JP6923314B2 - Epoxy (meth) acrylate and its curable composition - Google Patents

Description

The present invention relates to an epoxy (meth) acrylate containing a 9,9-bisarylfluorene skeleton, a curable composition containing the epoxy (meth) acrylate, a cured product thereof, and a method for producing the cured product.

A compound having a 9,9-bisarylfluorene skeleton is excellent in optical properties such as high refractive index and transparency and heat resistance, so that it is an optical lens, an optical film (for example, a color filter, a protective film, etc.). , Optical hard coat agents, optical adhesives (or adhesives), etc. are being studied for use as various optical members. Among the compounds having a 9,9-bisarylfluorene skeleton, the compound having a (meth) acryloyl group can be easily cured by using radical polymerization, and is useful as an optical member from the viewpoint of productivity and the like.

For example, International Publication No. 2013/022065 (Patent Document 1) discloses a polyfunctional (meth) acrylate represented by the following formula.

(In the formula, R ^1a and R ^1b are substituents, R ^2a and R ^2b are alkylene groups, R ^3a and R ^3b are hydrogen atoms or methyl groups, R ^4a and R ^4b are substituents, k1 and k2 are 0 to 4 , M1 and m2 are integers of 0 or more, n1 and n2 are integers of 1 to 4, and p1 and p2 are integers of 0 to 4. However, n1 + p1 ≦ 5 and n2 + p2 ≦ 5).

In this document, it is described that the average value of m1 + m2 is 8.5 to 17 in the above formula, and in the examples, 9,9-bis (4-acryloyloxypolyethoxyphenyl) fluorene (total number of ethoxy groups added) is described. Compounds with an average value of 9.0 to 16.0) have been synthesized. In such a polyfunctional (meth) acrylate, the number of oxyalkylene groups added is adjusted to a specific range, so that the cured product has excellent scratch resistance (or flexibility). However, the hardness of the cured product is relatively low because the crosslink density tends to decrease due to the influence of the oxyalkylene group. Therefore, its use as a member is limited, and the development of a 9,9-bisarylfluorene skeleton-containing (meth) acrylate capable of forming a cured product having both high hardness and flexibility has been expected.

Further, as a typical example of the 9,9-bisarylfluorene skeleton-containing (meth) acrylate, an epoxy (meth) acrylate synthesized by a ring-opening reaction of an epoxy group is used. For example, Japanese Patent Application Laid-Open No. 7-48424 (Patent Document 2) discloses an epoxy (meth) acrylate resin represented by the following formula I.

(However, R indicates H or a lower alkyl group, and _{R'indicates H or CH 3.} An integer of n = 0 to 20).

In the examples of this document, a compound in which R and R'are a hydrogen atom and n is 0 and a compound in which R and R'are a hydrogen atom and n is 1 are synthesized, and have high heat resistance, solvent solubility and It is described that it has excellent photosensitivity. Since such an epoxy acrylate resin has a small n in the above formula I, the crosslink density tends to be relatively high, and the hardness is high probably because the rigid 9,9-bisphenylfluorene skeletons are present in close proximity to each other. It is easy to obtain a cured product of. However, due to lack of flexibility, its use as a member has been limited.

Further, Japanese Patent Application Laid-Open No. 2004-83855 (Patent Document 3) discloses a fluorene-containing epoxy acrylate resin represented by the following formula.

(In the formula, R ₁ and R ₂ independently represent a hydrogen atom or a methyl group, m independently represents an integer of 2 to 5, and n independently represents an integer of 0 to 10).

In the examples of this document, 9,9-bis [3,4-di (3-acryloyloxy-2-hydroxypropoxy) phenyl] fluorene (in the above formula, R ₂ is a hydrogen atom, m = 2, n = 0). The compound) is synthesized and cured to prepare a cured product. Since such a fluorene-containing epoxy acrylate resin has a large number of acryloyloxy groups, the crosslink density tends to be high, and the hardness of the cured product is high (pencil hardness measured according to JIS K-5400 is 5H). However, only compounds in which the number of repeating units n of the oxyalkylene group that contributes to flexibility is 0 are described, and this cured product has low flexibility.

Further, Japanese Patent Application Laid-Open No. 2015-040224 (Patent Document 4) discloses a fluorene skeleton-containing (meth) acrylate represented by the following formula.

(In the formula, Z is an aromatic hydrocarbon ring, R ¹ and R ² are substituents, R ³ is an alkylene group, X ¹ is a (meth) acryloyl group, X ² is a hydrogen atom or a (meth) acryloyl group-containing group. k is an integer of 0 to 4, m is an integer of 0 or more, n is an integer of 0 or more, and p is an integer of 1 or more. However, at least one X ² is a (meth) acryloyl group-containing group).

In the examples of this document, 9,9-bis [6- (2,3-diacryloyloxypropoxy) -2-naphthyl] fluorene (in the above formula, Z is a naphthalene ring, X ¹ and X ² are (meth). A composition containing an acryloyl group (a compound having k = m = n = 0 and p = 1) and a cured product thereof are being prepared. Similar to the above, such a fluorene (meth) acrylate also has a large number of acryloyloxy groups, so that the crosslink density tends to be high and the hardness of the cured product is high. However, also in this document, only the compound in which the number of repeating units n of the oxyalkylene group contributing to flexibility is 0 is specifically described, and this cured product has low flexibility.

Further, Japanese Patent Application Laid-Open No. 2012-206968 (Patent Document 5) discloses a fluorene-containing epoxy (meth) acrylate represented by the following formula (1).

(In the formula, ring Z is a benzene ring or a fused polycyclic aromatic hydrocarbon ring, R ¹ is an alkyl group, R ² is an alkylene group, R ³ is a hydrogen atom or methyl group, R ⁴ is a hydrocarbon group, etc. k is an integer of 0 to 4, m is an integer of 0 or 1 or more, n is an integer of 0 or 1 or more, and p is an integer of 1 or more. However, when ring Z is a benzene ring, n is 1 or more. And at least one R ⁴ is an aryl group).

In the examples, 9,9-bis [6- (3- (meth) acryloyloxy-2-hydroxypropoxy) -2-naphthyl] fluorene (in the above formula (1), Z is a naphthalene ring and R ³ is a hydrogen atom. Or a compound of methyl group, k = m = n = 0, p = 1) and; 9,9-bis [6- [2- (3-acryloyloxy-2-hydroxypropoxy) ethoxy] -2-naphthyl] fluorene (In the above formula (1), Z is a naphthalene ring, R ² is an ethylene group, R ³ is a hydrogen atom, and a compound having k = n = 0 and m = p = 1) is prepared. Such a fluorene-containing epoxy (meth) acrylate has a naphthalene ring having a continuous benzene ring structure introduced as the ring Z, and has a rigid skeleton, so that the hardness of the cured product is relatively high. Further, it is described that a hydroxyl group can be easily introduced into the side chain of the resin skeleton and the stress of the cured product can be relaxed. However, also in this document, only compounds having 0 or 1 repeating units of oxyalkylene groups that contribute to flexibility are specifically described, and high hardness and flexibility cannot be achieved at the same time.

In the epoxy (meth) acrylates described in Patent Documents 3 to 5, although the number of repeating units is specified in a wide range for the oxyalkylene group capable of imparting flexibility, the technical significance (or feature) thereof is , No particular mention is made in any of the documents. Specific studies on the introduction of the oxyalkylene group have not even been studied in Patent Documents 3 and 4, and in Patent Document 5, only compounds having a repeating unit number of 1 have been studied. Therefore, an epoxy (meth) acrylate in which the number of oxyalkylene groups added (or the number of moles added) is increased has not been substantially known.

Further, in general, the high hardness and flexibility of a cured product have a trade-off relationship in which improving one of them lowers the other. It was very difficult.

International Publication No. 2013/022065 (Claims, paragraphs [0003] [0013] [0041], Examples) JP-A-7-48424 (Claims, paragraph [0056], Examples) JP-A-2004-83855 (Claim 7, paragraph [0182], Examples 6 and 7) JP-A-2015-040224 (Claims, paragraph [0026], Examples) Japanese Unexamined Patent Publication No. 2012-206868 (Claims, paragraph [0055], Examples)

Therefore, an object of the present invention is a 9,9-bisarylfluorene skeleton-containing (meth) acrylate capable of forming a cured product having both high hardness and flexibility, a curable composition containing the (meth) acrylate, and a curable composition thereof. An object of the present invention is to provide a cured product and a method for producing the cured product.

Another object of the present invention is a 9,9-bisarylfluorene skeleton-containing (meth) acrylate that can improve hardness even if the crosslink density is low, a curable composition containing the (meth) acrylate, and a cured product thereof. An object of the present invention is to provide a method for producing the cured product.

As a result of diligent studies to achieve the above problems, the present inventors have introduced an oxyalkylene group (or an alkoxy group) into an epoxy (meth) acrylate having a 9,9-bisarylfluorene skeleton at a predetermined number of repetitions. Although it is expected that a cured product having low crosslink density and hardness can be obtained from a soft oxyalkylene group, it has been surprisingly found that a cured product having high hardness and flexibility can be obtained. The present invention has been completed.

That is, the epoxy (meth) acrylate of the present invention is an epoxy (meth) acrylate represented by the following formula (1).

(In the formula, rings Z ¹ and Z ² are aromatic hydrocarbon rings, R ^1a and R ^1b and R ^{2a and R 2b} are independently non-radical polymerizable substituents, and R ^3a and R ^3b are alkylene groups and R. ^4a and ^R4b are hydrogen atoms or methyl groups, k1 and k2 are integers of 0 to 4, m1 and m2 are integers of 0 or more, n1 and n2 are integers of 1 to 10, n1 + n2 are 2 to 30, p1 and p2 are. It indicates an integer of 0 to 4. However, when p1 + p2 ≧ 1 and ^{both rings Z 1} and Z ² are fused polycyclic aromatic hydrocarbon rings, n1 + n2 ≧ 3).

In the formula (1), it may be about one p1 and p2, respectively, the ring ^{Z 1} and ^{Z 2} and n1 + n2 may be the following (a) or (b).
(A) Rings Z ¹ and Z ² are benzene rings or biphenyl rings, respectively, and n1 + n2 is about 3 to 20. (B) Rings Z ¹ and Z ² are naphthalene rings, and n1 + n2 is about 4 to 20. ..

In the formula (1), the rings Z ¹ and Z ² may be a benzene ring or a naphthalene ring; R ^2a and R ^2b may be an alkyl group; R ^3a and R ^3b may be a C _2-3 alkylene. It may be a group; k1 and k2 may be integers of about 0 to 3; m1 and m2 may be integers of about 0 to 3; n1 and n2 may be 2 to 9 (for example, 2). It may be an integer of about 8); n1 + n2 may be about 4 to 18 (for example, 4 to 15).

The present invention includes a curable composition containing the epoxy (meth) acrylate. The curable composition may further contain a photopolymerization initiator.

