JP2019059961A - Polyester poly(meth)acrylate having fluorene skeleton, curable composition and cured product of the same and method for producing the same - Google Patents

Abstract

To provide a novel polyester poly(meth)acrylate having a fluorene skeleton capable of forming a cured product which achieves both a high refractive index and flexibility, a curable composition and a cured product of the same and a method for producing the same.SOLUTION: There is provided a polyester poly(meth)acrylate having a fluorene skeleton represented by the following formula (1-1), wherein a diol component (A) contains a diol component (A1) having a fluorene skeleton, a dicarboxylic acid component (B) contains a dicarboxylic acid component (B1) having a fluorene skeleton and the total amount of residues of the diol component (A1) having a fluorene skeleton and the dicarboxylic acid component (B1) having a fluorene skeleton is 70 mol% or more based on the total amount of residues the diol component (A) and the dicarboxylic acid component (B). (wherein, Rand Reach represent a hydrogen atom or a methyl group, n represents an integer of 1 or more and A and B each represent a residue of a diol component (A) and a dicarboxylic acid component (B).)SELECTED DRAWING: None

Description

The present invention relates to a novel polyester poly (meth) acrylate having a fluorene skeleton (for example, difunctional polyester (meth) acrylate), a curable composition containing the polyester poly (meth) acrylate, and a cured product thereof, and its production On the way.

Materials having a fluorene skeleton are known to exhibit excellent properties such as refractive index and heat resistance. A multifunctional (meth) acrylate having a fluorene skeleton has been proposed as a representative example of a compound that can be used in optical material applications and the like by utilizing such excellent properties of the fluorene skeleton.

For example, Japanese Patent Application Laid-Open No. 2007-91870 (Patent Document 1) is composed of a specific polyfunctional (meth) acrylate having a fluorene skeleton, a hydrolysis-condensable organosilicon compound having a polymerizable group, and a photoacid generator. The polymerizable composition is disclosed, and in the examples, 9,9-bis (4-acryloyloxyethoxyphenyl) fluorene is described as a multifunctional (meth) acrylate. However, cured products of acrylates having such a fluorene skeleton, although having a high refractive index, are hard and lack flexibility.

International Publication No. 2013/022065 (Patent Document 2) and JP-A 2013-5331
In the publication 0 (patent document 3), a polyfunctional group in which a (meth) acryloyloxy group and / or a (meth) acryloyloxy (poly) alkoxy group are respectively bonded to two phenyl groups bonded to the 9-position of fluorene Nature (meth) acrylates are disclosed. In Examples and Reference Examples, diacrylates of adducts obtained by adding 6.6 to 16.0 moles of ethylene oxide on average to 1 mole of 9,9-bis (4-hydroxyphenyl) fluorene (BPF) Is described. However, although the cured products of such diacrylates are derived from soft polyoxyethylene units and show scratch recovery (flexibility) in the scratch resistance test,
The refractive index decreases with the increase in the number of ethylene oxide additions, and high refractive index and flexibility can not be simultaneously achieved.

Further, in JP 2008-285647 A (Patent Document 4), a cured product having compatibility between flexibility and heat resistance and high refractive index is formed, and as a urethane acrylate excellent in handling property, 9, 9-bis (hydroxyaryl) fluorene or 9,9-bis (hydroxy (poly) alkoxyaryl) fluorene, a polyisocyanate compound having a polyol skeleton and a terminal isocyanate group, and an active hydrogen atom reactive with the isocyanate group There is disclosed a urethane (meth) acrylate which is reacted with a (meth) acrylic compound having one. However, although the cured product of such urethane acrylate exhibits flexibility derived from the polyol skeleton in the polyisocyanate compound, it can not improve the refractive index.

