 100 parts by mass of the above-mentioned polymerization initiator 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.

[0163] (solvent)

[0164] The curable composition is easily adjusted to a low viscosity, so it is fine even without solvent. However, a solvent may be included as needed to adjust workability. There are no particular limitations on solvents; examples 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 dichloromethane, chloroform, 1,2-dichloroethane, and chlorobenzene; and ethers, specifically chain ethers such as diethyl ether, tetrahydrofuran, and 1,4-dichloroethane. Alkyl ethers and other cyclic ethers; ketones, specifically dialkyl ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK), and cyclic ketones such as cyclohexanone; esters, specifically acetates 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 sulfoxides; amides, specifically N,N-dimethylformamide (DMF), N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; and nitriles, specifically acetonitriles. These solvents can be used individually or in combination of two or more as a mixed solvent.

[0165] There is no particular limitation on the proportion of solvent, which can be adjusted so that the concentration of solid components (components other than solvent) relative to the whole curable composition 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.

[0166] (additive)

[0167] The curable composition may contain conventional additives, such as colorants, stabilizers, fillers, antistatic agents, flame retardants, surfactants, plasticizers, curing agents, and polymerization inhibitors. Examples of stabilizers include heat stabilizers, antioxidants, and UV absorbers. These additives may be used individually or in combination of two or more.

[0168] The total proportion of additives relative to the solid components (other than solvents) of the curable composition is, for example, about 30% by mass or less, preferably in the following ranges: 20% by mass or less, 10% by mass or less, 5% by mass or less, for example, it can be 0.001 to 15% by mass, specifically about 0.01 to 3% by mass.

[0169] [Characteristics of Curing Compositions]

[0170] The refractive index (refractive index before curing) nD of the curable composition at a temperature of 25°C and a wavelength of 589 nm can be, for example, around 1.56 to 1.7, preferably in the following ranges: 1.57 to 1.65, 1.58 to 1.64, 1.59 to 1.63, 1.6 to 1.625, 1.605 to 1.62, 1.61 to 1.615. In cases where a high refractive index is particularly important, it can be, for example, around 1.6 to 1.645, preferably in the following ranges: 1.605 to 1.64, 1.61 to 1.635, 1.615 to 1.63, 1.62 to 1.625.

[0171] The viscosity of the curable composition at a temperature of 25°C can be, for example, around 10 to 200,000 mPa·s, preferably in the following ranges: 100 to 100,000 mPa·s, 500 to 50,000 mPa·s, 1,000 to 30,000 mPa·s, 1,500 to 10,000 mPa·s, 2,000 to 5,000 mPa·s, and 2,500 to 4,000 mPa·s. Where low viscosity is particularly important, the following ranges are preferred: 100 to 3,000 mPa·s, 150 to 2,000 mPa·s, 200 to 1,000 mPa·s, and 250 to 500 mPa·s.

[0172] The curable composition exhibits excellent storage stability. At a temperature of 25°C, no precipitates are observed even after 10 days or more, preferably 20 days or more, more preferably 30 days or more (e.g., about 30 to 40 days), and even more preferably after 60 days or more (e.g., about 90 to 180 days), and particularly preferably after 120 days or more (e.g., about 120 to 150 days).

[0173] The curable composition exhibits excellent curability; for example, it can be cured at a temperature of 25°C with a curing speed of approximately 2000 mJ / cm². 2 Below (e.g., 500~2000 mJ / cm) 2 ), preferably 1000mJ / cm 2 Below, more preferably 500 mJ / cm 2 The following cumulative light intensity is used to irradiate a high-pressure mercury lamp (or UV) to form a cured material (cured film) with a non-adhesive (sticky) surface and a thickness of about 100 μm.

[0174] It should be noted that, in this specification and claims, the refractive index, viscosity, storage stability, and curability of the curable composition can be determined according to the methods described in the examples below.

[0175] [cured material]

[0176] This disclosure includes cured products of curable compositions and methods for manufacturing the same, said curable compositions containing at least: (meth)acrylate (A) having a 9,9-bisarylfluorene backbone and (meth)acrylate naphthylmethyl methyl ester (B).

[0177] The cured product can be manufactured by a process of curing the above-mentioned curable composition (curing process). In the curing process, the curable composition can be cured by imparting active energy (or active energy rays) to it, thereby generating a cured product. Among the above-mentioned active energies, thermal energy and / or light energy, such as ultraviolet (UV), X-rays, and other light energy, are useful.

[0178] When using ultraviolet (UV) light energy for irradiation, the appropriate value can be selected based on the light irradiation energy (or cumulative light intensity), the type of components in the composition, and the intended use; for example, 50~10000 mJ / cm². 2 The preferred value is 70~8000mJ / cm. 2 More preferably 100~5000mJ / cm 2 Especially 500~3000mJ / cm 2 .

[0179] When heat treatment is performed using thermal energy, the heating temperature is, for example, 50~200°C, preferably 60~150°C, and more preferably 70~120°C.

[0180] There are no particular restrictions on the shape of the cured material. Depending on the application, it can be a three-dimensional structure such as a lens or tube, a two-dimensional structure such as a film, sheet, or plate (or cured film), or a one-dimensional structure such as a line, fiber, or rod.

[0181] The cured material can be manufactured by molding or (casting) the aforementioned curable composition into a specified mold, and then subjecting it to a curing process (heating and / or light irradiation) according to its shape. Alternatively, in the case of a two-dimensional cured material, the aforementioned curable composition can be coated onto a substrate or base material (e.g., metals such as aluminum; inorganic materials or ceramics such as titanium oxide, glass, or quartz; organic materials or plastics such as cyclic olefin resins or polycarbonate resins; porous materials such as wood, etc.), preferably a transparent substrate, to form a film-like coating (or thin film), and then subjected to a curing process.

