JP2017186513A - Epoxy (meth)acrylate and curable composition thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide 9,9-bisaryl fluorene skeleton-containing (epoxy) (meth)acrylate and a curable composition thereof which can form a cured product having both high hardness and flexibility in a good balance, and a cured product; and a method for producing the same.SOLUTION: There is provided 9,9-bisaryl fluorene skeleton-containing (epoxy) (meth)acrylate which is synthesized with a ring-opening reaction of an epoxy group and is represented by formula (1). In formula (1), n1 and n2 are integers of 1-10; n1+n2 is 2-30. A relationship of p1+p2≥1 is held, and when both of rings Zand Zare condensed polycyclic aromatic hydrocarbon rings, a relationship of n1+n2≥3 is held.SELECTED DRAWING: None

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.

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

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

Wherein 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, and k1 and k2 are 0-4. , 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, provided that n1 + p1 ≦ 5 and n2 + p2 ≦ 5).

  In this document, in the above formula, the average value of m1 + m2 is described as 8.5 to 17, and in the examples, 9,9-bis (4-acryloyloxypolyethoxyphenyl) fluorene (total number of ethoxy groups added) Is a compound having an average value of 9.0 to 16.0. Since such a polyfunctional (meth) acrylate adjusts the number of oxyalkylene groups added to a specific range, the cured product is excellent in 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, the use as a member is limited, and 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 9,9-bisarylfluorene skeleton-containing (meth) acrylate, epoxy (meth) acrylate synthesized with a ring-opening reaction of an epoxy group is used. For example, JP-A-7-48424 (Patent Document 2) discloses an epoxy (meth) acrylate resin represented by the following formula I.

(Wherein, R represents H or a lower alkyl group, R 'is an integer of .n = 0 to 20 showing an H or CH _3).

  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 to have high heat resistance, solvent solubility, and It describes that it is excellent in photosensitivity. Such an epoxy acrylate resin has a small n in the above formula I, so the crosslinking density tends to be relatively high, and the rigid 9,9-bisphenylfluorene skeletons are close to each other. It is easy to obtain a cured product. However, since it lacks flexibility, its use as a member has been limited.

  JP-A-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 are independently a hydrogen atom or a methyl group, m is independently an integer of 2 to 5, and n is independently 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). 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 crosslinking density tends to be high, and the hardness of the cured product is high (the pencil hardness measured in accordance with JIS K-5400 is 5H). However, only compounds in which the number of repeating units n of the oxyalkylene group contributing to flexibility is 0 are described, and this cured product has low flexibility.

  JP-A-2015-040224 (Patent Document 4) discloses a fluorene skeleton-containing (meth) acrylate represented by the following formula.

(Wherein 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, provided that 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 (wherein Z is a naphthalene ring, X ¹ and X ² are (meth) A composition containing an acryloyl group, k = m = n = 0, p = 1) and a cured product thereof. Such fluorene (meth) acrylate also has a large number of acryloyloxy groups, as described above, and thus the crosslinking density tends to be high, and the hardness of the cured product is high. However, also in this document, only a 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.

  JP2012-206968A (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 condensed polycyclic aromatic hydrocarbon ring, R ¹ is an alkyl group, R ² is an alkylene group, R ³ is a hydrogen atom or a 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 0 or an integer of 1 or more, and p is an integer of 1 or more, provided that 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 having a 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, k = n = 0, m = p = 1). In such a fluorene-containing epoxy (meth) acrylate, a naphthalene ring having a continuous benzene ring structure is introduced as the ring Z, and the cured product has a relatively high hardness because it has a rigid skeleton. 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, even in this document, only compounds having 0 or 1 repeating units of the oxyalkylene group contributing to flexibility are specifically described, and high hardness and flexibility cannot be achieved at the same time.

  In addition, in the epoxy (meth) acrylates described in Patent Documents 3 to 5, although the oxyalkylene group capable of imparting flexibility is defined in a wide range of repeating units, its technical significance (or characteristics) is No mention is made in any document. As for the specific study on the introduction of the oxyalkylene group, Patent Documents 3 and 4 have not been studied yet, and Patent Document 5 has also studied only a compound having 1 repeating unit. Therefore, an epoxy (meth) acrylate having an increased number of additions (or addition moles) of oxyalkylene groups has not been substantially known.

  In general, the high hardness and flexibility of a cured product are in a trade-off relationship that when one of them is improved, the other is reduced. It was very difficult.

International Publication No. 2013/022065 (Claims, paragraphs [0003] [0013] [0041], Examples) JP-A-7-48424 (Claims, paragraph [0056], Examples) JP 2004-83855 A (Claim 7, paragraph [0182], Examples 6 and 7) Japanese Patent Laying-Open No. 2015-040224 (Claims, paragraph [0026], Examples) JP 2012-206968 A (Claims, paragraph [0055], Examples)

  Accordingly, an object of the present invention is to provide 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 their It is providing the manufacturing method of hardened | cured material and the said hardened | cured material.

  Another object of the present invention is to provide a 9,9-bisarylfluorene skeleton-containing (meth) acrylate capable of improving the hardness even when the crosslinking density is low, a curable composition containing the (meth) acrylate, and a cured product thereof, and It is providing the manufacturing method of the said hardened | cured material.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have introduced an oxyalkylene group (or alkoxy group) with a predetermined number of repetitions into an epoxy (meth) acrylate having a 9,9-bisarylfluorene skeleton. Although it is expected that a cured product having a low crosslinking density and hardness can be obtained by 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).

(Wherein, rings Z ¹ and Z ² are aromatic hydrocarbon rings, R ^1a and R ^1b and R ^2a and R ^2b are each independently a non-radically polymerizable substituent, R ^3a and R ^3b are alkylene groups, R ^4a and R ^4b 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 is 2 to 30, p1 and p2 are Represents an integer of 0 to 4, provided that p1 + p2 ≧ 1 and n1 + n2 ≧ 3 when both rings Z ¹ and Z ² are fused polycyclic aromatic hydrocarbon rings.

In the formula (1), 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 each a benzene ring or a biphenyl ring, 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 are C _2-3 alkylene. K1 and k2 may be an integer of about 0 to 3; m1 and m2 may be an integer of about 0 to 3; and n1 and n2 are 2 to 9 (for example, 2 May be an integer on the order of ~ 8); n1 + n2 may be on the order of 4-18 (eg, 4-15).

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

  Moreover, the hardened | cured material which the said curable composition hardened | cured is also contained in this invention. In the cured product, the pencil hardness measured in accordance with JIS K5600-5-4 is 4B or higher (for example, HB or higher), and the mandrel by a flex resistance test measured in accordance with 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, this invention also includes the method of hardening | curing the said curable composition and manufacturing hardened | cured material.

  In the present specification, “(meth) acrylate” is used to include both acrylate and methacrylate.

  In the present invention, since a predetermined amount of an oxyalkylene group is introduced into an epoxy (meth) acrylate having a 9,9-bisarylfluorene skeleton, a cured product having both high hardness and flexibility can be formed. Moreover, in this invention, even if the crosslinking density of hardened | cured material falls by introduction | transduction of an oxyalkylene group, hardness can be improved.

[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 formula (1), the value of n1 + n2 is adjusted to a specific range. Has been.