Further, in JP 2013-227534 A (Patent Document 5), an acid having high refractive index, alkali solubility, and adhesion to a support can be improved, and further, an acid excellent in optical characteristics, heat resistance, dimensional stability, etc. Anhydride-modified fluorene-containing acrylic resins are disclosed. In the examples of this document, 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene is reacted with acrylic acid, and the generated fluorene-containing epoxy acrylate is reacted with tetracarboxylic acid dianhydride. It is described that acid anhydride modified fluorene containing acrylic resin was obtained. Although the obtained acrylic resin has a high refractive index, it has a high crosslinking point density due to the acryloyl group of the cured product, and also lacks flexibility due to the formation of a pseudo crosslinking point due to hydrogen bonding between carboxyl groups.

A polyester resin having a fluorene skeleton is also known as a melt-moldable thermoplastic resin utilizing the properties of the fluorene skeleton. For example, JP 2012-144746 A
Patent Document 6 discloses that, as a polyester resin excellent in various properties such as heat resistance, refractive index, optical properties, and solvent solubility, both a diol component as a polymerization component and a dicarboxylic acid component are at least Disclosed is a polyester resin containing a compound having a fluorene skeleton. In the examples, as polymerization components, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -2-methylphenyl) fluorene, 9, 1 selected from 9-bis (4-hydroxyphenyl) fluorene
9, 9-bis (2-chlorocarbonylethyl) fluorene, 2, 7
There is described a linear polyester resin obtained by polymerizing one dicarboxylic acid component selected from -di (chlorocarbonyl) -9,9-dimethylfluorene.

JP 2007-91870 A (claim 1, paragraph [0007], an embodiment) International Publication WO 2013/022065 (claim 1, embodiment, reference example) JP, 2013-53310, A (claim 1, example, reference example) JP, 2008-285647, A (claim 1, paragraph [0009]-[0012], an example) JP, 2013-227534, A (claim 1, paragraphs [0008]-[0012], an example) JP, 2012-144746, A (paragraph [0006]-[0010], an example)

Accordingly, an object of the present invention is to provide a novel polyester poly (meth) acrylate having a fluorene skeleton and a cured product having flexibility, a curable composition containing the polyester poly (meth) acrylate, and a cured product thereof, It is an object of the present invention to provide a method for producing polyester poly (meth) acrylate.

Another object of the present invention is to provide a polyester poly (meth) acrylate having a novel fluorene skeleton capable of forming a cured product having both high refractive index and flexibility, and this polyester poly (
Curable composition containing (meth) acrylate, cured product thereof, and polyester poly (
It is an object of the present invention to provide a method for producing meta) acrylate.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that polyester poly (meta)
It has been found that when a fluorene skeleton is introduced into an acrylate, a cured product having flexibility (flexibility) and a cured product having compatibility between the flexibility and a high refractive index can be obtained, and the present invention has been completed.

That is, the polyester poly (meth) acrylate (for example, difunctional polyester (meth) acrylate) of the present invention has the following formula (1-1)

(Wherein, R ^1a and R ^1b are each a hydrogen atom or a methyl group, n is an integer of 1 or more, and A and B are each a residue of a diol component (A) and a dicarboxylic acid component (B))
The polyester poly (meth) acrylate represented by at least one of the diol component (A) and the dicarboxylic acid component (B) has a fluorene skeleton.

Typically, the diol component (A) may contain a diol component (A1) represented by the following formula (2-1).

(Wherein, Z ¹ and Z ² each represent an aromatic hydrocarbon ring, R ^2a and R ^2b each represent an alkylene group, m 1 and m 2 each represent an integer of 0 or more, and R ^3a and R ^3b each represent an inactive substitution in the reaction Each of the groups p1 and p2 is an integer of 0 or more, each of R ^4a and R ^4b is a substituent inert to the reaction, and each of k 1 and k 2 is an integer of 0 to 4).