The present invention also includes a cured product obtained by curing the curable composition. In the cured product, the pencil hardness measured according to JIS K5600-5-4 is 4B or more (for example, HB or more), and the mandrel by the bending resistance test measured according to JIS K5600-5-1. The diameter may be 2 mm or less. The cured product may be an optical member (for example, a display film or a coating film).

Furthermore, the present invention also includes a method of producing a cured product by curing the curable composition.

In addition, in this specification, "(meth) acrylate" is used in the meaning including both acrylate and methacrylate.

In the present invention, since a predetermined amount of oxyalkylene group is introduced into the epoxy (meth) acrylate having a 9,9-bisarylfluorene skeleton, a cured product having both high hardness and flexibility can be formed in a well-balanced manner. Further, in the present invention, the hardness can be improved even if the crosslink density of the cured product is lowered by the introduction of the oxyalkylene group.

[Epoxy (meth) acrylate]
The 9,9-bisarylfluorene skeleton-containing (meth) acrylate of the present invention is an epoxy (meth) acrylate represented by the following formula (1), and in the formula (1), the value of n1 + n2 is adjusted to a specific range. Has been done.

(In the formula, rings Z ¹ and Z ² are aromatic hydrocarbon rings, R ^1a and R ^1b and R ^{2a and R 2b} are independently non-radical polymerizable substituents, and R ^3a and R ^3b are alkylene groups and R. ^4a and ^R4b are hydrogen atoms or methyl groups, k1 and k2 are integers of 0 to 4, m1 and m2 are integers of 0 or more, n1 and n2 are integers of 1 to 10, and p1 and p2 are integers of 0 to 4. shown. However, a p1 + p2 ≧ 1, and if both rings ^{Z 1} and ^{Z 2} is a fused polycyclic aromatic hydrocarbon ring, an n1 + n2 ≧ 3).

In the above formula (1), ^{examples of the aromatic hydrocarbon ring (or arene ring) represented by the rings Z 1} and Z ² include a monocyclic arene ring such as a benzene ring and a polycyclic arene ring. The polycyclic arene ring includes a condensed polycyclic arene ring (condensed polycyclic aromatic hydrocarbon ring), a ring-assembled arene ring (ring-assembled aromatic hydrocarbon ring), and the like.

Examples of the fused polycyclic arene ring include a fused bicyclic arene ring (for example, a _C10-16 fused bicyclic arene ring such as a naphthalene ring) and a fused tricyclic arene ring (for example, anthracene ring and phenanthrene ring). Etc.), such as fused bicyclic arene rings. Preferred condensed polycyclic arene rings include naphthalene rings and anthracene rings, and naphthalene rings are particularly preferable.

_{The ring-assembled arene ring includes a bi-C 6-12} arene ring such as a biphenyl ring, a binaphthyl ring, a phenylnaphthalene ring (for example, a 1-phenylnaphthalene ring, a 2-phenylnaphthalene ring, etc.), and a tellarene ring. Examples thereof include a ring (for example, a Tel C _6-12 arene ring such as a terphenylene ring). Preferred assembling ring arene rings include biC _6-10 arene rings, particularly biphenyl rings and the like.

^{The two rings Z 1} and Z ² attached to the 9-position of fluorene may be the same or different, and are usually often the same. Of the rings Z ¹ and Z ² , a benzene ring, a naphthalene ring, a biphenyl ring (particularly, a benzene ring or a naphthalene ring) and the like are preferable, and from the viewpoint of flexibility, a benzene ring is particularly preferable, and from the viewpoint of high refractive index, the benzene ring is particularly preferable. , Particularly the naphthalene ring is preferable.

The substitution positions of ^{the rings Z 1} and Z ² bonded to the 9-position of fluorene are not particularly limited. For example, when rings Z ¹ and Z ^{2 are naphthalene rings, the group corresponding to rings Z 1} and Z ² bonded to the 9-position of fluorene may be a 1-naphthyl group, a 2-naphthyl group, or the like. When the rings Z ¹ and Z ^{2 are biphenyl rings, the groups corresponding to the rings Z 1} and Z ² bonded to the 9-position of fluorene are 2-biphenyl group, 3-biphenyl group, 4-biphenyl group and the like. There may be.

In the above formula (1), the non-radical polymerizable substituents R ^1a and R ^1b include a hydrocarbon group [for example, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, t-butyl). Linear or branched C _1-6 alkyl groups such as groups), aryl groups (eg C _6-10 aryl groups such as phenyl groups), etc.], cyano groups, halogen atoms (eg fluorine atoms, etc.) Chlorine atom, bromine atom, etc.).

Among these groups R ^1a and R ^1b , alkyl groups (for example, linear or branched C _1-4 alkyl groups (particularly C _1-3 alkyl groups such as methyl groups)), cyano groups, halogen atoms. Is preferable, and an alkyl group is particularly preferable.

The substitution numbers k1 and k2 of the groups R ^1a and R ^1b are integers of 0 to 4 (for example, about 0 to 3), preferably integers of about 0 to 2, more preferably 0 or 1, and particularly 0. The substitution numbers k1 and k2 in the two benzene rings constituting the fluorene ring may be the same or different from each other, ^{and the types of the groups R 1a} and R ^1b may be the same or different from each other. When k1 and k2 are 2 or more, ^{the types of groups R 1a} and R ^1b in the same benzene ring may be the same or different from each other. The substitution positions of the groups R ^1a and R ^1b are not particularly limited, and may be, for example, the 2-position to the 7-position (2-position, 3-position, 7-position, etc.) of the fluorene ring.

In the above formula (1), the non-radical polymerizable substituents R ^2a and R ^2b include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom) and a hydrocarbon group [for example, an alkyl group (methyl group). , Ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group and other linear or branched C _1-10 alkyl groups, preferably linear or branched C _1-6 alkyl groups, more preferably linear or branched C _1-4 alkyl groups; cycloalkyl groups (eg, cyclopentyl groups, C _5-10 cycloalkyl groups such as cyclohexyl groups); aryl groups [for example, a phenyl group, alkylphenyl group (e.g., methylphenyl group (tolyl group), a dimethylphenyl group (xylyl), etc.), a biphenyl group, a C _6-12 aryl group such as a naphthyl group]; aralkyl groups (e.g. _{, C 6-10} aryl-C _1-4 alkyl groups such as benzyl group, phenethyl group, etc.], alkoxy groups (eg, methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, t-butoxy) Linear or branched C _1-10 alkoxy groups such as groups), cycloalkyloxy groups (eg C _5-10 cycloalkyloxy groups such as cyclohexyloxy groups), aryloxy groups (eg phenoxy groups) C _6-10 aryloxy group such as C 6-10 aryloxy group), aralkyloxy group (eg C _6-10 aryl-C _1-4 alkyloxy group such as benzyloxy group), alkylthio group (eg methylthio group, ethylthio group, etc.) propylthio, n- butylthio group, t-like _{C 1-10} alkylthio, such as butylthio group), cycloalkylthio groups (for example, a _{C 5-10} cycloalkylthio groups such as cyclohexyl thio group) an arylthio group (e.g., a thiophenoxy group _{C 6-10} arylthio groups such as C 6-10 arylthio groups), aralkylthio groups (eg C _6-10 aryl-C _1-4 alkylthio groups such as benzylthio groups), acyl groups (eg C _1-6 acyls such as acetyl groups) Groups, etc.), nitro groups, cyano groups, dialkylamino groups (eg, diC _1-4 alkylamino groups such as dimethylamino groups), dialkylcarbonylamino groups (eg, diacetylamino groups such as di (C _1-4)) Alkyl-carbonyl) amino group, etc.) can be exemplified.

Among these groups R ^2a and R ^2b , typically, a halogen atom, a hydrocarbon group (alkyl group, cycloalkyl group, aryl group, aralkyl group), an alkoxy group, an acyl group, a nitro group, a cyano group, and a substituent are substituted. Amino groups and the like can be mentioned. Preferred groups R ^2a and R ^2b include an alkyl group (a linear or branched C _1-6 alkyl group such as a methyl group) and an alkoxy group (a linear or branched C _{1-4 such as a methoxy group).} Alkoxy groups and the like), in particular alkyl groups (particularly linear or branched C _1-4 alkyl groups such as methyl groups). When the groups R ^2a and R ^2b are aryl groups, the groups R ^2a and R ^2b may form the ring-aggregated arene ring together with the rings Z ¹ and Z ^2. The types of groups R ^2a and R ^2b may be the same or different in the same or different ^{rings Z 1} and Z ^2.

Substituents which m1 and m2 of the radicals ^{R 2a} and ^{R 2b} may be any integer of 0 or more, can be appropriately selected depending on the type of ring ^{Z 1} and ^{Z 2.} For example, it may be an integer of about 0 to 8, preferably an integer of about 0 to 4 (for example, 0 to 3), more preferably an integer of about 0 to 2 (for example, 0 or 1), particularly 0. There may be. In particular, if m1 and m2 are 1, ring ^{Z 1} and ^{Z 2} is a benzene ring, a naphthalene ring or biphenyl ring, groups ^{R 2a} and ^{R 2b} may be a methyl group. The substitution positions of the groups R ^2a and R ^2b are not particularly limited, and the group- [O- (R ^3a O) _n1- CH ₂ CH (OH) CH _2- OC (= O) -CR ^4a = CH ₂ ] And Group- [O- (R ^3b O) _n2- CH ₂ CH (OH) CH _2- OC (= O) -CR ^4b = CH ₂ ] (These two groups are referred to as (meth) acryloyl group-containing groups. It may be replaced at a position other than the replacement position of).

In the above formula (1), the alkylene groups R ^3a and R ^3b include a linear or branched alkylene group, and examples of the linear alkylene group include an ethylene group, a trimethylene group, and a tetramethylene group. Can be exemplified as a linear C _2-6 alkylene group (preferably a linear C _2-3 alkylene group, more preferably a linear C _2-3 alkylene group, particularly an ethylene group), as a branched chain alkylene group. _{For example, a branched C 3-6} alkylene group (preferably a branched C _3-4 alkylene group, particularly a propylene group) such as a propylene group, a 1,2-butanjiyl group, or a 1,3-butanjiyl group may be used. Can be mentioned. Of these groups R ^3a and R ^3b , preferably a linear or branched C _2-6 alkylene group (for example, a linear or branched C _2-4 alkylene group), more preferably a linear. It may be in the form of a branched or branched C _2-3 alkylene group (particularly an ethylene group or a propylene group). ^{The types of the alkylene groups R 3a} and R ^3b may be the same or different between the respective (meth) acryloyl group-containing groups substituted with the same or different rings Z ¹ and Z ^{2, and are usually the same.} be. When n1 and n2 are 2 or more, ^{the types of the alkylene groups R 3a} and R ^{3b in} the same (meth) acryloyl group-containing group may be the same or different, and are usually the same.