(Wherein, rings Z ¹ and Z ² are aromatic hydrocarbon rings, R ^1a and R ^1b and R ^2a and R ^2b are each independently a non-radically polymerizable substituent, R ^3a and R ^3b are alkylene groups, R ^4a and R ^4b are a hydrogen atom or a methyl group, 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. Provided that n1 + n2 ≧ 3 when p1 + p2 ≧ 1 and both rings Z ¹ and Z ² are fused polycyclic aromatic hydrocarbon rings).

In the 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, a polycyclic arene ring, and the like. The polycyclic arene ring includes a condensed polycyclic arene ring (fused polycyclic aromatic hydrocarbon ring), a ring assembly arene ring (ring assembly aromatic hydrocarbon ring) and the like.

Examples of the condensed polycyclic arene ring include a condensed bicyclic arene ring (for example, a C _10-16 condensed bicyclic arene ring such as a naphthalene ring), a condensed tricyclic arene ring (for example, an anthracene ring, a phenanthrene ring). Etc.) and the like. Preferred examples of the condensed polycyclic arene ring include a naphthalene ring and an anthracene ring, and a naphthalene ring is particularly preferable.

Examples of the ring-assembled arene ring include biarene rings (for example, bi-C _6-12 arene rings such as biphenyl ring, binaphthyl ring, phenylnaphthalene ring (for example, 1-phenylnaphthalene ring, 2-phenylnaphthalene ring)) Examples thereof include a ring (for example, a tel C _6-12 arene ring such as a terphenylene ring). Preferred examples of the aggregate ring arene ring include a bi-C _6-10 arene ring, particularly a biphenyl ring.

The two rings Z ¹ and Z ² bonded to the 9-position of fluorene may be the same or different and are usually 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. From the viewpoint of flexibility, a benzene ring is particularly preferable, and from the viewpoint of a high refractive index. In particular, a naphthalene ring is preferable.

Incidentally, the substitution position of the ring Z ¹ and Z ² which binds to the 9-position of fluorene is not particularly limited. For example, when the rings Z ¹ and Z ² are naphthalene rings, the group corresponding to the 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. Further, 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 formula (1), the non-radically polymerizable substituents R ^1a and R ^1b are hydrocarbon groups [eg, alkyl groups (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group]. A linear or branched C _1-6 alkyl group such as a group), an aryl group (such as a C _6-10 aryl group such as a phenyl group)], a cyano group, a halogen atom (such as a fluorine atom, Chlorine atom, bromine atom, etc.).

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

The number of substitutions k1 and k2 of the groups R ^1a and R ^1b is an integer of 0 to 4 (for example, about 0 to 3), preferably an integer of about 0 to 2, more preferably 0 or 1, especially 0. In addition, 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 the groups R ^1a and R ^1b in the same benzene ring may be the same or different from each other. In addition, the substitution position of the groups R ^1a and R ^1b is 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 formula (1), as the non-radical polymerizable substituents R ^2a and R ^2b , a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), 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 the like linear or branched C _1-10 alkyl group, preferably linear or branched C _{A 1-6} alkyl group, more preferably a linear or branched C _1-4 alkyl group, etc .; a cycloalkyl group (eg, a C _5-10 cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, etc.); an aryl group [For example, phenyl group, alkylphenyl group (for example, methylphenyl group (tolyl group), dimethylphenyl group (xylyl group), etc.), biphenyl group, naphthy Such as _{C 6-12} aryl groups, such as group]; aralkyl groups (e.g., benzyl group, etc. _{C 6-10} aryl _{-C 1-4} alkyl group such as a phenethyl group), etc.], an alkoxy group (e.g., methoxy, ethoxy Group, propoxy group, n-butoxy group, linear or branched C _1-10 alkoxy group such as t-butoxy group, etc., cycloalkyloxy group (for example, C _5-5 such as cyclohexyloxy group, etc.) ₁₀ cycloalkyloxy group), aryloxy group (for example, C _6-10 aryloxy group such as phenoxy group), aralkyloxy group (for example, C _6-10 aryl-C _1-4 alkyl such as benzyloxy group) Oxy group, etc.), alkylthio group (for example, methylthio group, ethylthio group, propylthio group, n-butylthio) O group, t-like _{C 1-10} alkylthio, such as butylthio group), cycloalkylthio groups (for example, such as _{C 5-10} such cycloalkylthio group) an arylthio group (e.g., thiophenoxy group, such as cyclohexyl thio group _{C 6- 10} arylthio group), aralkylthio group (eg, C _6-10 aryl-C _1-4 alkylthio group such as benzylthio group), acyl group (eg, C _1-6 acyl group such as acetyl group), nitro Group, cyano group, dialkylamino group (for example, di- _C1-4 alkylamino group such as dimethylamino group), dialkylcarbonylamino group (for example, di ( _C1-4 alkyl-carbonyl) amino such as diacetylamino group) Group, etc.).

Of these groups R ^2a and R ^2b , typically, a halogen atom, a hydrocarbon group (alkyl group, cycloalkyl group, aryl group, aralkyl group), alkoxy group, acyl group, nitro group, cyano group, substituted An amino group etc. are 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, etc.), especially alkyl groups (especially linear or branched _C1-4 alkyl groups such as methyl groups). Incidentally, when the group ^{R 2a} and ^{R 2b} is an aryl group, a group ^{R 2a} and ^{R 2b,} together with the ring ^{Z 1} and ^{Z 2} may form the ring assembly arene ring. The types of the radicals R ^2a and R ^2b may be the same or different in the same or different rings Z ¹ and Z ² .

The substitution numbers m1 and m2 of the groups R ^2a and R ^2b may be integers of 0 or more, and can be appropriately selected according to the types of the rings 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 position of the group ^{R 2a} and ^{R 2b} is not particularly limited, 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] ( the two groups, called (meth) acryloyl group-containing group It may be substituted at a position other than the substitution position of (sometimes).

In the formula (1), the alkylene groups R ^3a and R ^3b include a linear or branched alkylene group. Examples of the linear alkylene group include an ethylene group, a trimethylene group, and a tetramethylene group. And a linear C _2-6 alkylene group (preferably a linear C _2-4 alkylene group, more preferably a linear C _2-3 alkylene group, particularly an ethylene group). Is, 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, 1,2-butanediyl group, or 1,3-butanediyl group. Can be mentioned. Of these groups R ^3a and R ^3b, a linear or branched C _2-6 alkylene group (for example, a linear or branched C _2-4 alkylene group) is preferable, and a linear chain is more preferable. Or a branched C _2-3 alkylene group (particularly an ethylene group or a propylene group). In addition, among the (meth) acryloyl group-containing groups substituted on the same or different rings Z ¹ and Z ² , the types of alkylene groups R ^3a and R ^3b may be the same or different, and are usually the same. is there. When n1 and n2 are 2 or more, the types of 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 repeating oxyalkylene groups (OR ^3a and OR ^3b ) can be selected from a range of 1 or more integers (for example, an integer 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), more preferably an integer of about 2 to 7 (for example, 3 to 6). In each (meth) acryloyl group-containing group substituted with the same or different rings Z ¹ and Z ² , n 1 and n 2 may be the same or different. The number of repetitions n1 and n2 may be an average value (arithmetic average or arithmetic average) in the molecular assembly of the compound represented by the formula (1), and is about the same as the range of the integers. Also good.

  The total number of repeating numbers n1 and n2 means the total number (total number of additions) of oxyalkylene groups in one molecule of epoxy (meth) acrylate represented by the formula (1), and may be simply referred to as n1 + n2. is there. In addition, n1 + n2 means the total number of all n1 and n2 which exists by the number of p1 and p2, when p1 and / or p2 are two or more. In the present invention, by adjusting the value of n1 + n2 to a predetermined range, high hardness and flexibility in the cured product can be balanced.