[0182] The refractive index (refractive index after curing) nD of the cured material at a temperature of 25°C and a wavelength of 589nm can be, for example, around 1.57 to 1.7, preferably in the following ranges: 1.58 to 1.67, 1.59 to 1.66, 1.6 to 1.65, 1.62 to 1.645, 1.625 to 1.64, and 1.63 to 1.635. When a high refractive index is particularly important, it can be, for example, around 1.62 to 1.665, preferably in the following ranges: 1.625 to 1.66, 1.63 to 1.655, 1.635 to 1.65, and 1.64 to 1.645.

[0183] The 5% weight reduction temperature of the cured material can be, for example, around 150~500℃, preferably in the following ranges: 180~400℃, 200~350℃, 210~320℃, 220~300℃, 230~290℃, 240~280℃, and 250~270℃.

[0184] The glass transition temperature (Tg) of the cured material can be, for example, around 10 to 200°C, preferably in the following ranges: 50 to 150°C, 70 to 140°C, 80 to 130°C, 90 to 120°C, and 100 to 110°C. In cases where high flexibility (or flexural durability) is particularly important, the following ranges are preferred: 20 to 40°C and 25 to 35°C.

[0185] The cured material exhibits excellent flexibility (or flexural durability). For example, a cured material (cured film) with a temperature of 25°C and a film thickness of approximately 100 μm can be bent 180° without cracking. Furthermore, in a cured material (cured film) with a temperature of 25°C and a film thickness of approximately 100 μm, even after repeated bending more than 10,000 times (e.g., about 50,000 to 1,000,000 times), preferably more than 100,000 times (e.g., about 150,000 to 500,000 times), and more preferably more than 180,000 times (e.g., about 200,000 to 300,000 times), the cured film will not develop creases or breakage (and there will be no abnormal appearance).

[0186] It should be noted that, in this specification and claims, the refractive index, 5% weight reduction temperature, glass transition temperature Tg, flexibility, and flexural durability of the cured product can be determined according to the methods described in the examples below.

[0187] [Representative Composition]

[0188] Representative curable compositions of this disclosure include curable compositions containing: (meth)acrylate represented by the above formula (1) as a (meth)acrylate having a 9,9-bisarylfluorene skeleton, and naphthyl methyl methacrylate, wherein curable compositions (I) to (III) are preferred.

[0189] (Curing composition (I))

[0190] Curable composition (I) is containing

[0191] In the above formula (1),

[0192] R 1 Indicates a hydrocarbon group such as alkyl, aryl, or aralkyl (e.g., C 1-10 (hydrocarbon group), m1 represents an integer from 0 to 2,

[0193] Z 1a and Z 1b Independently representing C rings such as benzene ring, naphthalene ring, and biphenyl ring. 6-12 Aromatic rings,

[0194] R 2a and R 2b Independently representing hydrocarbon groups such as alkyl, aryl, aralkyl, etc. (e.g., C 1-10 (Hydrocarbon group), m2a and m2b independently represent integers from 0 to 2.

[0195] A 1a and A 1b Independently represent C 2-4 Alkylene, n1a and n1b independently represent numbers from 0 to 3, or n1a + n1b represent numbers from 0 to 6 (meth)acrylates, and

[0196] Naphthyl methyl (meth)acrylate,

[0197] Furthermore, the ratio of the (meth)acrylate having the 9,9-bisarylfluorene skeleton [especially the (meth)acrylate represented by the above formula (1)] to the above naphthyl methyl methacrylate is the former / the latter (mass ratio) = 20 / 80~80 / 20 (preferably 25 / 75~75 / 25).

[0198] Curable compositions.

[0199] The preferred curable composition (I) is containing

[0200] In the above formula (1),

[0201] R 1 Indicate C 1-6 Alkyl and other alkyl groups, C 6-10 aryl and other aryl or C 6-10 Aryl-C 1-4 Alkyl groups, etc., where m1 represents an integer from 0 to 2.

[0202] Z 1a and Z 1b Independently representing C rings such as benzene ring and naphthalene ring.6-10 Aromatic rings,

[0203] R 2a and R 2b Independently represent C 1-6 Alkyl and other alkyl groups, C 6-10 aryl and other aryl or C 6-10 Aryl-C 1-4 Alkyl groups and other aryl groups, where m2a and m2b independently represent integers from 0 to 2.

[0204] A 1a and A 1b Independently represent C 2-3 Alkylene, n1a and n1b independently represent numbers from 0 to 2, or n1a + n1b represent numbers from 0 to 4 (meth)acrylates, and

[0205] Naphthyl methyl (meth)acrylate

[0206] Furthermore, the ratio of the (meth)acrylate having the 9,9-bisarylfluorene skeleton [especially the (meth)acrylate represented by the above formula (1)] to the above naphthyl methyl methacrylate is the former / the latter (mass ratio) = 30 / 70~70 / 30 (preferably 35 / 65~65 / 35).

[0207] Curable compositions.

[0208] A more preferred curable composition (I) is comprising

[0209] In the above formula (1),

[0210] R 1 Indicate C 1-4 Alkyl groups (preferably C16, such as methyl groups) 1-3 Alkyl group), m1 represents an integer from 0 to 2.

[0211] Z 1a and Z 1b Independently representing the benzene ring,

[0212] R 2a and R 2b Independently represent C 1-4 Alkyl groups (preferably C16, such as methyl groups) 1-3 (alkyl group), m2a and m2b independently represent integers from 0 to 2 (preferably 0 or 1).