N1 and n2 indicating the number of repetitions of the oxyalkylene groups (OR ^3a and OR ^3b ) can be selected from a range of 1 or more integers (for example, integers of about 1 to 20), for example, 1 to 15 (for example, 2 to 2). It may be an integer of about 9), preferably an integer of about 1 to 10 (for example, 2 to 8), and more preferably an integer of about 2 to 7 (for example, 3 to 6). Further, in each (meth) acryloyl group-containing group substituted with the same or different rings Z ¹ and Z ² , n1 and n2 may be the same or different, respectively. The repetition numbers n1 and n2 may be average values (arithmetic mean or arithmetic mean) in the molecular assembly of the compound represented by the formula (1), and are about the same as the range of the integers. May be good.

The total number of repetitions n1 and n2 means the total number of oxyalkylene groups (total addition number) in one molecule of the epoxy (meth) acrylate represented by the above formula (1), and may be simply n1 + n2. be. Note that n1 + n2 means the total number of all n1 and n2 existing as many as the number of p1 and p2 when p1 and / or p2 is 2 or more. In the present invention, by adjusting the value of n1 + n2 within a predetermined range, it is possible to achieve both high hardness and flexibility in the cured product in a well-balanced manner.

When rings Z ¹ and Z ² are monocyclic aromatic hydrocarbon rings or ring-assembled aromatic hydrocarbon rings (eg, benzene rings or biphenyl rings, especially benzene rings, etc.), n1 + n2 is, for example, 2-30. It can be selected from a range of integers of about, for example, an integer of about 3 to 25 (eg, 3 to 20), preferably an integer of about 3 to 18 (eg, 4 to 16), more preferably 4 to 15 (eg, for example). It may be an integer of about 4 to 14), particularly an integer of about 5 to 14 (for example, 5 to 13), and is usually 4 to 18 (for example, 5 to 15), preferably 6 to 13 (for example, 6). It may be an integer of about 12).

However, when rings Z ¹ and Z ² are both condensed polycyclic aromatic hydrocarbon rings (particularly, naphthalene ring, etc.), the cured product tends to be rigid and the flexibility tends to decrease, so n1 + n2 ≧ 3. , Preferably n1 + n2 ≧ 4, more preferably n1 + n2 ≧ 5 (for example, n1 + n2 ≧ 6), where n1 + n2 is, for example, an integer of about 3 to 30, preferably 4 to 20 (for example, 4 to 18). It may be an integer of about, more preferably an integer of about 5 to 15 (for example, 5 to 13).

Further, n1 + n2 may be an integer as described above, but may be an average value (or an average number of added moles) of the molecular aggregates of the compounds represented by the formula (1). n1 + n2 can be selected from a range of, for example, about 2 to 30, ^{and regardless of the type of rings Z 1} and Z ² , for example, 2.5 to 25 (for example, 3 to 20), preferably 3.5 to 18 (preferably 3.5 to 18). For example, 4 to 16), more preferably 4 to 15 (for example, 4.5 to 14.5), particularly 5 to 14 (for example, 5.5 to 13.5), and usually 4 It may be about 18 (for example, 5 to 15.5), preferably about 6 to 13 (for example, 6.5 to 12.5). If the value of n1 + n2 is too small, the crosslink density of the cured product tends to be high, and the flexibility due to the oxyalkylene group is difficult to be exhibited, so that there is a possibility that high hardness and flexibility cannot be balanced at the same time. On the contrary, if the value of n1 + n2 is too large, the crosslink density of the cured product is remarkably lowered, and high hardness and flexibility cannot be balanced in a well-balanced manner, and further, 9,9- per unit amount (for example, unit weight). Since the bisarylfluorene skeleton content (for example, the number of moles contained) also decreases, excellent properties such as high refractive index and high heat resistance derived from the skeleton may decrease. In the present invention, even if the value of n1 + n2 is relatively large (for example, 3 to 20, preferably 4 to 18 (for example, 4 to 16), and more preferably 5 to 15 (for example, 5 to 12)). However, a cured product with a good balance of high hardness and flexibility can be obtained. In addition, n1 + n2 can be measured by a conventional method, for example, in the synthesis of the first hydroxy compound represented by the formula (3) described later, the second represented by the formula (4) which is a raw material. From the ratio of the amount of the hydroxy compound to the amount of the alkylene oxide or the alkylene carbonate consumed, it can be measured by a method of calculating as an arithmetic mean or an arithmetic mean (for example, the method described in Patent Document 1).

In the formula (1), the groups R ^4a and R ^4b are hydrogen atoms or methyl groups. In each (meth) acryloyl group-containing group substituted with the same or different rings Z ¹ and Z ^{2 , the groups R 4a} and R ^{4 b} may be the same or different, respectively, and are usually the same.

In the formula (1), the substitution numbers p1 and p2 of the (meth) acryloyl group-containing group are integers of 0 or more, for example, an integer of 0 to 4, preferably an integer of 1 to 3, and more preferably 1 or It may be 2 (particularly 1). However, p1 + p2 ≧ 1. If p1 and p2 are too large, the crosslink density tends to be high, which may reduce the flexibility. Incidentally, substituents which p1 and p2, in each ring ^{Z 1} and ^{Z 2,} may be the same or different.

(Meth) acryloyl group-containing groups can be substituted in a suitable position on the ring Z ¹ and Z ^2, for example, when ring Z ¹ and Z ² is a benzene ring, the suitable position position 2～6- When it can be substituted and p1 and p2 are 1, it is often substituted at the 2-, 3-, 4-position (particularly, 3-position or 4-position) of the phenyl group. When p1 and p2 are 2, they are often replaced with 2-position and 4-position, 3-position and 4-position (particularly 2-position and 4-position) and the like. When p1 and p2 are 3 or more, the substitution position is not particularly limited. Further, when the rings Z ¹ and Z ² are naphthalene rings, they are often substituted with any of the 5-8-positions of the naphthyl group. For example, when p1 and p2 are 1, fluorene The 1-position or 2-position of the naphthalene ring is substituted with respect to the 9-position (replacement in the relationship of 1-naphthyl or 2-naphthyl), and the 1,5-position and 2,6 are substituted with respect to this substitution position. In many cases, the (meth) acryloyl group-containing group is substituted in a relationship such as the − position (particularly the relationship at the 2,6-position). When p1 and p2 are 2 or more, the replacement position is not particularly limited. Further, in the ring-assembled arene rings Z ¹ and Z ² , the substitution position of the (meth) acryloyl group-containing group is not particularly limited. For example, when p1 and p2 are 1, the arene bonded to the 9-position of fluorene. It may be replaced with a ring and / or an arene ring adjacent to this arene ring. For example, the 3- or 4-position of the biphenyl rings Z ¹ and Z ² may be bonded to the 9-position of fluorene. When the 3-position of the biphenyl rings Z ¹ and Z ² is attached to the 9-position of fluorene, the substitution position of the (meth) acryloyl group-containing group is 2-,4-, 5-, 6- of the biphenyl ring. , 2'-, 3'-, 4'-position, usually 6-, 3'-, 4'-position, preferably 6-, 4'-position (particularly, 6-position) ) May be replaced. When the 4-position of the biphenyl rings Z ¹ and Z ² is bonded to the 9-position of fluorene, the substitution position of the (meth) acryloyl group-containing group is 2-, 3-, 2'-, 3 of the biphenyl ring. It may be in any of the'- and 4'-positions, and is usually replaced with the 2-, 3'-, 4'-positions, preferably the 2-, 4'-positions (particularly the 2-positions). May be good. When p1 and p2 are 2 or more, the replacement position is not particularly limited.

Among the epoxy (meth) acrylates represented by the formula (1), typical compounds include, for example, in the formula (1), rings Z ¹ and Z ² are benzene rings, p1 = p2 = 1, n1. Compounds with = n2 = 1, that is, 9,9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) alkoxyphenyl] fluorenes; in the above formula (1), rings Z ¹ and Z ² are Benzene ring or naphthalene ring, compounds with p1 = p2 = 1, n1 and n2 of 2-10, ie 9,9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) polyalkoxyphenyl] fluorene Kind: 9,9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) polyalkoxynaphthyl] fluorenes and the like.

9,9-Bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) alkoxyphenyl] As fluorenes, in the above formula (1), rings Z ¹ and Z ² are substituted or unsubstituted benzene rings. Compounds in which k1 = k2 = 0, R ^3a and R ^3b are C _2-4 alkylene groups, n1 = n2 = 1, p1 = p2 = 1, for example, (1a) 9,9-bis [4- (2- (2-) (3- (Meta) acryloyloxy-2-hydroxypropoxy) ethoxy) phenyl] phenyl] fluorene, 9,9-bis [4- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) propoxy) phenyl] fluorene Such as 9,9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) C _2-4 alkoxyphenyl] fluorene; (1b) 9,9-bis [4- (2- (3- (meth)) ) Acryloyloxy-2-hydroxypropoxy) ethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) propoxy) -3-methyl Phenyl] fluorene, 9,9-bis [4- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) -3-isopropylphenyl] fluorene, 9,9-bis [4- (2- (2-) (3- (Meta) acryloyloxy-2-hydroxypropoxy) ethoxy) -3-isobutylphenyl] fluorene, 9,9-bis [4- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) ) -3-t-Butylphenyl] Fluorene, 9,9-bis [4- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) -3,5-dimethylphenyl] fluorene, 9, 9-bis [4- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) -3-t-butyl-6-methylphenyl] fluorene, 9,9-bis [4- (2- (2-) (3- (Meta) acryloyloxy-2-hydroxypropoxy) ethoxy) -2,5-dimethylphenyl] 9,9-bis such as fluorene [(3- (meth) acryloyloxy-2-hydroxypropoxy) C _{2- 4} Alkoxy-mono or di C _1-4 alkylphenyl] fluorene; (1c) 9,9-bis [4- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) -3-shiku Rohexylphenyl] fluorene, 9,9-bis [4-(2- (3- (meth) acryloyloxy-2-hydroxypropoxy) propoxy) -3-cyclohexylphenyl] fluorene and other 9,9-bis [(3) -(Meta) acryloyloxy-2-hydroxypropoxy) C _2-4 Alkoxy-C _5-10 Cycloalkylphenyl] Fluolene; (1d) 9,9-bis [4- (2- (3- (meth) acryloyloxy) -2-Hydroxypropoxy) ethoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) propoxy) -3-phenylphenyl] fluorene Such as 9,9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) C _2-4 alkoxy-C _6-10 arylphenyl] fluorene and the like can be exemplified.