When the rings Z ¹ and Z ² are monocyclic aromatic hydrocarbon rings or ring-aggregated aromatic hydrocarbon rings (for example, a benzene ring or a biphenyl ring, particularly a benzene ring), n1 + n2 is, for example, 2 to 30 Can be selected from an integer range of about, for example, an integer of about 3-25 (eg, 3-20), preferably an integer of about 3-18 (eg, 4-16), more preferably 4-15 (eg, 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 both of the rings Z ¹ and Z ² are condensed polycyclic aromatic hydrocarbon rings (particularly naphthalene ring, etc.), n1 + n2 ≧ 3 from the viewpoint that the cured product is likely to be rigid and flexibility is likely to be reduced. N1 + n2 ≧ 4, more preferably n1 + n2 ≧ 5 (for example, n1 + n2 ≧ 6), and n1 + n2 is, for example, an integer of about 3 to 30, preferably 4 to 20 (for example, 4 to 18). An integer of about, more preferably an integer of about 5 to 15 (for example, 5 to 13) may be used.

In addition, n1 + n2 may be an integer as described above, but may be an average value (or average added mole number) of a molecular assembly of the compound represented by the formula (1). n1 + n2, for example, be selected from the range of about 2 to 30, regardless of the type of ring ^{Z 1} and ^{Z 2,} for example, from 2.5 to 25 (e.g., 3 to 20), preferably 3.5 to 18 ( For example, it may be 4 to 16), more preferably 4 to 15 (for example, 4.5 to 14.5), particularly about 5 to 14 (for example, 5.5 to 13.5). -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 also difficult to be exhibited. On the other hand, if the value of n1 + n2 is too large, the crosslink density of the cured product is remarkably lowered, so that high hardness and flexibility cannot be achieved in a balanced manner, and 9,9− per unit amount (for example, unit weight). Since the bisarylfluorene skeleton content (for example, the number of moles contained) is also reduced, there is a possibility that excellent characteristics such as high refractive index and high heat resistance derived from the skeleton may be reduced. 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), more preferably about 5 to 15 (for example, 5 to 12). However, it is possible to obtain a cured product that balances high hardness and flexibility in a balanced manner. 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) used as a raw material From the ratio of the amount of the hydroxy compound and the amount of alkylene oxide or alkylene carbonate consumed, it can be measured by a method of calculating as an arithmetic average or arithmetic average value (for example, the method described in Patent Document 1).

In the formula (1), the groups R ^4a and R ^4b are a hydrogen atom or a methyl group. In each (meth) acryloyl group-containing group substituted on the same or different rings Z ¹ and Z ² , the groups R ^4a and R ^4b may be the same or different 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, more preferably 1 or 2 (especially 1) may be sufficient. However, p1 + p2 ≧ 1. If p1 and p2 are too large, the crosslinking density tends to be high, and the flexibility may be reduced. 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 p1 and p2 are 1, it is often substituted at the 2-, 3-, 4-position (particularly the 3-position or 4-position) of the phenyl group. When p1 and p2 are 2, they are often substituted at 2-position and 4-position, 3-position and 4-position (particularly 2-position and 4-position). When p1 and p2 are 3 or more, the substitution position is not particularly limited. In addition, when the rings Z ¹ and Z ² are naphthalene rings, they are often substituted at any of the 5- to 8-positions of the naphthyl group. For example, when p1 and p2 are 1, The 1-position or 2-position of the naphthalene ring is substituted with respect to the 9-position (substitution is made in relation to 1-naphthyl or 2-naphthyl), and the 1,5-position, 2,6 with respect to this substitution position In many cases, a (meth) acryloyl group-containing group is substituted in a relationship such as -position (particularly, a relationship in 2,6-position). Moreover, when p1 and p2 are 2 or more, a substitution position is not specifically limited. In addition, in the ring assembly arene rings Z ¹ and Z ² , the substitution position of the (meth) acryloyl group-containing group is not particularly limited. For example, when p 1 and p 2 are 1, arene bonded to the 9-position of fluorene The ring and / or the arene ring adjacent to the arene ring may be substituted. For example, the 3-position 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 ring Z ¹ and Z ² is bonded to the 9-position of fluorene, the substitution position of the (meth) acryloyl group-containing group is the 2-, 4-, 5-, 6- of the biphenyl ring. , 2'-, 3'-, 4'-position, usually 6-, 3'-, 4'-position, preferably 6-, 4'-position (especially 6-position) ) May be substituted. When the 4-position of the biphenyl ring 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 the '-, 4'-position, and is usually substituted at the 2-, 3'-, 4'-position, preferably the 2-, 4'-position (particularly the 2-position). Also good. Moreover, when p1 and p2 are 2 or more, a substitution position is not specifically limited.

Among the epoxy (meth) acrylates represented by the formula (1), as typical compounds, for example, in the formula (1), the rings Z ¹ and Z ² are benzene rings, p1 = p2 = 1, n1 = N2 = 1, that is, 9,9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) alkoxyphenyl] fluorenes; in the formula (1), the rings Z ¹ and Z ² are Benzene ring or naphthalene ring, p1 = p2 = 1, compound in which n1 and n2 are 2 to 10, that is, 9,9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) polyalkoxyphenyl] fluorene 9,9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) polyalkoxynaphthyl] fluorenes and the like It is.

As 9,9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) alkoxyphenyl] fluorenes, in the 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- (3- (Meth) acryloyloxy-2-hydroxypropoxy) ethoxy) phenyl] fluorene, 9,9-bis [4- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) propoxy) phenyl] fluorene 9,9-bis such [(3- (meth) _{acryloyloxy-2-hydroxypropoxy) C 2-4} alkoxyphenyl] fluorene; (1b) 9, -Bis [4- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2- (3- (meth) acryloyl) Oxy-2-hydroxypropoxy) propoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) -3-isopropylphenyl] Fluorene, 9,9-bis [4- (2- (3- (meth) 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 [ -(2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) -3,5-dimethylphenyl] fluorene, 9,9-bis [4- (2- (3- (meth) acryloyloxy-) 2-hydroxypropoxy) ethoxy) -3-tert-butyl-6-methylphenyl] fluorene, 9,9-bis [4- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) -2 9,9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) C _2-4 alkoxy-mono or diC _1-4 alkylphenyl] fluorene, such as, 5-dimethylphenyl] fluorene; (1c) 9,9-bis [4- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) -3-cyclohexyl Nenyl] fluorene, 9,9-bis [(3- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) propoxy) -3-cyclohexylphenyl] fluorene and the like. meth) _{acryloyloxy-2-hydroxypropoxy) C 2-4} alkoxy _{-C 5-10} cycloalkyl phenyl] fluorene; (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, etc. 9,9-bis [(3- (meth) _{acryloyloxy-2-hydroxypropoxy) C 2-4} Al , And others carboxymethyl _{-C 6-10} aryl phenyl] fluorene.