[0213] A 1a and A 1b (Meth)acrylates, where n1a and n1b independently represent ethylene or propylene (preferably ethylene), and n1a and n1b independently represent numbers from 0 to 2 (preferably 0 to 1), or n1a+n1b represent numbers from 0 to 3 (preferably 0 to 2).

[0214] Naphthyl methyl (meth)acrylate [preferably 1-naphthyl methyl (meth)acrylate],

[0215] Furthermore, the ratio of the (meth)acrylate having the 9,9-bisarylfluorene skeleton [especially the (meth)acrylate represented by the above formula (1)] to the above naphthyl methyl methacrylate is the former / the latter (mass ratio) = 40 / 60 to 60 / 40 (preferably 45 / 55 to 55 / 45).

[0216] Curable compositions.

[0217] (Curing composition (II))

[0218] Curable composition (II) is containing

[0219] In the above formula (1),

[0220] R 1 Indicates a hydrocarbon group such as alkyl, aryl, or aralkyl (e.g., C 1-10 (hydrocarbon group), m1 represents an integer from 0 to 2,

[0221] Z 1a and Z 1b Independently representing C rings such as benzene ring, naphthalene ring, and biphenyl ring. 6-12 Aromatic rings,

[0222] R 2a and R 2b Independently representing hydrocarbon groups such as alkyl, aryl, aralkyl, etc. (e.g., C 1-10 (Hydrocarbon group), m2a and m2b independently represent integers from 0 to 2.

[0223] A 1a and A 1b Independently represent C 2-4 Alkylene, n1a and n1b independently represent numbers from 3 to 10, or n1a + n1b represent numbers from 6 to 20 (meth)acrylates, and

[0224] Naphthyl methyl (meth)acrylate,

[0225] Furthermore, the ratio of the (meth)acrylate having the 9,9-bisarylfluorene skeleton [especially the (meth)acrylate represented by the above formula (1)] to the above naphthyl methyl methacrylate is the former / the latter (mass ratio) = 20 / 80~98 / 2 (preferably 30 / 70~95 / 5).

[0226] Curable compositions.

[0227] The preferred curable composition (II) is containing

[0228] In the above formula (1),

[0229] R 1 Indicate C 1-6 Alkyl and other alkyl groups, C 6-10 aryl and other aryl or C 6-10 Aryl-C 1-4 Alkyl groups, etc., where m1 represents an integer from 0 to 2.

[0230] Z 1a and Z 1b Independently representing C rings such as benzene ring and naphthalene ring. 6-10 Aromatic rings,

[0231] R 2a and R 2b Independently represent C 1-6 Alkyl and other alkyl groups, C 6-10 aryl and other aryl or C 6-10 Aryl-C 1-4 Alkyl groups and other aryl groups, where m2a and m2b independently represent integers from 0 to 2.

[0232] A 1a and A 1b Independently represent C 2-3 Alkylene, n1a and n1b independently represent numbers from 4 to 9 (preferably 4 to 8), or n1a+n1b represent numbers from 7 to 18 (preferably 8 to 16) of (meth)acrylates, and

[0233] Naphthyl methyl (meth)acrylate,

[0234] Furthermore, the ratio of the (meth)acrylate having the 9,9-bisarylfluorene skeleton [especially the (meth)acrylate represented by the above formula (1)] to the above naphthyl methyl methacrylate is the former / the latter (mass ratio) = 40 / 60~92 / 8 (preferably 50 / 50~90 / 10).

[0235] Curable compositions.

[0236] A more preferred curable composition (II) is one containing

[0237] In the above formula (1),

[0238] R 1 Indicate C 1-4 Alkyl groups (preferably C16, such as methyl groups) 1-3 Alkyl group), m1 represents an integer from 0 to 2.

[0239] Z 1a and Z 1b Independently representing the benzene ring,

[0240] R2a and R 2b Independently represent C 1-4 Alkyl groups (preferably C16, such as methyl groups) 1-3 (alkyl group), m2a and m2b independently represent integers from 0 to 2 (preferably 0 or 1).

[0241] A 1a and A 1b (Meth)acrylates, where n1a and n1b independently represent ethylene or propylene (preferably ethylene), and n1a and n1b independently represent numbers from 5 to 7 (preferably 5 to 6), or n1a+n1b represent numbers from 9 to 14 (preferably 10 to 12).

[0242] Naphthyl methyl (meth)acrylate [preferably 1-naphthyl methyl (meth)acrylate],

[0243] Furthermore, the ratio of the (meth)acrylate having the 9,9-bisarylfluorene skeleton [especially the (meth)acrylate represented by the above formula (1)] to the above naphthyl methyl methacrylate is the former / the latter (mass ratio) = 55 / 45 to 85 / 15 (preferably 60 / 40 to 80 / 20, more preferably 65 / 35 to 75 / 25, especially 67 / 33 to 73 / 27).

[0244] Curable compositions.

[0245] (Cureable Composition (III))

[0246] Curable composition (III) is containing

[0247] In the above formula (1),

[0248] R 1 Indicates a hydrocarbon group such as alkyl, aryl, or aralkyl (e.g., C 1-10 (hydrocarbon group), m1 represents an integer from 0 to 2,

[0249] Z 1a and Z 1b Independently representing polycyclic aromatic rings (preferably naphthalene rings, biphenyl rings, etc. C 10-20 (polycyclic aromatic rings, etc.)

[0250] R 2a and R 2b Independently representing hydrocarbon groups such as alkyl, aryl, aralkyl, etc. (e.g., C 1-10 (Hydrocarbon group), m2a and m2b independently represent integers from 0 to 2.