9,9-Bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) polyalkoxyphenyl] As fluorenes, in the above formula (1), rings Z ¹ and Z ² are substituted or unsubstituted benzene rings. , K1 = k2 = 0, R ^3a and R ^3b are C _2-4 alkylene groups, n1 and n2 are 2 to 10 and p1 = p2 = 1, respectively, that is, the compounds of (1a) to (1d). Corresponding to, compounds in which n1 and n2 are 2-10, respectively, eg, (1e) 9,9-bis [4- (2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy)). Ethoxy) ethoxy) phenyl] fluorene, 9,9-bis [4- (2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) propoxy) propoxy) phenyl] fluorene, 9,9-bis [ 4- (2- (2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) ethoxy) phenyl] fluorene and other 9,9-bis [(3- (meth) acryloyloxy) -2-Hydroxypropoxy) di to deca C _2-4 alkoxyphenyl] fluorene; (1f) 9,9-bis [4- (2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) ) Ethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) propoxy) propoxy) -3-methylphenyl] fluorene , 9,9-Bis [4- (2- (2- (2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) ethoxy) ethoxy) -3-isopropylphenyl] fluorene, 9,9- Bis [4- (2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) ethoxy) -3,5-dimethylphenyl] fluorene and other 9,9-bis [(3- (meth) ) Acryloyloxy-2-hydroxypropoxy) di to deca C _2-4 alkoxy-mono or di C _1-4 alkylphenyl] fluorene; (1 g) 9,9-bis [4- (2- (2- (3- (3-) 3-) (Meta) acryloyloxy-2-hydroxypropoxy) ethoxy) ethoxy) -3-cyclohexylphenyl] fluorene, 9,9-bis [4- (2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy)] )Professional Poxy) propoxy) -3-cyclohexylphenyl] fluorene, 9,9-bis [4- (2- (2- (2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) ethoxy) ethoxy)- 9,9-Bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) di to deca C _2-4 alkoxy-C _5-10 cycloalkylphenyl] fluorene, such as 3-cyclohexylphenyl] fluorene; (1h) 9,9-Bis [4- (2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) ethoxy) -3-phenylphenyl] fluorene, 9,9-Bis [4- (2) -(2- (3- (Meta) acryloyloxy-2-hydroxypropoxy) propoxy) propoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2- (2- (2- (3- (3-) 3-) (Meta) acryloyloxy-2-hydroxypropoxy) ethoxy) ethoxy) ethoxy) -3-phenylphenyl] 9,9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) di to deca C _2-4 Alkoxy-C _6-10 arylphenyl] Fluolene and the like can be exemplified.

9,9-Bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) polyalkoxynaphthyl] As fluorenes, in the above formula (1), rings Z ¹ and Z ² are substituted or unsubstituted naphthalene rings. , K1 = k2 = 0, R ^3a and R ^3b are C _2-4 alkylene groups, n1 and n2 are 2 to 10 and p1 = p2 = 1, respectively, for example, (1i) 9,9-bis [6. -(2- (2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) ethoxy) -2-naphthyl] fluorene, 9,9-bis [6- (2- (2- (3- (3-( Meta) acryloyloxy-2-hydroxypropoxy) propoxy) propoxy) -2-naphthyl] fluorene, 9,9-bis [6- (2- (2- (2- (3- (meth) acryloyloxy-2-hydroxy) Propoxy) ethoxy) ethoxy) ethoxy) -2-naphthyl] fluorene, 9,9-bis [5- (2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) ethoxy) -1- Examples thereof include 9,9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) di to deca C _2-4 alkoxynaphthyl] fluorene such as fluorene.

These epoxy (meth) acrylates may be used alone or in combination of two or more to form a molecular assembly. A preferable epoxy (meth) acrylate is a compound in the above formula (1) in which rings Z ¹ and Z ² are benzene rings or naphthalene rings, p1 = p2 = 1, n1 and n2 are 2 to 10, respectively, that is, 9 , 9-Bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) polyalkoxyphenyl] fluorene; 9,9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) polyalkoxynaphthyl] Fluorenes are mentioned, and among them, the above-mentioned (1e) 9,9-bis [4- (2-(2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) ethoxy) phenyl] fluorene and the like. 9,9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) di to deca C _2-4 alkoxyphenyl] fluorene; (1f) 9,9-bis [4- (2- (2- (2-( 3- (Meta) acryloyloxy-2-hydroxypropoxy) ethoxy) ethoxy) -3-methylphenyl] 9,9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) di to deca C such as fluorene _2-4 alkoxy-mono or di-C _1-4 alkylphenyl] fluorene; (1h) 9,9-bis [4- (2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) 9,9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) di to deca C _2-4 alkoxy-C _6-10 arylphenyl] fluorene, such as ethoxy) -3-phenylphenyl] fluorene; 1i) 9,9-bis [6- (2- (2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) ethoxy) -2-naphthyl] fluorene, 9,9-bis [5-( 2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) ethoxy) -1-naphthyl] fluorene and other 9,9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) ) Di to deca C _2-4 alkoxynaphthyl] fluorene and the like are preferable, and in particular, in the above formula (1), rings Z ¹ and Z ² are benzene rings, R ^2a and R ^2b are alkyl groups, and m1 and m2 are 0, respectively. Compounds of ~ 2, that is, the above-mentioned (1e) 9,9-bis [4- (2- (2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) e) d. Toxi) ethoxy) phenyl] fluorene and other 9,9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) di to deca C _2-4 alkoxyphenyl] fluorene; (1f) 9,9-bis [ 9,9-bis [(3- (meth) acryloyloxy-) such as 4- (2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) ethoxy) -3-methylphenyl] fluorene. 2-Hydroxypropoxy) di to deca C _2-4 alkoxy-mono or di C _1-4 alkylphenyl] fluorene and the like are preferable.

[Manufacturing method of epoxy (meth) acrylate]
The method for producing the epoxy (meth) acrylate represented by the formula (1) is not particularly limited as long as the number of oxyalkylene groups added, that is, n1 + n2 can be adjusted within a predetermined range, and a conventional method, for example, the following. The method (A) may be used in which the epoxy compound represented by the formula (2) is reacted with the (meth) acrylic acid component (see JP-A-2009-155256).

(In the formula, rings Z ¹ and Z ² , R ^1a and R ^1b , R ^2a and R ^2b , R ^3a and R ^3b , k1 and k2, m1 and m2, n1 and n2, p1 and p2, respectively, 1) Same as the description).

Further, a method (B) of reacting the first hydroxy compound represented by the following formula (3) with glycidyl (meth) acrylate (see, for example, the methods described in Patent Documents 3 to 5) and the like. You may.

(In the formula, rings Z ¹ and Z ² , R ^1a and R ^1b , R ^2a and R ^2b , R ^3a and R ^3b , k1 and k2, m1 and m2, n1 and n2, p1 and p2, respectively, 1) Same as the description).

From the viewpoint of reactivity and the like, it is usually prepared by the method (A).

As the epoxy compound represented by the formula (2) used in the method (A), a commercially available product may be used, and a conventional method, for example, the first formula represented by the formula (3) can be used. It may be prepared by a method of reacting a hydroxy compound with epichlorohydrin (for example, epichlorohydrin, epibromohydrin, etc.). Therefore, when the epoxy (meth) acrylate represented by the formula (1) is prepared by either the method (A) or the method (B), the first hydroxy compound represented by the formula (3) is prepared. By controlling the number of oxyalkylene group additions (n1 + n2) in the above to a predetermined range, the addition of oxyalkylene groups in the epoxy compound represented by the formula (2) and the epoxy (meth) acrylate represented by the formula (1). The number (n1 + n2) may be adjusted. Further, the epoxy compound represented by the formula (2) and the first hydroxy compound represented by the formula (3) may be molecular aggregates, respectively, and the respective oxyalkylene group addition numbers (n1 + n2). May be the average value of the molecular aggregates as in the case of the epoxy (meth) acrylate represented by the above formula (1).

(First hydroxy compound represented by the above formula (3))
In the above formula (3), rings Z ¹ and Z ² , R ^1a and R ^1b , R ^2a and R ^2b , R ^3a and R ^3b , k1 and k2, m1 and m2, n1 and n2, p1 and p2, respectively. Preferred embodiments and the like are the same as described above. As a typical first hydroxy compound represented by the formula (3), for example, the compounds (1a) to (1i) exemplified as a representative example of the epoxy (meth) acrylate represented by the formula (1). Examples thereof include hydroxy compounds corresponding to, that is, compounds (3a) to (3i) in which a 3- (meth) acryloyloxy-2-hydroxypropoxy group is replaced with a hydrogen atom. These compounds may be contained as a molecular assembly alone or in combination of two or more.

The first hydroxy compound represented by the formula (3) is not particularly limited, and a commercially available product may be used, and a conventional method, for example, the second hydroxy compound represented by the following formula (4) can be used. And the alkylene oxide or alkylene carbonate corresponding to the ^{oxyalkylene groups OR 3a} and OR ^3b in the above formula (3) may be reacted with each other.

(Wherein, x1 and x2 each represent 0 or 1, ring ^{Z 1} and ^{Z 2, R 1a} and ^{R 1b, R 2a} and ^{R 2b, R 3a} and ^R 3b, k1 and k2, m1 and m @ 2, p1 and p2 is the same as the description in the above formula (1), respectively).

In the above formula (4), ^{preferred embodiments of rings Z 1} and Z ² , R ^1a and R ^1b , R ^2a and R ^2b , R ^3a and R ^3b , k1 and k2, m1 and m2, p1 and p2 are described. , The same as described above. As a typical example of the second hydroxy compound represented by the formula (4), a compound having the number of repetitions of the oxyalkylene group x1 = x2 = 1, for example, the first hydroxy represented by the formula (3). Compounds similar to the compounds (3a) to (3d) exemplified as typical examples of the compounds and compounds in which the rings Z ¹ and Z ² of the compound (3a) are replaced with naphthalene rings (for example, 9,9-bis [6--] _{9,9-bis [hydroxy C 2-4} alkoxynaphthyl] fluorenes such as hydroxyethoxy-2-naphthyl] fluorene and 9,9-bis [5- (2-hydroxypropoxy) -1-naphthyl] fluorene; Compound (3j)), and compounds in which the number of repetitions of the oxyalkylene group x1 = x2 = 0, for example, the hydroxyalkoxy groups of the compounds (3a) to (3d) and (3j) are replaced with hydroxyl groups. Examples thereof include compounds (4a) to (4d) and (4j). These compounds may be used alone or in combination of two or more. When the compound has x1 = x2 = 1, the first hydroxy compound represented by the formula (3) (further, the epoxy (meth) acrylate represented by the formula (1)) is colored. Easy to suppress.

As the second hydroxy compound represented by the formula (4), a commercially available product may be used, and in the presence of a conventional method, for example, an acid catalyst such as an inorganic or organic acid or a co-catalyst such as thiols. It may be synthesized by a method of reacting 9-fluorenones such as 9-fluorenone with phenols or aryloxyalcohols (for example, the method described in JP-A-2007-91870). Examples of phenols include phenol, biphenylol, naphthol and the like, and examples of aryloxy alcohols include 2-phenoxyethanol, 2-phenoxypropanol, 2- (phenylphenoxy) ethanol and 2- (naphthoxy) ethanol. Etc. can be exemplified. By using aryloxy (poly) alkoxy alcohols instead of phenols or aryloxy alcohols, the above can be directly described without passing through the second hydroxy compound represented by the above formula (4). The first hydroxy compound represented by the formula (3) may be synthesized, but from the viewpoint of reactivity and the like, a method of synthesizing via the second hydroxy compound represented by the formula (4) is available. preferable.