As 9,9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) polyalkoxyphenyl] fluorenes, in 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, that is, the compounds of the above (1a) to (1d) And n1 and n2 are each 2 to 10, for example, (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) 9,9- such as nyl] fluorene, 9,9-bis [4- (2- (2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) ethoxy) ethoxy) phenyl] fluorene) Bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) di to deca C _{2-4alkoxyphenyl} ] fluorene; (1f) 9,9-bis [4- (2- (2- (3- (meta ) 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- (3- (meth) acryloyloxy-) -Hydroxypropoxy) ethoxy) ethoxy) ethoxy) -3-isopropylphenyl] fluorene, 9,9-bis [4- (2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) ethoxy) 9,9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) di to deca C _2-4 alkoxy-mono or diC _1-4 alkylphenyl] such as −3,5-dimethylphenyl] fluorene Fluorene; (1 g) 9,9-bis [4- (2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) ethoxy) -3-cyclohexylphenyl] fluorene, 9,9-bis [4- (2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) propoxy) propyl Poxy) -3-cyclohexylphenyl] fluorene, 9,9-bis [4- (2- (2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) ethoxy) ethoxy) -3- 9,9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) di to deca C _2-4 alkoxy-C _5-10 cycloalkylphenyl] fluorene such as cyclohexylphenyl] fluorene; (1h) 9, 9-bis [4- (2- (2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) ethoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2- ( 2- (3- (meth) acryloyloxy-2-hydroxypropoxy) propoxy) propoxy) -3-phenylphenyl] 9,9, such as fluorene, 9,9-bis [4- (2- (2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) ethoxy) ethoxy) -3-phenylphenyl] fluorene) Examples thereof include 9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) di to deca C _2-4 alkoxy-C _6-10 arylphenyl] fluorene.

As 9,9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) polyalkoxynaphthyl] fluorenes, in 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, 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- ( (Meth) acryloyloxy-2-hydroxypropoxy) propoxy) propoxy) -2-naphthyl] fluorene, 9,9-bis [6- (2- (2- (2- (3- (meth) acryloyl) Xyl-2-hydroxypropoxy) ethoxy) ethoxy) ethoxy) -2-naphthyl] fluorene, 9,9-bis [5- (2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) And 9,9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) di to deca C _2-4 alkoxynaphthyl] fluorene such as ethoxy) -1-naphthyl] fluorene.

These epoxy (meth) acrylates may be used alone or in combination of two or more to form a molecular assembly. As a preferable epoxy (meth) acrylate, in the formula (1), the rings Z ¹ and Z ² are benzene rings or naphthalene rings, p1 = p2 = 1, n1 and n2 are each 2 to 10, that is, 9 , 9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) polyalkoxyphenyl] fluorenes; 9,9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) polyalkoxynaphthyl] Fluorenes are mentioned, among them (1e) 9,9-bis [4- (2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) ethoxy) phenyl] fluorene, etc. 9,9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) di- to deca _{C 2-} Alkoxyphenyl] fluorene; (1f) 9,9-bis [4- (2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) ethoxy) -3, such as methyl phenyl] fluorene 9 , 9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) di- to deca _{C 2-4} alkoxy - mono- or _{di-C 1-4} alkyl phenyl] fluorene; (1h) 9,9-bis [4 9,9-bis [(3- (meth) acryloyloxy-2 such as-(2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) ethoxy) -3-phenylphenyl] fluorene - hydroxypropoxy) di- to deca _{C 2-4} alkoxy _{-C 6-10} aryl phenyl] fluorene; (1i) 9,9-bis 6- (2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) ethoxy) -2-naphthyl] fluorene, 9,9-bis [5- (2- (2- (3- (3- 9,9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) di to deca C _2-4 such as (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) ethoxy) -1-naphthyl] fluorene Alkoxynaphthyl] fluorene and the like are preferable, and in particular, in the formula (1), the ring Z ¹ and Z ² are benzene rings, R ^2a and R ^2b are alkyl groups, and m1 and m2 are each 0 to 2, that is, (1e) 9,9-bis [4- (2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) ethoxy ) Phenyl] fluorene such as 9,9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) di- to deca _{C 2-4} alkoxyphenyl] fluorene; (1f) 9,9-bis [4- ( 9,9-bis [(3- (meth) acryloyloxy-2-hydroxy, such as 2- (2- (3- (meth) acryloyloxy-2-hydroxypropoxy) ethoxy) ethoxy) -3-methylphenyl] fluorene Propoxy) di to deca C _2-4 alkoxy-mono or diC _1-4 alkylphenyl] fluorene and the like are preferred.

[Method for producing epoxy (meth) acrylate]
The production method of 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 is a conventional method, for example, It may be a method (A) in which an epoxy compound represented by the formula (2) (see JP 2009-155256 A) and a (meth) acrylic acid component are reacted.

(Wherein 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, 1) Same as the description).

  In addition, there is a method (B) in which the first hydroxy compound represented by the following formula (3) is reacted with glycidyl (meth) acrylate (see, for example, methods described in Patent Documents 3 to 5). May be.

(Wherein 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, 1) Same as the description).

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

  In addition, the epoxy compound represented by the said formula (2) used by the said method (A) may use a commercial item, for example, the 1st method represented by the said formula (3), for example. You may prepare by the method etc. with which a hydroxy compound and epihalohydrin (for example, epichlorohydrin, epibromohydrin, etc.) are made to react. Therefore, even when the epoxy (meth) acrylate represented by the formula (1) is prepared by any of the methods (A) or (B), the first hydroxy compound represented by the formula (3) The oxyalkylene group addition number in the epoxy compound represented by the formula (2) and the epoxy (meth) acrylate represented by the formula (1) is controlled by controlling the number of oxyalkylene group additions (n1 + n2) in a predetermined range. 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 each be a molecular assembly, and the number of added oxyalkylene groups (n1 + n2). Alternatively, the average value of the molecular assembly may be the same as the epoxy (meth) acrylate represented by the formula (1).

(First hydroxy compound represented by the formula (3))
In the formula (3), each of the 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 Preferred embodiments are the same as described above. As typical first hydroxy compounds represented by the formula (3), for example, compounds (1a) to (1i) exemplified as typical examples of the epoxy (meth) acrylate represented by the formula (1). , Ie, compounds (3a) to (3i) in which a 3- (meth) acryloyloxy-2-hydroxypropoxy group is replaced with a hydrogen atom. These compounds may be contained alone or in combination of two or more as a molecular assembly.

The first hydroxy compound represented by the formula (3) is not particularly limited, and a commercially available product may be used. For example, the second hydroxy compound represented by the following formula (4) may be used. And an alkylene oxide or alkylene carbonate corresponding to the oxyalkylene groups OR ^3a and OR ^3b in the formula (3) may be prepared.

(Wherein, x1 and x2 each represents 0 or 1, and 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 is the same as described in the formula (1)).

In the formula (4), preferred embodiments of the 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 as follows. , The same as described above. As a typical example of the second hydroxy compound represented by the formula (4), a compound in which the number of repeating oxyalkylene groups x1 = x2 = 1, for example, the first hydroxy compound represented by the formula (3) is used. 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 [hydroxyC _2-4 alkoxynaphthyl] fluorenes such as hydroxyethoxy-2-naphthyl] fluorene, 9,9-bis [5- (2-hydroxypropoxy) -1-naphthyl] fluorene; Compound (sometimes referred to as compound (3j)), and compounds in which the number of repeating oxyalkylene groups x1 = x2 = 0, for example, the compounds (3a) to (3d) and Compound a hydroxyalkoxy group replaced with hydroxyl groups of the 3j) (4a) and the like ~ (4d) and (4j). These compounds can be used alone or in combination of two or more. In addition, when it is a compound which is x1 = x2 = 1, coloring of the 1st hydroxy compound represented by the said Formula (3) (Furthermore, the epoxy (meth) acrylate represented by the said Formula (1)) is carried out. Easy to suppress.