The diol component represented by the above formula (2-1) is, for example, an aromatic carbonized material in which Z ¹ and Z ² are selected from C _6-14 aromatic hydrocarbon rings (eg, benzene ring, naphthalene ring and biphenyl ring) Hydrogen ring), R ^2a and R ^2b are linear or branched alkylene groups (eg, linear or branched C _2-6 alkylene group), m1 and m2 are integers of 0 to 10 (
For example, even if it is an integer of 0 to 5 and R ^3a and R ^3b are an alkyl group (for example, methyl group) and p 1 and p 2 are an integer for 0 to 4 (for example, an integer of 0 to 2) Good.

The diol component (A) further includes an aliphatic diol component (A2-1) and an alicyclic diol component (A).
2-2) and at least one diol component (A2) selected from the aromatic diol component (A2-3)
) May be included. The other diol component (A2) may be, for example, at least an aliphatic diol component (eg, C _2-6 alkane-diol) (A2-1). The ratio of the diol component (A1) having a fluorene skeleton to the other diol component (A2) may be the former / latter (molar ratio) = 10/90 to 100/0.

In addition, the dicarboxylic acid component (B) is at least one selected from an aliphatic dicarboxylic acid component (B2-1), an alicyclic dicarboxylic acid component (B2-2) and an aromatic dicarboxylic acid component (B2-3) The aromatic dicarboxylic acid component (B2-3) may contain a dicarboxylic acid component, and may contain a dicarboxylic acid component (B1) having a fluorene skeleton. The dicarboxylic acid component (B1) having a fluorene skeleton is selected from dicarboxylic acids represented by the following formula (3-1), dicarboxylic acids represented by the following formula (3-2), and ester-forming derivatives thereof It may contain at least one dicarboxylic acid component.

(Wherein, X ^1a and X ^1b each represent a divalent hydrocarbon group which may have a substituent, q represents an integer of 0 to ^4, and R ^4a and R ^4b , and k 1 and k 2 are the same as above) ).

The dicarboxylic acid component (B) has a linear or branched C _1- in which X ^1a is linear or branched in the above formula (3-1).
_At least one component selected from compounds which are ₆ alkylene groups, C _2-12 alkane-dicarboxylic acids, C _5-10 cycloalkane-dicarboxylic acids, C _6-24 arene-dicarboxylic acids and their ester-forming derivatives It may be.

A dicarboxylic acid component (B1) having a fluorene skeleton or another dicarboxylic acid component (B2)
The amount of the organic solvent used may be about 50 to 100 mol% with respect to all the dicarboxylic acid components (B).

  In the above formula (1-1), the number n of repeating units may be 1 to 10.

The total amount of residues of the diol component (A1) having a fluorene skeleton and the dicarboxylic acid component (B1) having a fluorene skeleton contained in the polyester poly (meth) acrylate of the present invention is the diol component (A) and the dicarboxylic acid component (B) 50 mol% or more may be sufficient with respect to the total amount of the residue (A and B) of.

The present invention also includes a polyester polyol (or a polyester polyol composition) represented by the following formula (1-2).

(In the formula, n, A and B are the same as described in the formula (1-1)).

Further, the polyester poly (meth) acrylate of the present invention is produced by reacting a diol component (A) with a dicarboxylic acid component (B) to form a polyester having a hydroxyl group at the end, and (meth) It may be produced by reacting with acrylic acid or its ester-forming derivative.

The present invention also encompasses a curable composition comprising the above-described polyester poly (meth) acrylate and a cured product thereof.

In the present specification and claims, the term “dicarboxylic acid component” refers to not only dicarboxylic acids but also ester-forming derivatives of dicarboxylic acids (eg, lower alkyl esters, acid halides, acid anhydrides) unless otherwise specified. Used in a sense that includes Also, "(Meta)
By "acrylate" is meant both acrylate and methacrylate. Furthermore, “polyester poly (meth) acrylate” means an oligoester (meth) acrylate, and in the above formula (1-1), it is an assembly (or composition) of compounds different in repeating unit n. Good. "Polyester polyol" means an oligoester polyol,
In the above formula (1-2), a collection (or composition) of compounds in which repeating units n are different may be used.