^{Examples of the alkylene oxide corresponding to the oxyalkylene groups OR 3a} and OR 3b in the formula (3) include _{C 2-6} alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide, preferably C _2-4 alkylene oxides, and more preferably C 2-4 alkylene oxides. _Examples thereof include C2-3 alkylene oxide (particularly ethylene oxide). ^{As the alkylene carbonate corresponding to the oxyalkylene groups OR 3a} and OR ^3b in the above formula (3) _{, C 2-6} alkylene carbonate such as ethylene carbonate, propylene carbonate and butylene carbonate, preferably C _2-4 alkylene carbonate, more preferably. _Examples include C 2-3 alkylene carbonate (particularly ethylene carbonate).

By the reaction of the second hydroxy compound represented by the formula (4) with the alkylene oxide or the alkylene carbonate, the alkylene oxide or the alkylene carbonate is ring-opened (in the case of the alkylene carbonate, the alkylene oxide undergoes a decarboxylation reaction), and the oxy The alkylene groups OR ^3a and OR ^3b are introduced (or added). In this reaction, by adjusting the amount of the alkylene oxide or alkylene carbonate used with respect to the second hydroxy compound represented by the formula (4), the oxyalkylene of the first hydroxy compound represented by the formula (3). The number of additional groups (n1 + n2) may be adjusted. Theoretically, for example, in the second hydroxy compound represented by the formula (4), when x1 = x2 = 0, the alkylene oxide with respect to 1 mol of the second hydroxy compound represented by the formula (4). Alternatively, the amount of the alkylene carbonate used may be a total of several moles (or n1 + n2 moles) of n1 and n2. Specifically, in the second hydroxy compound represented by the above formula (4), the amount of alkylene oxide or alkylene carbonate used for 1 mol of the compound having p1 = p2 = 1 and x1 = x2 = 0 is, for example, It can be selected from the range of about 2 to 30 mol, for example, 2.5 to 25 (for example, 3 to 20) mol, preferably 3.5 to 18 (for example, 4 to 16) mol, and more preferably 4 to 15 (for example). For example, it may be about 4.5 to 14.5) moles, especially about 5 to 14 (for example, 5.5 to 13.5) moles, and usually 6 to 13 (for example, 6.5 to 12.5) moles. ) It may be about a mole.

Further, when the number of repetitions of the oxyalkylene group x1 and / or x2 is 1, that is, when one or more oxyalkylene groups are added to the 9,9-bisarylfluorene skeleton, x1 = x2 = 0. The amount used may be obtained by subtracting the number of added oxyalkylene groups (x1 + x2 mol) from the amount used in the case. Note that x1 + x2 means the total value of all existing x1 and x2 when p1 and / or p2 is 2 or more.

The reaction of the second hydroxy compound represented by the formula (4) with the alkylene oxide or the alkylene carbonate may be carried out in the absence of a catalyst, but may usually be carried out in the presence of a catalyst. Examples of the catalyst include a base catalyst and an acid catalyst, and usually a base catalyst can be used. Examples of the base catalyst include metal hydroxides (alkali metals such as sodium hydroxide or alkaline earth metal hydroxides), metal carbonates (alkali metals such as sodium carbonate or alkaline earth metal carbonates, sodium hydrogencarbonate, etc.). Alkali metal or alkaline earth metal hydrogen carbonate, etc.), inorganic bases such as ammonia; amines [eg, tertiary amines (trialkylamines such as triethylamine, triisopropylamine, tributylamine, benzyldimethylamine, etc.) Aromatic tertiary amines such as benzyldialkylamine, N, N-dimethylaniline, heterocyclic tertiary amines such as 1-methylimidazole), etc.], carboxylic acid metal salts (alkali acetates such as sodium acetate and calcium acetate). Examples thereof include organic bases such as metals or alkaline earth metal salts) and basic ion exchange resins (for example, strongly basic anion exchange resins having a quaternary ammonium base). The catalyst (base catalyst) may be used alone or in combination of two or more.

The amount of the catalyst used can be adjusted according to the type of the catalyst, and is, for example, 0.001 to 1 part by weight (for example, 0. 003 to 0.5 parts by weight), preferably 0.005 to 0.3 parts by weight, and more preferably 0.01 to 0.1 parts by weight.

The reaction may be carried out in a solvent. The solvent is not particularly limited and can be selected according to the raw material to be used. For example, when alkylene oxide is used, an ether solvent (dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane, etc. Anisole and the like); Halogen-based solvents (halogenated hydrocarbons such as methylene chloride and chloroform); Hydrocarbon-based solvents (aromatic hydrocarbons such as toluene and xylene) and the like. When alkylene carbonate is used, in addition to the above-exemplified solvent, alcohols (linear or branched C _1-4 alcohol such as methanol and ethanol, ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol) are used. (Poly) C _2-3 alkylene glycol, etc.) may be used. These solvents may be used alone or in combination of two or more to form a mixed solvent. The amount of the solvent used is, for example, 1 to 30 parts by weight, preferably 1.5 to 20 parts by weight, more preferably 2 to 2 parts by weight, based on 1 part by weight of the second hydroxy compound represented by the formula (4). It may be about 10 parts by weight.

The reaction is often carried out at, for example, 0 to 170 ° C., preferably 10 to 150 ° C., more preferably about 20 to 130 ° C., depending on the type of the compound (alkylene oxide, alkylene carbonate) to be added. In particular, when alkylene carbonate is used, in order to efficiently carry out the decarboxylation reaction, the reaction is often carried out at, for example, 70 to 150 ° C., preferably about 80 to 120 ° C. The reaction time is, for example, 30 minutes to 48 hours, usually 1 to 24 hours, preferably about 2 to 10 hours.

The reaction may be carried out with stirring, in air or in an inert atmosphere (nitrogen atmosphere, noble gas atmosphere such as helium or argon), or under normal pressure or pressure. Further, if necessary, the reaction may be carried out while removing the generated gas (carbon dioxide or the like).

The product (the first hydroxy compound represented by the above formula (3)) may be purified from the reaction mixture after completion of the reaction by using a conventional purification method (extraction, crystallization, etc.).

By such a method, the first hydroxy compound represented by the above formula (3) in which the number of oxyalkylene groups added (n1 + n2) is adjusted can be obtained. By subjecting the first hydroxy compound represented by the formula (3) to the method (A) or (B), an epoxy (meth) acrylate represented by the formula (1) can be produced. can.

(Method (A))
In the method (A), the epoxy compound represented by the formula (2) is reacted with the (meth) acrylic acid component (method (A-2)) to cause the epoxy represented by the formula (1). A (meth) acrylate can be prepared, and the epoxy compound is a method of reacting the first hydroxy compound represented by the above formula (3) with epichlorohydrin (for example, epichlorohydrin, epibromohydrin, etc.) (A-1). ) And so on.

In the above formula (2), rings Z ¹ and Z ² , R ^1a and R ^1b , R ^2a and R ^2b , R ^3a and R ^3b , k1 and k2, m1 and m2, n1 and n2, p1 and p2, respectively. Preferred embodiments and the like are the same as those described in the section of epoxy (meth) acrylate represented by the above formula (1). Typical epoxy compounds represented by the formula (2) correspond to, for example, compounds (1a) to (1i) exemplified as typical examples of the epoxy (meth) acrylate represented by the formula (1). Examples thereof include epoxy compounds, that is, compounds (2a) to (2i) in which a 3- (meth) acryloyloxy-2-hydroxypropoxy group is replaced with a glycidyl group.

Method (A-1)
In the reaction of the first hydroxy compound represented by the formula (3) with epihalohydrin, the amount of epihalohydrin used with respect to 1 mol of the hydroxyl group of the first hydroxy compound represented by the formula (3) is, for example, 1. It may be about 30 mol, preferably 1.5 to 25 mol, more preferably 2 to 20 mol, particularly 2.5 to 15 mol (for example, 3 to 10 mol).

A catalyst may be appropriately used in the reaction of the first hydroxy compound represented by the formula (3) with epihalohydrin. Examples of the catalyst include a base (base catalyst), for example, a base catalyst exemplified in the reaction of the second hydroxy compound represented by the above formula (4) with an alkylene oxide or an alkylene carbonate. The bases may be used alone or in combination of two or more.

The amount of the catalyst (for example, a base catalyst) used depends on the type of catalyst, and is, for example, 0.01 with respect to 1 mol of the hydroxyl group of the first hydroxy compound represented by the above formula (3). It may be about 10 mol, preferably 0.05 to 5 mol, and more preferably about 0.1 to 3 mol.

The reaction may also be carried out in the presence of a phase transfer catalyst. Examples of the interphase transfer catalyst include ammonium salts [for example, tetraalkylammonium salts (eg, tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, methyltrioctylammonium chloride, methyltridecylammonium). Tetra C _1-20 alkylammonium halides such as chloride), quaternary ammonium salts such as aralkyltrialkylammonium salts (eg benzyltri C _1-4 alkylammonium halides such as benzyltrimethylammonium chloride), etc. Be done. The phase transfer catalyst may be used alone or in combination of two or more.

The amount of the phase transfer catalyst used is, for example, 0.1 to 20 parts by weight, preferably 0.2, based on 100 parts by weight of the total amount of the first hydroxy compound and epihalohydrin represented by the above formula (3). It may be about 10 parts by weight (for example, 0.3 to 8 parts by weight), more preferably about 0.5 to 5 parts by weight (for example, 1 to 5 parts by weight).

The reaction may be carried out in a solvent-free environment or in a solvent. Solvents (organic solvents) include hydrocarbons (aliphatic hydrocarbons such as hexane, heptane, octane, aromatic hydrocarbons such as toluene and xylene); halogenated hydrocarbons (methylene chloride, chloroform, 1 , 2-Dichloroethane, etc.); Ether solvents (dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane, anisole, etc.); Ketones (dialkyl ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), etc. Can be mentioned. The solvent may be used alone or in combination of two or more as a mixed solvent. Of these solvents, ketones (particularly methyl isobutyl ketone) are preferred. When the catalyst is a liquid, the catalyst may be used as a solvent. The amount of the solvent used may be, for example, about 1 to 1000 parts by weight, preferably about 5 to 500 parts by weight, based on 100 parts by weight of the first hydroxy compound represented by the formula (3). ..

The reaction temperature and reaction time can be appropriately selected according to the type of raw material used. The reaction temperature may be, for example, 30 to 120 ° C., preferably 35 to 100 ° C., and more preferably about 40 to 70 ° C. The reaction time may be, for example, 30 minutes to 48 hours, usually 1 to 36 hours, preferably about 2 to 24 hours.

The reaction may be carried out while refluxing or removing by-products. The reaction may be carried out with stirring, in air or in an inert atmosphere (nitrogen atmosphere, noble gas atmosphere such as helium, argon, etc.), under normal pressure, under pressure or under reduced pressure. You may. In particular, when the reaction is carried out under reduced pressure, coloring can be reduced and the reaction time can be shortened.