  As the second hydroxy compound represented by the formula (4), a commercially available product may be used, and a conventional method, for example, in the presence of an acid catalyst such as an inorganic or organic acid or a promoter such as a thiol, You may synthesize | combine by the method (For example, the method of Unexamined-Japanese-Patent No. 2007-91870 etc.) etc. which react 9-fluorenones, such as 9-fluorenone, and phenols or aryloxy alcohols. Examples of phenols include phenol, biphenylol, and naphthol. Examples of aryloxy alcohols include 2-phenoxyethanol, 2-phenoxypropanol, 2- (phenylphenoxy) ethanol, and 2- (naphthoxy) ethanol. Etc. can be exemplified. In addition, by using aryloxy (poly) alkoxy alcohols instead of phenols or aryloxy alcohols, directly without passing through the second hydroxy compound represented by the formula (4), The first hydroxy compound represented by the formula (3) may be synthesized, but from the viewpoint of reactivity and the like, there is a method of synthesizing via the second hydroxy compound represented by the formula (4). preferable.

As the alkylene oxide corresponding to the oxyalkylene groups OR ^3a and OR ^3b in the formula (3), C _2-6 alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, preferably C _2-4 alkylene oxide, more preferably And C _2-3 alkylene oxide (particularly ethylene oxide). As the alkylene carbonate corresponding to the oxyalkylene groups OR ^3a and OR ^3b in the formula (3), C _2-6 alkylene carbonate such as ethylene carbonate, propylene carbonate, butylene carbonate, preferably C _2-4 alkylene carbonate, more preferably Is C _2-3 alkylene carbonate (particularly ethylene carbonate).

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

  When the oxyalkylene group repeating number 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 the amount used by subtracting the number of oxyalkylene groups added (x1 + x2 mol) from the amount used. In addition, said x1 + x2 means the total value of all the existing x1 and x2, when p1 and / or p2 are two or more.

  The reaction between the second hydroxy compound represented by the formula (4) and alkylene oxide or alkylene carbonate may be performed in the absence of a catalyst, but may be generally performed 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. Base catalysts 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 hydrogen carbonate, etc.) Alkali metals or alkaline earth metal hydrogen carbonates), inorganic bases such as ammonia; amines [for example, tertiary amines (triethylamine, triisopropylamine, trialkylamines such as tributylamine, benzyldimethylamine, etc. Benzyldialkylamines, aromatic tertiary amines such as N, N-dimethylaniline, heterocyclic tertiary amines such as 1-methylimidazole, etc.], carboxylic acid metal salts (sodium acetate, alkali acetates such as calcium acetate) Metal or alkaline earth metal salts), basic ions Exchange resin (e.g., a like quaternary ammonium base strongly basic anion exchange resin having a) an organic base, and others. The catalyst (base catalyst) may be used alone or in combination of two or more.

  The usage-amount of a catalyst can be adjusted according to the kind of catalyst, and is 0.001-1 weight part (for example, 0.001 weight part) with respect to 1 weight part of 2nd hydroxy compounds represented by the said Formula (4). 003 to 0.5 parts by weight), preferably 0.005 to 0.3 parts by weight, and more preferably about 0.01 to 0.1 parts by weight.

The reaction may be performed in a solvent. The solvent is not particularly limited and can be selected according to the raw material to be used. For example, when using an alkylene oxide, an ether solvent (dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane, Anisole, etc.); halogenated solvents (halogenated hydrocarbons such as methylene chloride and chloroform); hydrocarbon solvents (aromatic hydrocarbons such as toluene and xylene) and the like. When alkylene carbonate is used, in addition to the solvents exemplified above, alcohols (linear or branched C _1-4 alcohols such as methanol and ethanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol) (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, and more preferably 2 to 2 parts by weight with respect to 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 performed at, for example, about 0 to 170 ° C., preferably 10 to 150 ° C., more preferably about 20 to 130 ° C., depending on the type of compound to be added (alkylene oxide, alkylene carbonate) and the like. In particular, when alkylene carbonate is used, in order to efficiently perform the decarboxylation reaction, for example, the reaction is often performed at 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 performed with stirring, may be performed in air or in an inert atmosphere (such as a nitrogen atmosphere or a rare gas atmosphere such as helium or argon), or may be performed under normal pressure or under pressure. Moreover, you may react, removing the gas (carbon dioxide etc.) which generate | occur | produces as needed.

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

  By such a method, the 1st hydroxy compound represented by the said Formula (3) by which the addition number (n1 + n2) of the oxyalkylene group was adjusted can be obtained. An epoxy (meth) acrylate represented by the formula (1) can be produced by subjecting the first hydroxy compound represented by the formula (3) to the method (A) or (B). it can.

(Method (A))
In the method (A), the epoxy compound represented by the above formula (1) is reacted with the (meth) acrylic acid component (method (A-2)) to thereby represent the epoxy represented by the above formula (1). (Meth) acrylate can be prepared, and the epoxy compound is a method in which the first hydroxy compound represented by the formula (3) and an epihalohydrin (for example, epichlorohydrin, epibromohydrin, etc.) are reacted (A-1 ) And the like.

In the formula (2), each of the 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 A preferable aspect etc. are the same as the description of the term of the epoxy (meth) acrylate represented by the said Formula (1). The representative epoxy compound represented by the formula (2) corresponds to, for example, the compounds (1a) to (1i) exemplified as typical examples of the epoxy (meth) acrylate represented by the formula (1). Examples of the epoxy compound include 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) and the epihalohydrin, the amount of the epihalohydrin used relative 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 about 2.5 to 15 mol (eg 3 to 10 mol).

  In the reaction of the first hydroxy compound represented by the formula (3) and the epihalohydrin, a catalyst may be appropriately used. Examples of the catalyst include a base (base catalyst), for example, the base catalyst exemplified in the reaction of the second hydroxy compound represented by the formula (4) with alkylene oxide or alkylene carbonate. You may use a base individually or in combination of 2 or more types.

  The amount of the catalyst (for example, a base catalyst) used depends on the type of the catalyst, but for example, for example, 0.01 mol per 1 mol of the hydroxyl group of the first hydroxy compound represented by the formula (3). -10 mol, preferably 0.05 to 5 mol, more preferably about 0.1 to 3 mol.

The reaction may be performed in the presence of a phase transfer catalyst. Examples of the phase transfer catalyst include ammonium salts [eg, 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) and the like. It is done. The phase transfer catalysts 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 to 100 parts by weight of the total amount of the first hydroxy compound represented by the formula (3) and the epihalohydrin. It may be about 10 to 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 performed in the absence of a solvent or in a solvent. Examples of the solvent (organic solvent) include hydrocarbons (aliphatic hydrocarbons such as hexane, heptane, and octane, aromatic hydrocarbons such as toluene and xylene); halogenated hydrocarbons (methylene chloride, chloroform, 1 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. Is mentioned. You may use a solvent individually or in combination of 2 or more types as a mixed solvent. Of these solvents, ketones (particularly methyl isobutyl ketone) are preferred. In addition, when the said catalyst is a liquid, you may use the said catalyst 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 with respect to 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, 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 performed while refluxing or may be performed while removing by-products. In addition, the reaction may be performed with stirring, may be performed in air or in an inert atmosphere (such as a nitrogen atmosphere, a rare gas atmosphere such as helium or argon), and is performed under normal pressure, increased pressure, or reduced pressure. May be. In particular, when the reaction is performed 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 separated by a conventional method such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, or a combination thereof. Separation and purification may be performed by another 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 a (meth) acrylic acid component. Acrylate can be prepared.