In the present invention, the cured product obtained by curing the curable composition has high flexibility or flexibility, probably because the novel polyester poly (meth) acrylate has a specific polyester structure having at least a fluorene skeleton. ing. In addition, such a cured product can achieve both high refractive index and flexibility.

[Polyester poly (meth) acrylate]
The polyester poly (meth) acrylate of the present invention has the following formula (1-1)

(Wherein, R ^1a and R ^1b are each a hydrogen atom or a methyl group, n is an integer of 1 or more, and A and B are each a residue of a diol component (A) and a dicarboxylic acid component (B))
And at least one of the diol component (A) and the dicarboxylic acid component (B) contains a fluorene skeleton. That is, the polyester poly (meth) acrylate of the present invention has at least a fluorene skeleton in the polyester structure. When the curable composition containing such polyester poly (meth) acrylate cures, it can form a cured product having flexibility or flexibility despite having a rigid fluorene skeleton. Although the reason is not clear, the (meth) acryloyl group to be a crosslinking point is at both ends of the polyester, and a fluorene skeleton or a cardo structure exists between the crosslinking points, and the crosslinking structure has a certain degree of freedom. It is guessed. Furthermore, the (meth) acrylate and the cured product are
The refractive index is high, probably because of having a fluorene skeleton. Therefore, both flexibility and high refractive index can be achieved.

In the above formula (1-1), the groups R ^1a and R ^1b may be the same or different, but generally,
It may be the same group (ie, a hydrogen atom or a methyl group).

In the above formula (1-1), the number n of repeating units of the polyester structure is 1 to 100 (
For example, it can be selected from the range of about 1 to 50), for example, an integer of about 1 to 30, preferably an integer of 1 to 20 (for example, an integer of 2 to 15), more preferably an integer of 1 to 10 (for example, It may be an integer of 3 to 8), particularly an integer of 1 to 5 (for example, an integer of 1 to 3). If the number n of repeating units is too large, the viscosity may be increased, and the handling properties of the polyester poly (meth) acrylate and the curable composition thereof may be reduced. In addition, n may mean an average value (arithmetic average value or arithmetic average value) as an aggregate of polyester poly (meth) acrylates of the present invention, and the preferable range of the average value is the range of the above integers. It is the same. Further, the average value (arithmetic average value or arithmetic average value) can be calculated by a conventional method, and can be calculated, for example, from the area ratio in the gel permeation chromatography (GPC) measurement chart.

[Diol component (A)]
The diol component (A) may contain a diol component (A1) having a fluorene skeleton (hereinafter sometimes referred to as a fluorenediol component (A1)).

(Diol component (A1))
Fluoreneol component (A1) is a 9,9-bis (hydroxyalkyl) fluorene, for example, 9,9-bis (hydroxymethyl) fluorene, 9,9-bis (2-hydroxyethyl) fluorene, 9,9- 9,9-Bis (hydroxy C _1-10 alkyl) fluorenes such as bis (2-hydroxypropyl) fluorene, 9,9-bis (3-hydroxypropyl) fluorene, 9,9-bis (6-hydroxyhexyl) fluorene (For example, 9, 9
-Bis (hydroxy _C2-6 alkyl) fluorene etc. are mentioned, and typically, the compound represented by following formula (2-1) may be sufficient. Also, these full orange all ingredients (A
1) can be used alone or in combination of two or more.

(Wherein, Z ¹ and Z ² each represent an aromatic hydrocarbon ring, R ^2a and R ^2b each represent an alkylene group, m 1 and m 2 each represent an integer of 0 or more, and R ^3a and R ^3b each represent an inactive substitution in the reaction Each of the groups p1 and p2 is an integer of 0 or more, each of R ^4a and R ^4b is a substituent inert to the reaction, and each of k 1 and k 2 is an integer of 0 to 4).