The produced compound (epoxy compound represented by the above formula (2)) is prepared by a conventional method, for example, a separation means such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, or a combination thereof. It may be separated and purified by the separation means.

Method (A-2)
The epoxy (meth) represented by the formula (1) is obtained by subjecting the epoxy compound represented by the formula (2) obtained by the method (A-1) to a reaction with the (meth) acrylic acid component. Acrylate can be prepared.

Examples of the (meth) acrylic acid component include (meth) acrylic acid, and commercially available products and the like can be used.

The ratio of the epoxy compound represented by the formula (2) to the (meth) acrylic acid component is, for example, 1 mol or more (for example, 1 to 5 mol, preferably 1 to 5 mol) with respect to 1 mol of the glycidyl group of the epoxy compound. It may be 1.05 to 3 mol, more preferably about 1.1 to 2.5 mol).

The reaction between the epoxy compound represented by the formula (2) and the (meth) acrylic acid component may be carried out in the presence of a catalyst, if necessary. Examples of the catalyst include the base catalyst exemplified in the reaction between the second hydroxy compound represented by the above formula (4) and an alkylene oxide or an alkylene carbonate. The bases may be used alone or in combination of two or more.

The amount of the catalyst (for example, a base catalyst) used depends on the type of catalyst, and is, for example, 0.01 to 10 mol with respect to 1 mol of the glycidyl group of the epoxy compound represented by the above formula (2). It may be preferably about 0.05 to 5 mol, more preferably about 0.1 to 3 mol.

The reaction may also be carried out in the presence of a phase transfer catalyst. Examples of the phase transfer catalyst include the phase transfer catalyst exemplified in the section of the reaction of the first hydroxy compound represented by the above formula (3) and epihalohydrin. The phase transfer catalyst may be used alone or in combination of two or more.

The amount of the phase transfer catalyst used is, for example, 0.01 to 20 parts by weight, preferably 0, based on 100 parts by weight of the total amount of the epoxy compound represented by the formula (2) and the (meth) acrylic acid component. It may be about 0.02 to 10 parts by weight (for example, 0.03 to 5 parts by weight), more preferably about 0.05 to 3 parts by weight (for example, 0.1 to 1 part by weight).

The reaction may be carried out in the presence of a polymerization inhibitor (or thermal polymerization inhibitor). Examples of the thermal polymerization inhibitor include benzoquinones, hydroquinones (eg, hydroquinone, hydroquinone monomethyl ether (methquinone), p-tert-butylhydroquinone, p-benzoquinone, etc.), catechols (eg, p-tert-butylcatechol, etc.), Examples thereof include amines (for example, N, N-diethylhydroxylamine, etc.), 1,1-diphenyl-2-picrylhydrazil, tri-p-nitrophenylmethyl, phenothiazine, and the like. The thermal polymerization inhibitor may be used alone or in combination of two or more.

The ratio of the thermal polymerization inhibitor may be, for example, about 0.001 to 5 parts by weight (for example, 0.005 to 1 part by weight) with respect to 100 parts by weight of the (meth) acrylic acid component, and is usually used. It may be about 0.01 to 0.5 parts by weight (for example, 0.02 to 0.1 parts by weight).

The reaction may be carried out in the presence of a solvent. The solvent is not particularly limited, and is, for example, ketones (for example, dialkyl ketones such as acetone, diisopropyl ketone and methyl isobutyl ketone, cyclic ketones such as cyclohexanone); ethers (for example, chains such as diethyl ether and diisopropyl ether). Ethers; cyclic ethers such as tetrahydrofuran and dioxane); alkylene glycol monoalkyl ether acetates (eg, methyl cellosolve acetate, propylene glycol monomethyl ether acetate, etc.); esters (eg, ethyl acetate, etc.); nitriles (eg, acetonitrile) Etc.); Amidos (eg, dimethylformamide, dimethylacetamide, etc.); Sulfoxides; Hydrocarbons [aliphatic hydrocarbons (eg, hexane, heptane, etc.), alicyclic hydrocarbons (eg, cyclohexane, etc.), aromatics Ketones (eg, toluene, xylene, ethylbenzene, etc.)]; Halogen-based solvents (eg, methylene chloride, chloroform, 1,2-dichloroethane, etc.) and the like can be mentioned. These solvents may be used alone or as a mixed solvent in which two or more kinds are combined. The amount of the solvent used may be, for example, about 1 to 1000 parts by weight, preferably about 5 to 500 parts by weight, based on 100 parts by weight of the epoxy compound represented by the formula (2).

The reaction temperature is not particularly limited, but is, for example, 20 to 200 ° C. (for example, 40 to 180 ° C.), preferably 50 to 160 ° C. (for example, 60 to 150 ° C.), and more preferably 70 to 140 ° C. (for example, 80 ° C.). It may be about ~ 130 ° C.). The reaction time may be, for example, 30 minutes to 48 hours, preferably 1 to 24 hours, and more preferably 2 to 10 hours. The reaction may be carried out with stirring, in air or in an inert atmosphere (nitrogen atmosphere, noble gas atmosphere such as helium or argon, etc.), under normal pressure, under pressure or under reduced pressure. You may.

The reaction mixture thus obtained may contain an unreacted component, a catalyst, a condensate and the like in addition to the target product (epoxy (meth) acrylate represented by the above formula (1)). Therefore, purification may be performed using a conventional method, for example, a separation means such as filtration, concentration, neutralization, extraction, crystallization, recrystallization, column chromatography, or a separation means combining these.

Since the epoxy (meth) acrylate obtained by such a method and represented by the formula (1) has a 9,9-bisarylfluorene skeleton, it has a high refractive index and can be used as an optical member. It can be preferably used. The refractive index (temperature 25 ° C., wavelength 589 nm) of the epoxy (meth) acrylate represented by the formula (1) can be selected from the range of, for example, about 1.5 to 1.65, for example, 1.52-1. It may be about 0.6, preferably 1.53 to 1.59, and more preferably about 1.54 to 1.57. The refractive index can be measured by a multi-wavelength Abbe refractometer or the like.

Further, in the present invention, since the number of oxyalkylene groups added (n1 + n2) is adjusted within a predetermined range, the viscosity is relatively low and the handleability is excellent despite the high refractive index. The viscosity of the epoxy (meth) acrylate represented by the formula (1) at a temperature of 25 ° C. can be selected from the range of, for example, about 5000 to 150,000 mPa · s (for example, 1000 to 60000 mPa · s), for example, 20000 to 50000 mPa. -S, preferably about 30,000 to 45,000 mPa · s, and more preferably about 35,000 to 40,000 mPa · s. The viscosity can be measured by the method described in Examples described later.

[Curable composition]
The epoxy (meth) acrylate of the present invention may be used alone, or may be mixed with other components such as a polymerization initiator, other polymerizable compounds, and a solvent to form a curable composition.

(Polymerization initiator)
The curable composition of the present invention may contain a thermal polymerization initiator and / or a photopolymerization initiator.

Examples of the thermal polymerization initiator include organic peroxides [dialkyl peroxides (eg, di-t-butyl peroxide, etc.); diacyl peroxides (eg, lauroyl peroxide, benzoyl peroxide, etc.); peracids. (Or Peracid Esters) (eg, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peracetate, etc.); Ketone peroxides; Peroxy carbonates; Peroxyketals]; Azo compounds [eg, 2 , 2'-Azonitrile compounds such as azobis (isobutyronitrile); azoamide compounds; azoamidine compounds, etc.] and the like can be exemplified. These thermal polymerization initiators can be used alone or in combination of two or more.

Examples of the photopolymerization initiator (or photoradical polymerization initiator) include benzoins (for example, benzoin; benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether); acetophenones (acetophenone, 2). -Hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, etc.); Aminoacetophenones (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone- 1, etc.); Anthraquinones (anthraquinone, anthraquinone-2-sulfonate, etc.); Thioxanthones (eg, thioxanthone, isopropoxychlorothioxanthone, etc.); Ketals (acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.); (For example, benzophenone, 4-hydroxybenzophenone, etc.); 2,4,5-triarylimidazole dimer (eg, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2) , 4-Dimethoxyphenyl) -4,5-diphenylimidazole dimer, etc.); Xanthons; 2,4,6-trihalomethyltriazines; Acridine derivatives (eg, 9-phenylacridin, 1,7-bis (9) , 9'-acrydinyl) heptane, etc.); bisacylphosphine oxides (eg, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, etc.) can be exemplified. These photopolymerization initiators may be used alone or in combination of two or more.

The proportion of the polymerization initiator (heat and / or photopolymerization initiator) is the total amount of the (meth) acryloyl group-containing component in the curable composition (for example, the epoxy (meth) acrylate represented by the above formula (1) and the epoxy (meth) acrylate. 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight (for example, 1 to 8 parts by weight), more preferably 2 to 5 parts by weight, relative to 100 parts by weight (such as the total amount of other polymerizable compounds described below). It may be about a part by weight. Of these polymerization initiators, it is preferable to contain at least a photopolymerization initiator.

Further, the photopolymerization initiator may be combined with a photosensitizer. Photosensitizers include tertiary amines [eg, trialkylamines; trialkanolamines (triethanolamine, etc.); ethyl N, N-dimethylaminobenzoate [p- (dimethylamino) ethyl benzoate, etc.] , N, N-Dimethylaminobenzoic acid amyl [p- (dimethylamino) benzoate amyl, etc.] and other dialkylaminobenzoic acid alkyl esters; 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) Examples thereof include conventional photosensitizers such as bis (dialkylamino) benzophenone such as benzophenone; dialkylaminobenzophenone such as 4- (dimethylamino) benzophenone and 4-methoxy-4'-dimethylaminobenzophenone]. These photosensitizers may be used alone or in combination of two or more.

The ratio of the photosensitizer may be 1 to 200 parts by weight, preferably 5 to 150 parts by weight, and more preferably 10 to 100 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.

(Other polymerizable compounds)
The curable composition of the present invention may further contain a polymerizable compound having one or more polymerizable functional groups (for example, (meth) acryloyl group, vinyl group, etc.) in the molecule. Sensitivity (or curability), fluidity, chemical resistance, heat resistance, mechanical strength, etc. may be improved. Other polymerizable compounds are often monofunctional or polyfunctional (meth) acrylates with a (meth) acryloyl group.