[0251] A 1a and A 1b Independently represent C 2-4Alkylene, n1a and n1b independently represent numbers from 0 to 3, or n1a + n1b represent numbers from 0 to 6 (meth)acrylates, and

[0252] Naphthyl methyl (meth)acrylate,

[0253] Furthermore, the ratio of the (meth)acrylate having the 9,9-bisarylfluorene skeleton [especially the (meth)acrylate represented by the above formula (1)] to the above naphthyl methyl methacrylate is the former / the latter (mass ratio) = 10 / 90~80 / 20 (preferably 12 / 88~60 / 40).

[0254] Curable compositions.

[0255] The preferred curable composition (III) is containing

[0256] In the above formula (1),

[0257] R 1 Indicate C 1-6 Alkyl and other alkyl groups, C 6-14 aryl and other aryl or C 6-10 Aryl-C 1-4 Alkyl or aralkyl (preferably aryl or aralkyl), where m1 represents an integer from 1 to 2.

[0258] Z 1a and Z 1b Independently represent C 10-18 Polycyclic aromatic rings,

[0259] R 2a and R 2b Independently represent C 1-6 Alkyl and other alkyl groups, C 6-14 aryl and other aryl or C 6-10 Aryl C 1-4 Alkyl groups, such as aralkyl groups (preferably aralkyl groups), where m2a and m2b independently represent integers from 0 to 2.

[0260] A 1a and A 1b Independently represent C 2-3 Alkylene, n1a and n1b independently represent numbers from 0 to 2, or n1a + n1b represent numbers from 0 to 4 (meth)acrylates, and

[0261] Naphthyl methyl (meth)acrylate,

[0262] Furthermore, the ratio of the (meth)acrylate having the 9,9-bisarylfluorene skeleton [especially the (meth)acrylate represented by the above formula (1)] to the above naphthyl methyl methacrylate is the former / the latter (mass ratio) = 15 / 85 to 50 / 50 (preferably 18 / 82 to 45 / 55).

[0263] Curable compositions.

[0264] A more preferred curable composition (III) is one containing

[0265] In the above formula (1),

[0266] R 1 Indicates aryl (preferably phenyl, naphthyl, biphenyl, etc. C 6-12 Aryl, more preferably C 6-10 Aryl, especially naphthyl), m1 represents an integer from 1 to 2.

[0267] Z 1a and Z 1b Independently represent C 10-14 Polycyclic aromatic rings (preferably naphthalene rings, biphenyl rings, etc.) 10-12 (polycyclic aromatic rings)

[0268] R 2a and R 2b Independently representing aralkyl groups (preferably benzyl or other phenyl C) 1-3 (alkyl group), m2a and m2b independently represent integers from 0 to 2 (preferably 0 or 1).

[0269] A 1a and A 1b (Meth)acrylates, where n1a and n1b independently represent ethylene or propylene (preferably ethylene), and n1a and n1b independently represent numbers from 0 to 2 (preferably 0 to 1), or n1a+n1b represent numbers from 0 to 3 (preferably 0 to 2).

[0270] Naphthyl methyl (meth)acrylate [preferably 1-naphthyl methyl (meth)acrylate],

[0271] Furthermore, the ratio of the (meth)acrylate having the 9,9-bisarylfluorene skeleton [especially the (meth)acrylate represented by the above formula (1)] to the above naphthyl methyl methacrylate is the former / the latter (mass ratio) = 20 / 80~40 / 60 (preferably 25 / 75~35 / 65).

[0272] Curable compositions.

[0273] The curable compositions (I) to (III) can be appropriately combined with the preferred embodiments disclosed in this specification.

[0274] Example

[0275] The present disclosure will now be described in more detail based on embodiments, but the present disclosure is not limited to these embodiments. Details of raw materials, evaluation methods, etc., are shown below.

[0276] [raw material]

[0277] DNFPA: 9,9-bis(3-acryloyloxypropyl)-2,7-bis(2-naphthyl)fluorene, synthesized according to Example 1 of International Publication No. 2021 / 131942.

[0278] BPEFA: 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene (manufactured by Osaka Gas Chemical Co., Ltd.)

[0279] BPEF-9EOA: A diacrylate of an adduct of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF) with an average addition of 9 moles of ethylene oxide (EO), synthesized according to the method described in Reference Example 4 of Japanese Patent Application Publication No. 2013-53310.

[0280] DNBBzOPPEFA: 9,9-bis[(3-benzyl-4-(2-acryloyloxyethoxy)-5-phenyl)phenyl]fluorene, was synthesized in Synthesis Example 1 described later.

[0281] NMT-A: Naphthylmethyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd. as "LightAcrylate NMT-A"

[0282] POBA: m-phenoxybenzyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd. as "LightAcrylate POB-A"

[0283] Photopolymerization initiator A: "IRGACURE 184" manufactured by Ciba Specialty Chemicals Japan Co., Ltd.

[0284] Photopolymerization initiator B: "Darocur TPO" manufactured by BASF Japan.

[0285] [Synthesis example 1]

[0286] Synthesis of 9,9-bis[(3-benzyl-4-(2-acryloyloxyethoxy)-5-phenyl)phenyl]-2,7-dinaphthylfluorene

[0287] In a separable flask, add 33.83 g (0.1 mol) of 2,7-dibromo-9-fluorenone, 57.51 g (0.22 mol, 2.2 eq) of 2-benzyl-6-phenylphenol, 87.2 g of toluene, 11.8 g (0.48 mol) of p-toluenesulfonic acid monohydrate, and 1.2 g (0.04 mol) of dodecanethiol. Stir under reflux (110℃~120℃) until the peak of 2,7-dibromo-9-fluorenone disappears in LC (liquid chromatography). Cool to 80℃, then add 68 g of N,N-dimethylformamide (DMF) to dissolve the fluorenone components uniformly. Wash the resulting solution with 68 g of deionized water, then remove the aqueous layer. Repeat this washing operation twice. The organic layer was dehydrated by azeotropic extraction to obtain 171.73 g of a solution containing 9,9-bis[(3-benzyl-4-hydroxy-5-phenyl)phenyl]-2,7-dibromofluorene (DBrBBzOPPF).