In the above formula (2-1), examples of the aromatic hydrocarbon ring represented by the rings Z ¹ and Z ² include monocyclic aromatic hydrocarbon rings (monocyclic arene rings) such as benzene ring, polycyclic Aromatic hydrocarbon rings (polycyclic arene rings) and the like, and examples of polycyclic aromatic hydrocarbon rings include fused polycyclic aromatic hydrocarbon rings (fused polycyclic arene rings), ring-aggregated aromatic rings A hydrocarbon ring (ring assembly arene ring) and the like are included.

As the fused polycyclic aromatic hydrocarbon ring, for example, a fused bicyclic arene ring (for example, a fused bicyclic C _10-16 arene ring such as naphthalene), a fused tricyclic arene ring (for example, anthracene, phenanthrene) And the like, and fused di- to tetra-cyclic arene rings and the like. As a preferable fused polycyclic aromatic hydrocarbon ring, a naphthalene ring, an anthracene ring and the like can be mentioned, and in particular, a naphthalene ring is preferable.

As the ring-aggregated aromatic hydrocarbon ring, biarene ring, for example, bi-C _6-12 arene ring such as biphenyl ring, binaphthyl ring, phenyl naphthalene ring (1-phenyl naphthalene ring, 2-phenyl naphthalene ring, etc.), terarene ring For example, a ter C _6-12 arene ring such as a terphenylene ring can be exemplified. Preferred ring assembly aromatic hydrocarbon ring, bi C _{6
And -10} arene ring, particularly a biphenyl ring and the like.

As preferred rings Z ¹ and Z ² , a C _6-20 aromatic hydrocarbon ring (eg, C _6-14)
And aromatic hydrocarbon rings, in particular, benzene ring, naphthalene ring and biphenyl ring).
The two rings Z ¹ and Z ² may be the same or different rings, and usually may be the same ring.

Examples of the alkylene group represented by the groups R ^2a and R ^2b in the above formula (2-1) include a linear or branched alkylene group. As a linear alkylene group, for example, a C _2-6 alkylene group such as ethylene group, trimethylene group, tetramethylene group, pentamethylene group and the like,
Preferably a _C2-4 alkylene group, More preferably, a _C2-3 alkylene group, especially an ethylene group can be illustrated. As a branched alkylene group, for example, a C _3-6 alkylene group such as propylene group, 1,2-butanediyl group, 1,3-butanediyl group and the like, preferably C _3-4
Alkylene groups, in particular propylene groups may be mentioned. In addition, when m1 and m2 are 2 or more, you may comprise by the same or different kind of alkylene group, and usually, they may be the same.
Further, the groups R ^2a and R ^2b may be composed of the same or different types of alkylene groups, and may usually be the same.

The repeating unit numbers m1 and m2 of the groups OR ^2a and OR ^2b may each be an integer of 0 or more, for example, about 0 to 10 (eg, 1 to 7), preferably an integer of 1 to 5 (eg, 1 to 4), more preferably 1 to 3 (eg, 1 to 2), particularly 1
It may be M1 and m2 may be the same or different.

In addition, the total amount (m1 + m2) of m1 and m2 is the entire diol component (A1) (the above formula (2
1 to 1) by the average (arithmetic mean or arithmetic mean) of the molecular assembly of the diol represented by
It can be selected from the range of about 20 (e.g., 1 to 8), 1 to 15 (e.g., 2 to 13), preferably 1 to 7 (e.g., 1 to 6), and more preferably 2 to 6 (e.g. 4), especially 2
It may be on the order of -3 or may be on the order of 2 to 12 (e.g. 2 to 10), 5 to 15
It may be (for example, 9 to 12). If m1 or m2 (or m1 + m2) is too large, although the flexibility of the cured product is improved, there is a possibility that the high refractive index and the flexibility can not be compatible. In addition, the repeating unit number of the said average (arithmetic mean or arithmetic mean) can be easily calculated by the conventional method, for example, the method of patent document 2 or 3, etc.