Examples of the monofunctional (meth) acrylate include alkyl (meth) acrylates [for example, C _1-20 alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate]. Hydroxyalkyl (meth) acrylates (eg, hydroxyethyl (meth) acrylates); alkoxyalkyl (meth) acrylates (eg, methoxyethyl (meth) acrylates); Cycloalkyl (meth) acrylates (eg, cyclohexyl (meth)) Acrylate); aryl (meth) acrylate (eg, phenyl (meth) acrylate); aryloxyalkyl (meth) acrylate (eg, phenoxyethyl (meth) acrylate); aralkyl (meth) acrylate (eg, benzyl (meth)) Acrylate, etc.); Aryloxy ((poly) alkoxy) alkyl (meth) acrylate (eg, phenoxyethoxyethyl (meth) acrylate, etc.); Alkylaryloxyalkyl (meth) acrylate (eg, nonylphenoxyethyl (meth) acrylate, etc.) Alkylaryloxy (poly) alkoxyalkyl (meth) acrylates (eg, nonylphenoxy (poly) ethoxyethyl (meth) acrylates); arylaryloxyalkyl (meth) acrylates (eg, 2- (o-phenylphenoxy) ethyl (Meta) acrylates, etc.); arylaryloxy (poly) alkoxyalkyl (meth) acrylates (eg, phenylphenoxy (poly) ethoxyethyl (meth) acrylates, etc.); (meth) acrylates with sulfur atoms [eg, alkylthio (meth) acrylates. ) Acrylate (eg, methylthio (meth) acrylate, etc.); Arylthio (meth) acrylate (eg, phenylthio (meth) acrylate, etc.); Aralkylthio (meth) acrylate (eg, benzylthio (meth) acrylate, etc.); Meta) acrylate (eg, phenylthioethyl (meth) acrylate, etc.)]; N, N-dialkyl (meth) acrylamide (eg, N, N-dimethyl (meth) acrylamide, etc.); N, N-dialkylaminoalkyl (eg, N, N-dialkylaminoalkyl) Meta) acrylates (eg, N, N-dimethylaminoethyl (meth) acrylates, etc.); Bispheno Mono (meth) acrylates of compounds or alkylene oxide adducts thereof (eg, mono (meth) acrylates of ethylene oxide adducts of bisphenol A); (meth) acrylates having a fluorene skeleton (eg, 9- (meth) acryloyloxy). Methylfluorene, a compound having p1 + p2 = 1 and n1 or n2 of 11 or more in the above formula (1), etc.) can be exemplified.

Examples of the polyfunctional (meth) acrylate include bifunctional (meth) acrylates [for example, (poly) C such as ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, and dipropylene glycol di (meth) acrylate. _2-4 alkylene glycol di (meth) acrylate; di (meth) acrylate of bisphenol A (or its alkylene oxide adduct)]; trifunctional or higher (meth) acrylate [eg, glycerin tri (meth) acrylate, tri Tri to hexaol tris such as methylolpropantri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Hexa (meth) acrylate]; Urethane (meth) acrylate; Epoxy (meth) acrylate that does not belong to the scope of the present invention (for example, a compound having p1 + p2 ≧ 2 and n1 or n2 of 11 or more in the above formula (1), etc. ); (Meta) acrylate having a fluorene skeleton [for example, 9,9-bis [4- (2- (meth) acryloyloxy (poly) ethoxy) phenyl] fluorene, etc.] can be mentioned. These monofunctional and polyfunctional (meth) acrylates can also be used alone or in combination of two or more.

The ratio of these polymerizable compounds can be selected from, for example, about 0 to 50 parts by weight, preferably 0 to 30 (for example,) with respect to 100 parts by weight of the (meth) acrylate represented by the formula (1). , 1 to 20) parts by weight, more preferably about 0 to 10 parts by weight.

(Other additives)
In addition, the curable composition may contain a solvent, if necessary. The solvent is not particularly limited, and may be the solvent exemplified in the section of the method for producing an epoxy (meth) acrylate. These solvents can also be used alone or in combination of two or more as a mixed solvent. The ratio of the solvent is, for example, 100 to 2000 parts by weight, preferably 300 to 1500 parts by weight, based on 100 parts by weight of the total amount of the epoxy (meth) acrylate represented by the formula (1) and other polymerizable compounds. More preferably, it may be about 500 to 1000 parts by weight.

Further, the curable composition may be filled with conventional additives such as colorants, stabilizers (heat stabilizers, antioxidants, UV absorbers, etc.), polymerization inhibitors, and fillers, as long as the effects of the present invention are not impaired. It may contain an agent, an antistatic agent, a flame retardant, a surfactant, a plasticizer, an antifoaming agent, a coupling agent and the like. These additives can be used alone or in combination of two or more. The ratio of the additive is, for example, 0.1 to 20 parts by weight, preferably 0.5, based on 100 parts by weight of the total amount of the epoxy (meth) acrylate represented by the formula (1) and other polymerizable compounds. It may be about 10 parts by weight, more preferably about 1 to 5 parts by weight.

[Cured product]
The curable composition is easily cured by applying active energy (active energy ray). Thermal energy and / or light energy (ultraviolet rays, electron beams, X-rays, etc.) are useful as the active energy, and can be appropriately selected depending on the purpose and the like.

When heat energy is used, the heating temperature may be, for example, 50 to 250 ° C., preferably 60 to 120 ° C., and more preferably 70 to 100 ° C. The heating time may be, for example, 5 minutes to 12 hours, preferably 10 minutes to 8 hours, and more preferably about 30 minutes to 4 hours.

When light energy (for example, light irradiation such as ultraviolet irradiation) is used, the amount of light irradiation energy can be appropriately selected depending on the application, for example, 50 to 10000 mJ / cm ² , preferably 70 to 8000 mJ / cm ^2. More preferably, it may be about 100 to 5000 mJ / cm ² (for example, 300 to 3000 ^{mJ / cm 2).} As the light source, a deep UV lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a halogen lamp, a laser light source (for example, a light source such as a helium-cadmium laser or an excima laser) can be used.

Even when it is cured by light irradiation, heat treatment (baking treatment, after-baking, etc.) may be performed in order to improve the reactivity. The temperature and time of the heat treatment are the same as when the heat energy is used. Further, the reaction (or polymerization, cross-linking, or curing) may be carried out in an atmospheric atmosphere or an inert gas atmosphere (for example, a nitrogen atmosphere, a rare gas atmosphere such as helium, argon, etc.), under normal pressure, under pressure, or under reduced pressure. You may go below.

The cured product of the present invention has a surprisingly high hardness despite the introduction of a highly flexible oxyalkylene group, and has both high hardness and flexibility in a well-balanced manner. The reason is not clear, but it is presumed that a hydrogen bond is formed between the introduced oxyalkylene group and the hydroxyl group of the epoxy (meth) acrylate. As is clear from Patent Document 1, when an oxyalkylene group is introduced, the cured product tends to greatly improve the flexibility of the cured product, probably because a structure that is easily bent is incorporated and the crosslink density is also lowered. It is in. Therefore, the hardness, which is a property contrary to the flexibility, is greatly reduced. However, the epoxy (meth) acrylate of the present invention has a hydroxyl group (a hydroxyl group adjacent to the (meth) acryloyl group) in the side chain, and the number of oxyalkylene groups added (n1 + n2) is adjusted to a predetermined range. Probably because of this, the oxyalkylene group is relatively easy to move even in the cured product, and the oxygen atom of the oxyalkylene group and the hydroxyl group are likely to form a hydrogen bond, forming a pseudo cross-linking point, and the cross-linking density and It is considered that the hardness is improved. Moreover, when the crosslink density and hardness are improved, the initial flexibility is generally lost, but in the cured product of the present invention, the bond energy of hydrogen bonds is relatively low, and it is easy when an external force of a certain level or more acts. It is presumed that high hardness and flexibility can be achieved at the same time, probably because the bond is broken (the crosslink density decreases), the flexibility derived from the oxyalkylene group is developed, and a new hydrogen bond is formed when the external force is removed. NS.

Therefore, 100 parts by weight of the epoxy (meth) acrylate represented by the above formula (1) and 3 parts by weight of the photopolymerization initiator are mixed to obtain a curable composition, which is cured by UV irradiation (500 mJ / cm ² ). The pencil hardness of the cured product can be selected from the range of, for example, about 4B or more (for example, 3B to 6H), and for example, 3B or more (for example, 2B to 5H), preferably B or more (for example, B or more). For example, it may be about B to 3H), more preferably HB or more (for example, HB to 2H). The pencil hardness can be measured by a measuring method based on JIS K5600-5-4, for example, the method described in Examples described later.

The refractive index (temperature 25 ° C., wavelength 589 nm) of the cured product can be selected from the range of, for example, about 1.5 to 1.65, for example, 1.53 to 1.62, preferably 1.54 to 1. 6, more preferably about 1.55 to 1.58. The refractive index can be measured by a multi-wavelength Abbe refractometer or the like.

The flexibility (or bending resistance) of the cured product can be evaluated by, for example, a bending resistance test such as a cylindrical mandrel method, and is measured with a mandrel flexibility tester or the like in accordance with JIS K5600-5-1. be able to. The flexibility (flexibility) of the cured product is represented by the mandrel diameter (or the minimum diameter) at which the cured product starts to crack or peel from the substrate in the test, and is, for example, 20 mm or less, preferably 10 mm or less. , More preferably, it may be about 5 mm or less (for example, 2 mm or less (2 mm or less than 2 mm)). In particular, the cured product of the present invention is unlikely to crack or peel off from the base material even if it is less than the lower limit of measurement (2 mm). In the present specification and claims, the case where the cured film does not crack or peel off from the base material at the lower limit of measurement (2 mm) is the case where the mandrel diameter is "less than 2 mm" or "<2". There is.

The form of the cured product is not particularly limited, and may be a one-dimensional structure, a two-dimensional structure, for example, a cured film (for example, a film, a sheet, etc.), or a three-dimensional structure (for example, a film, a sheet, etc.). It may be a lens, etc.).

The method for producing the cured product is not particularly limited, and for example, the cured film is made of an inorganic material such as a base material or a substrate [for example, metal (aluminum, etc.), ceramics (titania, glass, quartz, etc.)) using the curable composition. , Organic materials such as plastics (polypropylene, cyclic olefin resin, polycarbonate, etc.), porous materials such as wood] to form a coating film (or thin film), which may be cured. .. Further, the three-dimensional structure may be produced by molding or casting (injecting) the curable composition into a predetermined mold and then performing a curing treatment (heating and / or light irradiation).

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The evaluation method and the raw materials used are shown below.

(Refractive index)
Using a multi-wavelength Abbe refractometer (manufactured by Atago Co., Ltd., DR-M2 <using a circulating constant temperature water tank 60-C3>), the temperature was maintained at 25 ° C., and the refractive index at 589 nm was measured.

(viscosity)
The viscosity at 25 ° C. was measured using a TV-22 type viscometer (cone plate type, "TVE-22L" manufactured by Toki Sangyo Co., Ltd.), and an optional rotor (01: 1 ° 34'x R24, according to the measured viscosity). It was measured at 07: 3 ° x R7.7) at 1 to 20 rpm (selected according to viscosity).

(Pencil hardness)
In accordance with JIS K5600-5-4, each cured film (thickness 10 μm) formed on a polyethylene terephthalate (PET) substrate (manufactured by Toyobo Co., Ltd.) with a thickness of 150 μm is measured with a pencil hardness tester (Shinto Kagaku (Shinto Kagaku (Shinto Kagaku)). It is fixed to "HEIDON-14") manufactured by Co., Ltd., and various pencils are pressed at an angle of 45 degrees to move on the cured film at a speed of 1 mm / sec while applying a load of 750 g. It was measured by visually confirming the presence or absence.