[0288] Add 20.14 g (0.22 mol, 2.2 eq) of ethylene carbonate, 10.06 g (0.7 mol) of potassium carbonate, and 59 g of DMF to the resulting solution. Stir under nitrogen atmosphere and reflux (110–120 °C) until the monosubstituted compound (the compound obtained by reacting DBrBBzOPPF with only one molecule of ethylene carbonate) reaches less than 3% in liquid chromatography (LC). Cool to 80 °C. Add 71.1 g of 24% (w / w) NaOH aqueous solution, stir at 80 °C for 2 hours, then add 67 g of DMF, 80 g of toluene, and 102 g of deionized water to dissolve them, removing the aqueous layer. Add 50 g of deionized water, remove the aqueous layer, and repeat this operation 5 times. Concentrate the organic layer, add methanol, and obtain 124.7 g of crude crystals. 166 g of methyl isobutyl ketone (MIBK) was added to the crude crystals and dissolved. Ion exchange resins (+) K1221 and (-) K1261 were then added. After stirring at 85°C for 2 hours, the solution was poured onto a diatomaceous earth layer covered with activated carbon and filtered. The solution was concentrated under reduced pressure and crystallized from methanol to obtain 64.7 g of 9,9-bis[(3-benzyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl]-2,7-dibromofluorene (DBrBBzOPPEF) (yield 69.7%).

[0289] Add 28.09 g (0.03 mol) of DBrBBzOPPEF, 11.42 g (0.066 mol, 2.2 eq) of 2-naphthylboronic acid, 49.83 g of MIBK, 7.0 g (0.066 mol) of sodium carbonate, 30.4 g of deionized water, 7.0 mg (0.03 mmol, 0.001 eq) of palladium acetate, and 13.2 mg (0.05 mmol, 0.002 eq) of triphenylphosphine. Degas under reduced pressure, replace with nitrogen, and stir under reflux (90–100 °C). The endpoint is set at the point where the peak of the monosubstituted product (the compound obtained by reacting DBrBBzOPPEF with only one molecule of 2-naphthylboronic acid) disappears in LC. Cool to 80 °C and remove the lower layer. Wash with 18 g of deionized water to remove the aqueous layer. Repeat this operation three times. Add 3.1 g of activated carbon to the organic layer, stir at 70 °C for 1 hour, and then filter. Add 18 g of ion-exchanged water to the obtained solution and remove the aqueous layer. Repeat this operation twice. Concentrate the solution under reduced pressure and crystallize it through methanol to obtain 24.5 g of 9,9-bis[(3-benzyl-4-(2-hydroxyethoxy)-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene (DNBBzOPPEF) (yield 79.8%).

[0290] Add 100.02 g (0.1 mol) of DNBBzOPPEF, 17.39 g (0.51 mol, 2.46 eq) of acrylic acid, 0.214 g (2.3 mmol, 0.02 eq) of p-methoxyphenol (methoxyquinone), 98.21 g of toluene, and 2.8 g (0.014 mol) of p-toluenesulfonic acid monohydrate. Stirring while removing the generated water under reflux (110–120 °C) until the monosubstituted product (the compound obtained by reacting DNBBzOPPEF with only one molecule of acrylic acid) reaches less than 20% in LC, then add toluene. Wash once with 35 g of 20% physiological saline, once with 20% physiological saline and 10% NaOH aqueous solution, twice with 35 g of 20% physiological saline, and twice with 35 g of deionized water. 25 g of activated carbon was added to the solution and stirred at room temperature for 1 hour. The solution was filtered with diatomaceous earth. 0.012 g of p-methoxyphenol was added to the diatomaceous earth-filtered solution and the solution was concentrated under reduced pressure to obtain 90.1 g of 9,9-bis[(3-benzyl-4-(2-acryloyloxyethoxy)-5-phenyl)phenyl]-2,7-di(2-naphthyl)fluorene (DNBBzOPPEFA) (yield 81.0%, HPLC purity 82.8%).

[0291] [Chemistry 4]

[0292]

[0293] The obtained DNBBzOPPEFA 1 H-NMR and 13 The C-NMR results are shown below.

[0294]

[0295]

[0296] [Evaluation Method]

[0297] (HPLC)

[0298] Using the Shimadzu Corporation's "LC-2030" as the HPLC (High Performance Liquid Chromatography) instrument and Tosoh Corporation's "ODS-80TM" as the column, the sample was dissolved in acetonitrile for determination, and the HPLC purity [area %] was calculated.

[0299] ( 1 H-NMR and 13 C-NMR)

[0300] The sample was dissolved in a heavy solvent containing tetramethylsilane as an internal standard and measured using a nuclear magnetic resonance apparatus (BRUKER "AVANCE III HD").

[0301] (Refractive index nD)

[0302] The refractive index before and after curing [refractive index of the curable composition and the cured product] was measured using a multi-wavelength Abbe refractometer (ATAGO "DR-M2 (circulating thermostatic water bath 60-C3)") at a temperature of 25°C and a wavelength of 589 nm (D-rays). For the refractive index measurement before curing, a curable composition (polymerizable component) without a photopolymerization initiator was used as the sample; for the refractive index measurement after curing, the cured product (cured film) obtained in the (curability) evaluation described later (samples with a curability evaluation of "○") was used as the sample.