  As said (meth) acrylic acid component, (meth) acrylic acid is mentioned, A commercial item etc. can be used.

  The ratio of the epoxy compound represented by the formula (2) and the (meth) acrylic acid component is, for example, 1 mol or more (for example, 1 to 5 mol, preferably 1 mol) with respect to 1 mol of the glycidyl group of the epoxy compound. 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 performed in the presence of a catalyst, if necessary. Examples of the catalyst include the base catalyst exemplified in the reaction of the second hydroxy compound represented by the formula (4) with alkylene oxide or alkylene carbonate. You may use a base individually or in combination of 2 or more types.

  Although the usage-amount of a catalyst (for example, basic catalyst) also depends on the kind of catalyst, for example, 0.01-10 mol with respect to 1 mol of glycidyl groups of the epoxy compound represented by the formula (2). , Preferably 0.05 to 5 mol, more preferably about 0.1 to 3 mol.

  The reaction may be performed 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 catalysts 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 with respect to 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 performed in the presence of a polymerization inhibitor (or a thermal polymerization inhibitor). Examples of thermal polymerization inhibitors include benzoquinone, hydroquinones (eg, hydroquinone, hydroquinone monomethyl ether (methoquinone), p-tert-butylhydroquinone, p-benzoquinone, etc.), catechols (eg, p-tert-butylcatechol, etc.), Examples include amines (for example, N, N-diethylhydroxylamine), 1,1-diphenyl-2-picrylhydrazyl, tri-p-nitrophenylmethyl, phenothiazine and the like. The thermal polymerization inhibitors may be used alone or in combination of two or more.

  The proportion 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. About 0.01-0.5 weight part (for example, 0.02-0.1 weight part) may be sufficient.

  The reaction may be performed in the presence of a solvent. The solvent is not particularly limited and includes, for example, ketones (for example, dialkyl ketones such as acetone, diisopropyl ketone, and methyl isobutyl ketone, cyclic ketones such as cyclohexanone); ethers (for example, chain structures 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); esters (eg, ethyl acetate); nitriles (eg, acetonitrile) Amides (eg, dimethylformamide, dimethylacetamide, etc.); sulfoxides; hydrocarbons [aliphatic hydrocarbons (eg, hexane, hepta) Etc.), alicyclic hydrocarbons (eg, cyclohexane, etc.), aromatic hydrocarbons (eg, toluene, xylene, ethylbenzene, etc.)]; halogenated solvents (eg, methylene chloride, chloroform, 1,2-dichloroethane, etc.) ) And the like. These solvents may be used alone or as a mixed solvent in combination of two or more. The usage-amount of a solvent may be 1-1000 weight part with respect to 100 weight part of epoxy compounds represented by the said Formula (2), for example, Preferably it may be about 5-500 weight part.

  Although reaction temperature is not specifically limited, For example, 20-200 degreeC (for example, 40-180 degreeC), Preferably it is 50-160 degreeC (for example, 60-150 degreeC), More preferably, it is 70-140 degreeC (for example, 80 ~ 130 ° C). The reaction time may be, for example, 30 minutes to 48 hours, preferably 1 to 24 hours, more preferably about 2 to 10 hours. The reaction may be carried out with stirring, in air or in an inert atmosphere (nitrogen atmosphere, rare gas atmosphere such as helium or argon), and carried out under normal pressure, under pressure or under reduced pressure. May be.

  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 formula (1)). Therefore, it may be purified using a conventional method, for example, separation means such as filtration, concentration, neutralization, extraction, crystallization, recrystallization, column chromatography, or a combination of these.

  Since the epoxy (meth) acrylate represented by the formula (1) obtained by such a method has a 9,9-bisarylfluorene skeleton, it has a high refractive index and is used as an optical member. It can be suitably used. The refractive index (temperature 25 ° C., wavelength 589 nm) of the epoxy (meth) acrylate represented by the formula (1) can be selected from a range of about 1.5 to 1.65, for example, 1.52 to 1 .6, preferably 1.53 to 1.59, more preferably about 1.54 to 1.57. The refractive index can be measured with a multiwavelength Abbe refractometer or the like.

  In the present invention, since the number of added oxyalkylene groups (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 a range of about 5000 to 150,000 mPa · s (for example, 10,000 to 60000 mPa · s), for example, 20000 to 50000 mPa -S, Preferably it is 30000-45000 mPa * s, More preferably, about 35000-40000 mPa * s may be sufficient. The viscosity can be measured by the method described in Examples described later.

[Curable composition]
Although the epoxy (meth) acrylate of the present invention may be used alone, it 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); diacyl peroxides (eg, lauroyl peroxide, benzoyl peroxide, etc.); (Or peracid esters) (eg, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peracetate, etc.); ketone peroxides; peroxycarbonates; peroxyketals]; azo compounds [eg, 2 , 2′-azobis (isobutyronitrile); azoamide compounds; azoamidine compounds, etc.]. 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-hydroxycyclohexyl phenyl ketone, etc.); aminoacetophenones (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone- Anthraquinones (anthraquinone, anthraquinone-2-sulfonate, etc.); thioxanthones (eg, thioxanthone, isopropoxychlorothioxanthone, etc.); ketals (acetophenone dimethyl keter) Benzophenones (eg, benzophenone, 4-hydroxybenzophenone, etc.); 2,4,5-triarylimidazole dimers (eg, 2- (o-chlorophenyl) -4,5-diphenyl) Imidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, etc.); xanthones; 2,4,6-trihalomethyltriazines; acridine derivatives (eg, 9-phenyl) Examples include acridine, 1,7-bis (9,9′-acridinyl) heptane, etc.); bisacylphosphine oxides (eg, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide) and the like. . These photopolymerization initiators may be used alone or in combination of two or more.

  The ratio 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 formula (1) and 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 per 100 parts by weight) It may be about parts by weight. Among these polymerization initiators, it is preferable to include at least a photopolymerization initiator.

  Moreover, you may combine a photoinitiator with a photosensitizer. Photosensitizers include tertiary amines [e.g., trialkylamines; trialkanolamines (such as triethanolamine); ethyl N, N-dimethylaminobenzoates [such as ethyl p- (dimethylamino) benzoate] Dialkylaminobenzoic acid alkyl esters such as amyl N, N-dimethylaminobenzoate [amyl amyl p- (dimethylamino) benzoate]; 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) Conventional sensitizers such as bis (dialkylamino) benzophenone such as benzophenone; dialkylaminobenzophenone such as 4- (dimethylamino) benzophenone and 4-methoxy-4′-dimethylaminobenzophenone] and the like. These photosensitizers may be used alone or in combination of two or more.

  The proportion of the photosensitizer may be about 1 to 200 parts by weight, preferably about 5 to 150 parts by weight, and more preferably about 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, and the like may be improved. The other polymerizable compound is often a monofunctional or polyfunctional (meth) acrylate having a (meth) acryloyl group.