(Flexibility or bending resistance (mandrel diameter))
In accordance with JIS K5600-5-1, each cured film (thickness 150-200 μm) is formed on a PET substrate (manufactured by Toyobo Co., Ltd.) with a thickness of 150 μm, and a mandrel flexibility tester (mandrel flexibility tester Co., Ltd.) ) Measured using "HD-5110") manufactured by Ueshima Seisakusho. The flexibility was evaluated by the diameter (or minimum diameter) [mm] of the mandrel at which cracks and / or peeling occurred in the cured film.

(Ingredients, etc.)
BPEF-9EO: An adduct in which an average of 9 mol of oxyethylene groups (or ethylene oxide) is added to 1 mol of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, Osaka Gas Chemical ( BPEF-9EOG: BPEF-9EO diglycidyl ether BPEF-5EO: 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene 1 mol, on average 5 mol of oxyethylene group Additive with (or ethylene oxide) added, BPEF-5EOG: BPEF-5EO diglycidyl ether BNEF-13EO: 9,9-bis (6- (2-hydroxyethoxy) -2-naphthyl) manufactured by Osaka Gas Chemical Co., Ltd. ) Additive with 13 mol of oxyethylene group (or ethylene oxide) added to 1 mol of fluorene, BNEF-13EOG: BNEF-13EO diglycidyl ether BPEF-9EOA: BPEF manufactured by Osaka Gas Chemical Co., Ltd. -9EO diacrylate, manufactured by Osaka Gas Chemical Co., Ltd. (meth) Acrylic acid Component: Acrylic acid Solvent: Methylisobutylketone (MIBK)
Thermal polymerization inhibitor: Metquinone Catalyst: Tetramethylammonium bromide (TMAB)
Photopolymerization initiator: Irgacure 184, manufactured by BASF Japan Ltd.

(Synthesis Example 1)
(A) Synthesis of BPEF-9EOG In a reactor with Dean-Stark, 66.8 g (0.08 mol) of BPEF-9EO, 74 g (0.8 mol) of epichlorohydrin and 0.8 g of tetramethylammonium bromide (TMAB) (TMAB). 0.0051 mol) was added. The inside of the system was replaced with nitrogen, the temperature was raised to about 50 ° C., the components were mixed, and then 9.6 g (0.24 mol) of flaky sodium hydroxide was added over 1 hour or more. After completion of the addition, the inside of the system was replaced with nitrogen again, the reaction was carried out at 60 ° C. for 9 hours, and the disappearance of the raw material compound was confirmed by high performance (or high performance) liquid chromatography (HPLC). After completion of the reaction, epichlorohydrin was removed under reduced pressure under the condition of 60 ° C., and 130 g of toluene was added while heating to 60 to 80 ° C. The obtained mixed solution was suction-filtered to remove by-products (NaCl), and the residue was washed with toluene. In order to proceed with the ring closure reaction for forming an epoxy group, 53 g of a 30 wt% sodium hydroxide aqueous solution was added dropwise to the filtrate, and the mixture was stirred at 70 ° C. for 1 hour under a nitrogen atmosphere. Then, 260 g of toluene was added to the obtained mixed solution, and the mixture was extracted and washed 5 to 6 times at an extraction temperature of 60 to 80 ° C. using distilled water, dehydrated, concentrated at 90 ° C., dried under reduced pressure, and BPEF-. Obtained 9 EOG.

(B) Synthesis of Epoxy Acrylate (BPEF-9EOGA) BPEF-9EOG (236.8 g), acrylic acid (45.0 g), MIBK (31.2 g), methquinone (2.2 g) in a three-necked flask equipped with Dean Stark. Was added. The inside of the system was replaced with nitrogen and the temperature was raised to 50 ° C. to dissolve the reagent. Then, flaky tetramethylammonium bromide (0.4 g) was added, and the mixture was replaced with nitrogen again, and then reacted under heating under reflux with stirring for 9 hours. After completion of the reaction, the reaction solution was suction-filtered and the filtrate was concentrated and dried to obtain an epoxy acrylate (referred to as BPEF-9EOGA). The solid content concentration of BPEF-9EOGA was 99.4% by weight, the refractive index (25 ° C., 589 nm) was 1.550, and the viscosity (25 ° C.) was 38,500 mPa · s.

(Example 1)
100 parts by weight of BPEF-9EOGA obtained in Synthesis Example 1 and 3 parts by weight of Irgacure 184 were added, and the mixture was stirred and mixed at 70 ° C. for 1 hour. Then, an epoxy acrylate cured product was obtained ^{by UV irradiation (500 mJ / cm 2} ) with "ECS-151U" manufactured by Eye Graphics.

The pencil hardness of the cured product was HB, the refractive index (25 ° C., 589 nm) was 1.558, and the mandrel diameter was less than 2 mm.

(Comparative Example 1)
A cured product was prepared in the same manner as in Example 1 except that BPEF-9EOA was used instead of BPEF-9EOGA.

The cured product had a pencil hardness of 6B, a refractive index (25 ° C., 589 nm) of 1.576, and a mandrel diameter of less than 2 mm.

(Synthesis Example 2)
(A) Synthesis of BPEF-5EOG BPEF-5EOG was synthesized in the same manner as in Synthesis Example 1 (a) except that BPEF-5EO was used instead of BPEF-9EO.

(B) Synthesis of Epoxy Acrylate (BPEF-5EOGA) An epoxy acrylate (referred to as BPEF-5EOGA) was obtained in the same manner as in Synthesis Example 1 (b) except that BPEF-5EOG was used instead of BPEF-9EOG. The solid content concentration of BPEF-5EOGA was 99.5% by weight, the refractive index (25 ° C., 589 nm) was 1.568, and the viscosity (25 ° C.) was 113,500 mPa · s.

(Example 2)
An epoxy acrylate cured product was obtained in the same manner as in Example 1 except that BPEF-5EOGA was used instead of BPEF-9EOGA. The cured product had a pencil hardness of H, a refractive index (25 ° C., 589 nm) of 1.573, and a mandrel diameter of less than 2 mm.

(Synthesis Example 3)
(A) Synthesis of BNEF-13EOG BNEF-13EOG was synthesized in the same manner as in Synthesis Example 1 (a) except that BNEF-13EO was used instead of BPEF-9EO.

(B) Synthesis of Epoxy Acrylate (BNEF-13EOGA) An epoxy acrylate (referred to as BNEF-13EOGA) was obtained in the same manner as in Synthesis Example 1 (b) except that BNEF-13EOG was used instead of BPEF-9EOG. The solid content concentration of BNEF-13EOGA was 96.4% by weight, the refractive index (25 ° C., 589 nm) was 1.566, and the viscosity (25 ° C.) was 67,200 mPa · s.

(Example 3)
An epoxy acrylate cured product was obtained in the same manner as in Example 1 except that BNEF-13EOGA was used instead of BPEF-9EOGA. The cured product had a pencil hardness of 3B, a refractive index (25 ° C., 589 nm) of 1.572, and a mandrel diameter of less than 2 mm.

The evaluation results are shown in Table 1.

As is clear from Table 1, the hardness of the examples was higher than that of the comparative example 1 while maintaining the flexibility (mandrel diameter). Therefore, it was possible to achieve both flexibility and high hardness.

The compound of the present invention has high hardness and flexibility in addition to excellent properties such as high heat resistance and high refractive index derived from the 9,9-bisarylfluorene skeleton, and has various heat or light. It can be used for curable (meth) acrylic resin applications.

Specifically, the compound of the present invention (or a cured product obtained by using the compound of the present invention) includes an ink material, a light emitting material (for example, a light emitting material for an organic EL), an organic semiconductor, a graphitization precursor, and a gas. Separation film (for example, CO ₂ gas separation film), coating agent (for example, optical overcoating agent or hard coating agent such as coating agent for LED (light emitting diode) element), lens [pickup lens (for example, DVD (Pickup lenses for digital versatile discs, etc.), microlenses (eg, microlenses for liquid crystal projectors, etc.), optics lenses, etc.], polarizing films (eg, polarizing films for liquid crystal displays, etc.), antireflection films (for example, Anti-reflection film for display devices, etc.), touch panel materials, flexible substrate materials, display materials [for example, PDP (plasma display), LCD (liquid crystal display), VFD (vacuum fluorescent display), SED (surface conduction type electron emission) Element display), FED (electric power emission display), NED (nano-emissive display), cathode ray tube, electronic paper and other display (especially thin display) films (filters, protective films, etc.)], fuel cell membranes, optical fibers , Optical waveguides, holograms, resist materials, adhesives (for example, photocurable adhesives such as optical adhesives) and the like. In particular, the compound of the present invention can be suitably used for an optical member, and can be suitably used for a film or a coating film for a display because it can achieve both high hardness and flexibility.

Claims (10)

The following formula (1)

(In the formula, rings Z ¹ and Z ² are aromatic hydrocarbon rings, R ^1a and R ^1b and R ^{2a and R 2b} are independently non-radical polymerizable substituents, and R ^3a and R ^3b are alkylene groups and R. ^4a and ^R4b are hydrogen atoms or methyl groups, k1 and k2 are integers of 0 to 4, m1 and m2 are integers of 0 or more, n1 and n2 are integers of 1 to 10, n1 + n2 are 3 to 20 , p1 and p2 are. Indicates an integer from 0 to 1. However, p1 + p2 ≧ 1).
Epoxy (meth) acrylate represented by. Equation (1) Oite, p1 and p2 are each 1, ring ^{Z 1} and ^{Z 2} and n1 + n2 is an epoxy (meth) acrylate according to claim 1, wherein the following (a) or (b).
(A) Rings Z ¹ and Z ² are benzene rings or biphenyl rings, respectively, and n1 + n2 are 3 to 20. (B) Rings Z ¹ and Z ² are naphthalene rings, and n1 + n2 are 4 to 20. In formula (1), rings Z ¹ and Z ² are benzene rings or naphthalene rings, R ^2a and R ^2b are alkyl groups, R ^3a and R ^3b are C _2-3 alkylene groups, and k1 and k2 are integers of 0 to 3. The epoxy (meth) acrylate according to claim 1 or 2, wherein m1 and m2 are integers of 0 to 3, n1 and n2 are integers of 2 to 9, and n1 + n2 are 4 to 18. A curable composition comprising the epoxy (meth) acrylate according to any one of claims 1 to 3. The curable composition according to claim 4, further comprising a photopolymerization initiator. A cured product obtained by curing the curable composition according to claim 4 or 5. The sixth aspect of claim 6, wherein the pencil hardness measured according to JIS K5600-5-4 is 4B or more, and the mandrel diameter measured according to JIS K5600-5-1 is 2 mm or less according to the bending resistance test. Hardened product. The cured product according to claim 6 or 7, which is an optical member. The cured product according to any one of claims 6 to 8, which is a display film or a coating film. A method for producing a cured product by curing the curable composition according to claim 4 or 5.