[0303] To explain, the refractive index of DNFPA before curing in Comparative Example 1 was obtained by dissolving it in toluene to prepare solutions with concentrations of 25.0% and 48.7% by mass, and measuring the refractive index of the resulting solutions. A calibration curve (an approximate straight line using the least squares method) was then constructed based on this. The concentration was extrapolated to 100% by mass in the calibration curve.

[0304] In addition, the refractive index of the cured product of Comparative Example 1 after DNFPA curing was determined as follows. 100 parts by weight of the polymerizable component (DNFPA) were collected in a brown bottle, and 3 parts by weight of photopolymerization initiator A were added. The mixture was diluted with toluene (dissolved by heating to 60°C). The resulting diluted solution (curable composition) was then spin-coated (1000 rpm, 30 seconds) onto the surface of a silicon wafer approximately 3 cm × 3 cm in size. The coating was then irradiated with UV (500 mJ / cm²) using a high-pressure mercury lamp (EYE GRAPHICS, "ECS-151U"). 2 To prepare a non-adhesive (sticky) cured product (a cured film several μm thick), a high-speed spectroscopic ellipsometry (JA Woollam M-2000) was used to measure the refractive index nD of the obtained cured product to ensure measurement accuracy.

[0305] (Viscosity)

[0306] The viscosity of the curable composition was measured using a TV-22 type viscometer (cone-plate type, manufactured by Toki Sangyo Co., Ltd., "TVE-22L"). Depending on the viscosity to be measured, a selectable rotor (01: 1°34′×R24, 07: 3°×R7.7) and rotation speed (0.5~20 rpm) were selected, and the measurement was performed at 25°C. It should be noted that a curable composition (polymerizable component) without a photopolymerization initiator was used as the sample.

[0307] (Storage stability)

[0308] The storage stability of the curable composition was assessed by preparing and evaluating the curable composition as follows.

[0309] Specifically, a sample (polymerizable component) was collected in a colorless, transparent bottle (a "screw tube" manufactured by Maruemu). Relative to 100 parts by mass of the collected polymerizable component, 3 parts by mass of photopolymerization initiator A (and 2 parts by mass of photopolymerization initiator B, as in Reference Examples 3 and 8) were added. The mixture was heated to 60°C to melt and mix, thus preparing a curable composition. The resulting curable composition (curable composition containing the photopolymerization initiator) was left to stand at room temperature (25°C) in the dark for 4 months (120 days) to confirm its condition and was evaluated according to the following criteria.

[0310] ◎…No precipitates were produced after 4 months (120 days).

[0311] ○…No precipitates were produced after one month (30 days).

[0312] ×…precipitates are produced within 1 month (30 days).

[0313] (Curing properties)

[0314] The curability of the curable composition is evaluated as follows, based on the formation of a cured product (cured film).

[0315] Specifically, a sample (polymerizable component) was collected in a colorless, transparent bottle (a "screw tube" manufactured by Maruemu). Relative to 100 parts by mass of the collected polymerizable component, 3 parts by mass of photopolymerization initiator A (and 2 parts by mass of photopolymerization initiator B in Example 8) were added, and the mixture was heated to 60°C to melt and mix, thus preparing a curable composition. This curable composition (curable composition containing the photopolymerization initiator) was coated onto a TAC (cellulose acetate) film using a coater to prepare a coating film with a thickness of approximately 100 μm. The coating film was then irradiated with UV light at room temperature (25°C) using a high-pressure mercury lamp (ECS-151U manufactured by Eye Graphics) with the cumulative light intensity shown in Tables 1-4. The curability was evaluated based on the tactile feel of the resulting coating film [cured product (cured film)] according to the following criteria.

[0316] ○……The cured surface is non-sticky (adhesive).

[0317] △……The surface of the cured material is sticky (adhesive).

[0318] ×……Not cured (sticky)

[0319] To clarify, in Comparative Example 1, since DNFPA is solid at 25°C, the curability was evaluated in the same manner as described above, except that the coating was prepared as follows. Specifically, 100 parts by weight of the polymerizable component (DNFPA) were taken in a brown bottle, and 3 parts by weight of photopolymerization initiator A were added, then diluted with toluene (dissolved by heating to 60°C). This diluted solution (curable composition) was then applied to a TAC (cellulose acetate) film using a coater to form a coating (approximately 100 μm thick).

[0320] To clarify, in Reference Example 2, since DNBBzOPPEFA is solid at 25°C, the curability was evaluated in the same manner as described above, except that the coating was prepared as follows. Specifically, 100 parts by weight of the polymerizable component (DNBBzOPPEFA) were taken into a brown bottle, and 3 parts by weight of photopolymerization initiator A and 2 parts by weight of photopolymerization initiator B were added. The solution was then diluted with methyl ethyl ketone (MEK) (dissolved by heating to 60°C). This diluted solution (curable composition) was then applied to a TAC (cellulose acetate) film using a coater to form a coating (approximately 100 μm thick).

[0321] (Glass transition temperature Tg)

[0322] The glass transition temperature (Tg) of the cured product was measured using a differential scanning calorimeter (DSC, TA Instruments "Discovery DSC25") under a nitrogen atmosphere at temperatures ranging from 30 to 220 °C (Comparative Examples 1-3 and Examples 1-3, and Reference Examples 2 and Example 8) or from -10 °C to 100 °C (Comparative Examples 4 and Examples 4-7) at a heating rate of 10 °C / min. It should be noted that the samples used were prepared in the same manner as the cured products (cured films) obtained during the curability evaluation (samples with a curability evaluation of "○").