As monofunctional (meth) acrylate, for example, alkyl (meth) acrylate [for example, C _1-20 alkyl (meth) acrylate such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, etc.]] Hydroxyalkyl (meth) acrylate (eg, hydroxyethyl (meth) acrylate); alkoxyalkyl (meth) acrylate (eg, methoxyethyl (meth) acrylate); cycloalkyl (meth) acrylate (eg, cyclohexyl (meth)) Acrylate); aryl (meth) acrylate (eg, phenyl (meth) acrylate); aryloxyalkyl (meth) acrylate (eg, phenoxyethyl (meth) acrylate); aralkyl (meth) ) Acrylates (eg benzyl (meth) acrylate); aryloxy ((poly) alkoxy) alkyl (meth) acrylates (eg phenoxyethoxyethyl (meth) acrylate); alkylaryloxyalkyl (meth) acrylates (eg , Nonylphenoxyethyl (meth) acrylate, etc.); alkylaryloxy (poly) alkoxyalkyl (meth) acrylate (eg, nonylphenoxy (poly) ethoxyethyl (meth) acrylate, etc.); arylaryloxyalkyl (meth) acrylate (eg, , 2- (o-phenylphenoxy) ethyl (meth) acrylate, etc.); arylaryloxy (poly) alkoxyalkyl (meth) acrylate (eg, phenylphenoxy (poly) ) Ethoxyethyl (meth) acrylate); (meth) acrylate having a sulfur atom [for example, alkylthio (meth) acrylate (for example, methylthio (meth) acrylate); arylthio (meth) acrylate (for example, phenylthio (meth) acrylate) Aralkylthio (meth) acrylate (eg benzylthio (meth) acrylate etc.); Arylthioalkyl (meth) acrylate (eg phenylthioethyl (meth) acrylate etc.)]; N, N-dialkyl (meth) Acrylamide (eg, N, N-dimethyl (meth) acrylamide); N, N-dialkylaminoalkyl (meth) acrylate (eg, N, N-dimethylaminoethyl (meth) acrylate); Bisphenols Or a mono (meth) acrylate of an alkylene oxide adduct thereof (for example, a mono (meth) acrylate of an ethylene oxide adduct of bisphenol A); a (meth) acrylate having a fluorene skeleton (eg, 9- (meth) acryloyloxymethylfluorene) In the formula (1), p1 + p2 = 1 and n1 or n2 is 11 or more).

As the polyfunctional (meth) acrylate, bifunctional (meth) acrylate [for example, (poly) C such as ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, etc. _2-4 alkylene glycol di (meth) acrylate; di (meth) acrylate or the like of bisphenol A (or an alkylene oxide adduct thereof); trifunctional or higher functional (meth) acrylate [for example, glycerin tri (meth) acrylate, tri Methylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Tri- to hexaol tri- to hexa- (meth) acrylate]; urethane (meth) acrylate; epoxy (meth) acrylate not belonging to the scope of the present invention (for example, in the formula (1), p1 + p2 ≧ 2, And a compound having n1 or n2 of 11 or more); (meth) acrylate having a fluorene skeleton [for example, 9,9-bis [4- (2- (meth) acryloyloxy (poly) ethoxy) phenyl] fluorene and the like] Etc. These monofunctional and polyfunctional (meth) acrylates can be used alone or in combination of two or more.

  The ratio of these polymerizable compounds can be selected from the range of, 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). 1-20) parts by weight, more preferably about 0-10 parts by weight.

(Other additives)
Moreover, the said curable composition may contain the solvent as needed. It does not specifically limit as a solvent, The solvent etc. which were illustrated in the term of the manufacturing method of the said epoxy (meth) acrylate may be sufficient. These solvents can be used alone or in combination of two or more thereof as a mixed solvent. The proportion of the solvent is, for example, 100 to 2000 parts by weight, preferably 300 to 1500 parts by weight with respect to 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 a conventional additive such as a colorant, a stabilizer (a heat stabilizer, an antioxidant, an ultraviolet absorber, etc.), a polymerization inhibitor, a filler, as long as the effects of the present invention are not impaired. Agents, antistatic agents, flame retardants, surfactants, plasticizers, antifoaming agents, coupling agents 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 to 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 to 10 parts by weight, more preferably about 1 to 5 parts by weight.

[Hardened product]
A curable composition hardens | cures easily by providing active energy (active energy ray). As the active energy, thermal energy and / or light energy (ultraviolet ray, electron beam, X-ray, etc.) is useful, and can be appropriately selected according to the purpose.

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

Moreover, when utilizing light energy (for example, light irradiation, such as ultraviolet irradiation), the amount of light irradiation energy can be suitably selected according to a use, for example, 50-10000 mJ / cm < ² >, Preferably it is 70-8000 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 excimer laser), or the like can be used.

  Note that in the case of curing by light irradiation, heat treatment (baking treatment or after-baking or the like) may be performed in order to improve the reactivity. The temperature and time of the heat treatment are the same as when using the heat energy. The reaction (or polymerization, crosslinking, or curing) may be performed in an air atmosphere or an inert gas atmosphere (for example, a nitrogen gas atmosphere, a rare gas atmosphere such as helium, argon, or the like), and is performed under normal pressure, increased pressure, or reduced pressure. You may do it below.

  The cured product of the present invention is surprisingly high in hardness despite the introduction of a highly flexible oxyalkylene group, and balances the conflicting properties of high hardness and flexibility. 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, usually, when an oxyalkylene group is introduced, the cured product has a tendency to greatly improve the flexibility of the cured product because it incorporates a structure that easily bends and the crosslinking density also decreases. It is in. For this reason, the hardness, which is a characteristic contrary to flexibility, is greatly reduced. However, the epoxy (meth) acrylate of the present invention has a hydroxyl group (hydroxyl group adjacent to the (meth) acryloyl group) in the side chain, and the number of added oxyalkylene groups (n1 + n2) is adjusted to a predetermined range. This is because 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 easily form a hydrogen bond, forming a pseudo-crosslinking point, It is thought that the hardness has improved. In addition, when the crosslinking density and hardness are improved, the initial flexibility is generally lost. However, 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 assumed that the bond is broken (decrease in crosslink density), the flexibility derived from the oxyalkylene group is expressed, and a new hydrogen bond is formed when the external force is removed. The

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

  The refractive index (temperature 25 degreeC, wavelength 589nm) of the said hardened | cured material can be selected from the range of about 1.5-1.65, for example, for example, 1.53-1.62, Preferably it is 1.54-1. 6, More preferably, it may be about 1.55 to 1.58. The refractive index can be measured with a multiwavelength 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 measured with a mandrel bending tester or the like according to JIS K5600-5-1. be able to. The flexibility (flexibility) of the cured product is represented by a mandrel diameter (or minimum diameter) at which the cured product cracks or peels off 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, even if the cured product of the present invention is less than the measurement lower limit (2 mm), cracks and peeling from the substrate are unlikely to occur. In the present specification and claims, when the measurement lower limit (2 mm) does not cause cracking of the cured film or peeling from the substrate, 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, Lens).

  The method for producing the cured product is not particularly limited. For example, the cured film is made of the curable composition as a base material or a substrate [for example, metal (aluminum, etc.), ceramics (titania, glass, quartz, etc.), etc. , Organic materials such as plastic (polypropylene, cyclic olefin resin, polycarbonate, etc.), porous materials such as wood, etc.] to form a coating film (or thin film), and may be produced by curing treatment . The three-dimensional structure may be produced by molding or casting (injecting) the curable composition into a predetermined mold and then curing (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 <use of circulating water bath 60-C3>), the temperature was kept at 25 ° C., and the refractive index at 589 nm was measured.

(viscosity)
Using a TV-22 viscometer (cone plate type, “TVE-22L” manufactured by Toki Sangyo Co., Ltd.), the viscosity at 25 ° C. was measured using an optional rotor (01: 1 ° 34 ′ × R24, 07: 3 ° × 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) base material (manufactured by Toyobo Co., Ltd.) having a thickness of 150 μm was converted into a pencil hardness meter (Shinto Kagaku ( "HEIDON-14" manufactured by Co., Ltd.), pressing various pencils at an angle of 45 degrees, moving the cured film at a speed of 1 mm / second while applying a load of 750 g, It was measured by checking the presence or absence visually.