[0323] (5% weight reduction in temperature)

[0324] The 5% weight reduction temperature of the cured product [°C] was determined using a thermogravimetric-differential thermal analyzer (TG-DTA, Rigaku Corporation, "Thermo Plus EVO2 TG-DTA8122") under a nitrogen atmosphere at temperatures ranging from 30 to 450°C (Comparative Examples 1-2 and Examples 1-3, and Reference Examples 2 and Example 8) or from 30°C to 350°C (Comparative Examples 4 and Examples 4-7), with a heating rate of 10°C / min. It should be noted that the samples used were prepared in the same manner as the cured products (cured films) obtained during the curability evaluation (samples with a curability evaluation of "○").

[0325] (Softness (or toughness))

[0326] The flexibility (or toughness) of the cured product (cured film) was evaluated according to the following criteria by confirming the state of a sample (cured film) with a film thickness of approximately 100 μm when bent 180° at room temperature (25°C). It should be noted that, as a sample, a cured film (isolated film) obtained by peeling off the TAC film from a sample prepared in the same manner as the cured product (cured film) obtained during the curability evaluation (sample with a curability evaluation of "○") was used.

[0327] ○…No rupture occurred

[0328] ×... causes a rupture

[0329] (Bending resistance and durability)

[0330] The flexural durability of the cured product (cured film) was evaluated by repeatedly bending a sample (cured film) with a film thickness of approximately 100 μm using a bending tester (YUASA SYSTEM "DMLHP-CS") at room temperature (25°C). It should be noted that the sample used was a cured film (isolated film) obtained by peeling off the TAC film from a sample prepared in the same manner as the cured product (cured film) obtained during the curability evaluation (sample with a curability evaluation of "○").

[0331] Specifically, firstly, as Figure 1 As shown in (a), a pair of plates 12 and 13 of the bending tester 10 [a pair of plates for holding the film (cured film) 11] are fixed so that the respective film mounting surfaces 12a and 13a are located on the same plane, and the film (cured film) 11 is placed on the film mounting surfaces 12a and 13a. Then, with the ends 12b and 13b of each opposing plate as the base point (rotation center), the pair of plates 12 and 13 are rotated and moved (moved symmetrically left and right) in a direction that brings the respective film mounting surfaces 12a and 13a closer to each other, thereby forming Figure 1 (b) shows the state in which the membrane mounting surfaces 12a and 13a face each other across a gap R defined by a spacer (not shown), eventually becoming parallel (this movement operation is referred to as the "closing operation" below). The gap R between the membrane mounting surfaces 12a and 13a is adjusted to 4 mm. After the closing operation is performed, the pair of plates 12 and 13 are rotated and moved in the opposite direction to the closing operation, thus becoming parallel again. Figure 1 (a) shows the state (the membrane mounting surfaces 12a and 13a are on the same plane) (hereinafter, this moving operation is referred to as the "opening operation"). Repeat this series of opening and closing operations (closing and opening operations) while visually observing the surface of the membrane (cured membrane) 11, and count the number of bends until the membrane develops creases or breaks and an abnormal appearance occurs.

[0332] [Compare Examples 1-2, 4-5 and Reference Example 2]

[0333] Various evaluations were conducted using the proportions of polymeric components shown in Tables 1-4.

[0334] [Comparative Example 3, Reference Examples 1 and 3, and Examples 1-8]

[0335] Various evaluations were conducted using a mixture (curable composition) obtained by mixing the polymerizable components in the proportions shown in Tables 1-4 and heating it to 60°C to melt it.

[0336] The results are shown in Tables 1-4. It should be noted that the numbers in parentheses in the column for polymerizability refer to the proportion [parts by mass], and the numbers in parentheses in the column for curability refer to the cumulative light intensity [mJ / cm²] during the preparation of the cured product. 2 ].

[0337] [Table 1]

[0338]

[0339] [Table 2]

[0340]

[0341] [Table 3]

[0342]

[0343] [Table 4]

[0344]

[0345] As shown in Tables 1-4, in Reference Example 1, which combines DNFPA with aryl groups bonded at positions 1-8 of the fluorene skeleton and NMT-A, although a composition with high refractive index and low viscosity can be prepared, crystal precipitation was confirmed within one day after preparation, indicating poor storage stability. In contrast, in the example combining di(meth)acrylate with NMT-A and a 9,9-bis(aryl)fluorene skeleton with aryl groups bonded at positions 9,9 (instead of 1-8), a curable composition was obtained that not only achieved an excellent balance between high refractive index and low viscosity but also unexpectedly exhibited good storage stability. It should be noted that, as shown in Example 8, as long as aryl groups are bonded at positions 9,9, even if aryl groups are bonded at positions 1-8, unlike Reference Example 1, excellent storage stability is achieved. On the other hand, Reference Example 3, which uses conventional POBA instead of NMT-A, exhibits worse storage stability than Example 8.

[0346] Furthermore, even though the composition of Reference Example 1 has a high refractive index and low viscosity, its curability is "×" or "△", making it difficult to prepare a cured product. In contrast, the compositions in the examples exhibit good curability, enabling the easy or efficient preparation of cured products.

[0347] It should be noted that, from the viewpoint of excellent flexibility, Examples 4 to 7 are preferred in the embodiments. In these embodiments, even with an increased proportion of NMT-A having a rigid naphthalene framework, the flexibility observed in Comparative Example 4 was maintained. In particular, although Examples 4 to 7 exhibited a glass transition temperature Tg higher than room temperature (25°C) compared to Comparative Example 4, they unexpectedly maintained flexibility. Furthermore, the excellent flexibility of Examples 4 to 7, especially Examples 4 to 5, may also result in good flexural durability. From the viewpoint of achieving a good balance of high refractive index, low viscosity, curability, and heat resistance, in addition to flexibility, Example 5 is more preferred.

[0348] Furthermore, in the embodiments, from the viewpoint of balancing high refractive index and low viscosity, and excellent storage stability, embodiments 1-3 and embodiment 8 are preferred. For example, comparing embodiments 2-3 of this application with comparative example 3 of this application and comparative examples 4-5 of Japanese Patent Application Publication No. 2013-053310, it can be seen that embodiments 2-3 of this application are superior in balancing high refractive index and low viscosity. From the viewpoint of being able to more effectively balance high refractive index, low viscosity, and high storage stability, as well as curability and heat resistance, embodiments 2 and 8 are further preferred. Among them, embodiment 2 is particularly preferred in applications where heat resistance is of greater importance, and embodiment 8 is particularly preferred in applications where refractive index is of greater importance.

[0349] Industrial practicality

[0350] The curable compositions or cured products disclosed herein exhibit excellent optical properties such as high refractive index and can be used for various applications, such as: coatings or films, specifically paints, inks, protective films for electronic instruments and liquid crystal components, etc.; adhesives, pressure-sensitive adhesives; resin fillers; electrical and electronic materials or electrical and electronic components (electrical and electronic equipment), specifically antistatic agents, carrier transport agents, light emitters, organic photosensitive materials, thermal recording materials, photochromic materials, holographic recording materials, antistatic 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.; mechanical materials or mechanical components (machines), specifically automotive materials or components, aerospace-related materials or components, sliding components, etc.

[0351] In particular, it can be effectively used as optical components (optical elements) or optical materials, such as: optical adhesives (sealants) such as OCR (optically transparent resin), OCA (optically transparent adhesive) tapes or films, optical films (optical sheets), optical lenses, prisms, holograms, optical fibers, etc.

[0352] Examples of optical thin films include: polarizing films, polarizing elements and protective films for polarizing films, phase retardation films, alignment films, viewing angle widening (compensation) films, diffusers, prism sheets, light guides, 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 (ACF) films, electromagnetic wave shielding (EMI) films, films for electrode substrates, films for color filter substrates, blocking films, color filter layers, black matrix layers, adhesive layers or release layers between optical films, etc. Optical films can also be used in displays such as liquid crystal displays (LCDs), organic OLED displays (OLEDs), plasma displays (PDPs), field emission displays (FEDs), and electronic paper. It should be noted that since the cured material (cured film) of this disclosure can also improve flexibility or bending resistance durability, it can also be effectively used as an optical film in displays or image display devices that can be repeatedly bent (e.g., the display section of a foldable or rollable information terminal such as a foldable or rollable smartphone). Therefore, this disclosure also includes: a foldable or rollable information terminal containing the above-mentioned cured material (cured film), and a method for improving the durability (bending resistance durability of the display section) of a foldable or rollable information terminal using the above-mentioned cured material (cured film).

[0353] Examples of optical lenses include: eyeglass lenses, contact lenses, camera lenses, VTR zoom lenses, pickup lenses, Fresnel lenses, solar condenser lenses, objective lenses, and rod lens arrays.

[0354] Explanation of reference numerals in the attached figures

[0355] 10…………Bending Tester

[0356] 11…………membrane (cured film)

[0357] 12, 13...board

[0358] 12a, 13a... membrane mounting surfaces

[0359] 12b, 13b... Plate ends

Claims

1. A curable composition comprising (meth)acrylate having a 9,9-bisarylfluorene backbone and naphthyl methyl (meth)acrylate.

2. The curable composition according to claim 1, wherein, The (meth)acrylate having a 9,9-bisarylfluorene backbone comprises (meth)acrylate represented by the following formula (1). In the formula, R 1 Indicates a substituent, m1 represents an integer from 0 to 8. Z 1a and Z 1b Independently representing aromatic rings, R 2a and R 2b The substituents are represented independently, and m2a and m2b independently represent integers greater than 0. A 1a and A 1b Independently representing alkylene groups, n1a and n1b independently represent numbers greater than 0. R 3a and R 3b It can be used to represent either a hydrogen atom or a methyl group independently.

3. The curable composition according to claim 2, wherein, In the above equation (1), R 1 This represents a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, or a substituted amino group; m1 represents an integer from 0 to 2. Z 1a and Z 1b Independently represent C 6-18 Aromatic rings, R 2a and R 2b Each group independently represents a halogen atom, hydrocarbon group, alkoxy group, acyl group, nitro group, cyano group, or substituted amino group; m2a and m2b independently represent integers from 0 to 2. A 1a and A 1b Independently represent C 2-4 Alkylenes, n1a and n1b independently represent numbers from 0 to 10.

4. The curable composition according to claim 2, wherein, In the above equation (1), R 1 This represents a hydrocarbon group, and m1 represents an integer from 0 to 2. Z 1a and Z 1b Independently represent C 6-12 Aromatic rings, R 2a and R 2b Each group independently represents a hydrocarbon group, and m2a and m2b independently represent integers from 0 to 2. A 1a and A 1b Independently represent C 2-3 Alkylenes, n1a and n1b independently represent 0~8.

5. The curable composition according to any one of claims 1 to 4, wherein, The ratio of the (meth)acrylate having a 9,9-bisarylfluorene skeleton to the (meth)acrylate naphthylmethyl ester by mass is 20 / 80 to 85 / 15.

6. The curable composition according to any one of claims 1 to 4, wherein, The ratio of the (meth)acrylate having a 9,9-bisarylfluorene skeleton to the (meth)acrylate naphthylmethyl ester is, by mass ratio, 40 / 60 to 80 / 20.

7. A cured product, which is formed by curing the curable composition according to any one of claims 1 to 4.

8. A method for manufacturing a cured material, comprising a step of curing the curable composition according to any one of claims 1 to 4.

9. An optical component comprising the cured material of claim 7.

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