(Flexibility or bending resistance (mandrel diameter))
In accordance with JIS K5600-5-1, each cured film (thickness 150 to 200 μm) is formed on a 150 μm thick PET base material (manufactured by Toyobo Co., Ltd.), and a mandrel flexibility tester ((Co., Ltd.) ) Measured using “HD-5110” manufactured by Ueshima Seisakusho. In addition, the softness | flexibility was evaluated by the diameter (or minimum diameter) [mm] of the mandrel which a crack and / or peeling generate | occur | produce in a cured film.

(Raw materials)
BPEF-9EO: an adduct obtained by adding 9 mol of oxyethylene group (or ethylene oxide) on average to 1 mol of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, Osaka Gas Chemical ( BPEF-9EOG: diglycidyl ether of BPEF-9EO BPEF-5EO: 5 moles of oxyethylene group on average per mole of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (Or ethylene oxide) adduct, Osaka Gas Chemical Co., Ltd. BPEF-5EOG: BPEF-5EO diglycidyl ether BNEF-13EO: 9,9-bis (6- (2-hydroxyethoxy) -2-naphthyl ) An average of 13 moles of oxyethylene groups (or ethylene OH) per mole of fluorene Adducts added with oxide), Osaka Gas Chemical Co., Ltd. BNEF-13EOG: Diglycidyl ether of BNEF-13EO BPEF-9EOA: Diacrylate of BPEF-9EO, (Meth) acrylic acid component manufactured by Osaka Gas Chemical Co., Ltd. : Acrylic acid Solvent: Methyl isobutyl ketone (MIBK)
Thermal polymerization inhibitor: Metoquinone 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) ( 0.0051 mol) was added. The system was purged with nitrogen, the temperature was raised to about 50 ° C., and the above components were mixed. Then, 9.6 g (0.24 mol) of flaky sodium hydroxide was added over 1 hour. After completion of the addition, the system was again purged with nitrogen, reacted at 60 ° C. for 9 hours, and disappearance of the starting compound was confirmed by high-speed (or high-performance) liquid chromatography (HPLC). After completion of the reaction, epichlorohydrin was removed under reduced pressure at 60 ° C., and 130 g of toluene was added while heating to 60-80 ° C. The resulting mixture was filtered with suction to remove by-products (NaCl), and the residue was washed with toluene. In order to advance the ring-closing reaction for forming an epoxy group, 53 g of a 30 wt% aqueous sodium hydroxide solution was added dropwise to the filtrate, and the mixture was stirred at 70 ° C. for 1 hour in a nitrogen atmosphere. Thereafter, 260 g of toluene was added to the obtained mixed liquid, 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, BPEF− 9 EOG was obtained.

(B) Synthesis of epoxy acrylate (BPEF-9EOGA) BPEF-9EOG (236.8 g), acrylic acid (45.0 g), MIBK (31.2 g), methoquinone (2.2 g) in a three-necked flask with Dean Stark Was added. The system was purged with nitrogen and heated to 50 ° C. to dissolve the reagent. Thereafter, flaky tetramethylammonium bromide (0.4 g) was added, and the atmosphere was purged with nitrogen again. Then, the mixture was reacted for 9 hours with stirring under heating and reflux. After completion of the reaction, the reaction solution was subjected to suction filtration, and the filtrate was concentrated and dried to obtain an epoxy acrylate (BPEF-9EOGA). BPEF-9EOGA had a solid content concentration of 99.4% by weight, a refractive index (25 ° C., 589 nm) of 1.550, and a viscosity (25 ° C.) of 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 stirred at 70 ° C. for 1 hour and mixed. Then, the epoxy acrylate hardened | cured material was obtained by UV irradiation (500mJ / cm < ² >) by "ECS-151U" by an i-graphics company.

  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 produced in the same manner as in Example 1 except that BPEF-9EOA was used instead of BPEF-9EOGA.

  The pencil hardness of the cured product was 6B, the refractive index (25 ° C., 589 nm) was 1.576, and the mandrel diameter was 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 (BPEF-5EOGA) was obtained in the same manner as in Synthesis Example 1 (b) except that BPEF-5EOG was used instead of BPEF-9EOOG. 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 pencil hardness of the cured product was H, the refractive index (25 ° C., 589 nm) was 1.573, and the mandrel diameter was 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-9EOOG. 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 pencil hardness of the cured product was 3B, the refractive index (25 ° C., 589 nm) was 1.572, and the mandrel diameter was less than 2 mm.

  The evaluation results are shown in Table 1.

  As is apparent from Table 1, compared to Comparative Example 1, the Examples had higher hardness while maintaining 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. It can be used for curable (meth) acrylic resin applications.

Specifically, the compound of the present invention (or a cured product obtained using the compound of the present invention) is an ink material, a light emitting material (for example, a light emitting material for organic EL), an organic semiconductor, a graphitization precursor, a gas. Separation membrane (for example, CO ₂ gas separation membrane), coating agent (for example, optical overcoat agent or hard coating agent for LED (light emitting diode) element coating agent), lens [pickup lens (for example, DVD (Digital versatile discs, etc.), micro lenses (eg, micro lenses for liquid crystal projectors), spectacle lenses, etc.], polarizing films (eg, polarizing films for liquid crystal displays), anti-reflection films (eg, Anti-reflection film for display devices), touch panel materials, flexible substrate materials, displays Materials [for example, PDP (plasma display), LCD (liquid crystal display), VFD (vacuum fluorescent display), SED (surface conduction electron-emitting device display), FED (field emission display), NED (nano-emissive display), Films for displays (especially thin displays) such as cathode ray tubes and electronic paper (filters, protective films, etc.)], membranes for fuel cells, optical fibers, optical waveguides, holograms, resist materials, adhesives (for example, optical adhesives, etc.) It can be suitably used for curable adhesives and the like. In particular, the compound of the present invention can be suitably used for an optical member, and since both high hardness and flexibility can be achieved, it can be suitably used for a display film or a coating film.

Claims (10)

Following formula (1)

(Wherein, rings Z ¹ and Z ² are aromatic hydrocarbon rings, R ^1a and R ^1b and R ^2a and R ^2b are each independently a non-radically polymerizable substituent, R ^3a and R ^3b are alkylene groups, R ^4a and R ^4b 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 is 2 to 30, p1 and p2 are Represents an integer of 0 to 4, provided that when p1 + p2 ≧ 1 and both rings Z ¹ and Z ² are condensed polycyclic aromatic hydrocarbon rings, n1 + n2 ≧ 3.
An 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 each a benzene ring or a biphenyl ring, n1 + n2 is 3 to 20 (b) Rings Z ¹ and Z ² are naphthalene rings, and n1 + n2 is 4 to 20 In the formula (1), the 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 is 4 to 18.   The curable composition containing the epoxy (meth) acrylate in any one of Claims 1-3.   Furthermore, the curable composition of Claim 4 containing a photoinitiator.   Hardened | cured material which the curable composition of Claim 4 or 5 hardened | cured.   The pencil hardness measured according to JIS K5600-5-4 is 4B or more, and the mandrel diameter by a bending resistance test measured according to JIS K5600-5-1 is 2 mm or less. Cured 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.