In the above formula (2-1), groups [-(OR ^2a ) _m1 -OH] and [-(OR ^2b ) _m2-
OH] 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 phenyl group 2-, 3-, 4-position (in particular, In many cases, substitution is carried out at the 3-position or 4-position, and in the case where the rings Z ¹ and Z ² are naphthalene rings,
In many cases, it may be substituted at any position such as 1, 5-, 2, 5-, 1, 6-, 2, 6-, etc. Relations such as-, 2, 6-and so on
, 6-position relationship) in many cases. Also, in the ring assembly arene rings Z ¹ and Z ² , the substitution position is not particularly limited. For example, the arene ring bonded to the 9-position of fluorene or an arene ring adjacent to this arene ring may be substituted . For example, when the rings Z ¹ and Z ² are biphenyl rings, the 3- or 4-position of the biphenyl rings Z ¹ and Z ² is often bonded to the 9-position of fluorene, for example, 3 5-, 3-, 6-, 3, 3'-, 3
It may be substituted at any substitution position such as 4,4'-position, 4,2-position, 4,3'-position, 4,4'-position, preferably 3,5-position, 3,6 -Position, 3, 4'-position, 4, 2-position, 4, 4 '
It may be substituted at a substitution position of -position, more preferably 3,6-position or 4,2-position.

In the above formula (2-1), as the substituents R ^3a and R ^3b inert to the reaction, halogen atoms (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl groups (methyl group, A linear or branched C _1-10 alkyl group such as ethyl group, propyl group, isopropyl group, butyl group, s-butyl group or t-butyl group, preferably linear or branched C ₁ -C _1
6 alkyl group, more preferably linear or branched C _1-4 alkyl group etc., cycloalkyl group (C _5-10 cycloalkyl group such as cyclopentyl group, cyclohexyl group etc.), aryl group [phenyl Group, alkylphenyl group (methylphenyl (tolyl) group, dimethylphenyl (xylyl) group etc.), C _6-12 aryl group such as biphenyl group and naphthyl group, aralkyl group (C _6-10 such as benzyl group and phenethyl group) Aryl-C _1-4
Alkyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propoxy group, n
Linear or branched C _1-10 alkoxy group such as -butoxy group, isobutoxy group, t-butoxy group, etc .; cycloalkoxy group (eg, C _{5- 5} such as cyclohexyloxy group etc.)
₁₀ ) cycloalkyloxy group, etc.), aryloxy group (eg, phenoxy group etc. C)
_6-10 aryloxy group etc.), aralkyloxy group (eg C _6-10 aryl-C _1-4 alkyloxy group such as benzyloxy group etc.), alkylthio group (eg methylthio group, ethylthio group, propylthio group, etc.) n-butylthio group, C _1-10 alkylthio group such as t-butylthio group, etc., cycloalkylthio group (eg, C _5-10 cycloalkylthio group such as cyclohexylthio group, etc.), arylthio group (eg, thiophenoxy group) _{C 6-10} such arylthio groups), such as, aralkylthio group (e.g., _{C 6-10} aryl _{-C 1-4} alkylthio group such as benzylthio group), an acyl group (e.g.,
(C _1-6 acyl group such as acetyl group), nitro group, cyano group, dialkylamino group (
For example, di C _1-4 alkylamino group such as dimethylamino group, etc.), dialkylcarbonylamino group (eg di C _1-4 alkyl-carbonylamino group such as diacetylamino group, etc.) and the like can be exemplified.

Among these groups R ^3a and R ^3b , representatively, halogen atoms, alkyl groups, aryl groups, alkoxy groups, acyl groups, nitro groups, cyano groups, substituted amino groups and the like can be mentioned.
Preferred groups R ^3a and R ^3b include alkyl groups (such as linear or branched C _1-6 alkyl groups such as methyl group), aryl groups, and alkoxy groups (such as linear or branched groups such as methoxy group) Particularly preferred is an alkyl group (eg, a methyl group) such as a C _1-4 alkoxy group). When the groups R ^3a and R ^3b are aryl groups, the groups R ^3a and R ^3b may together with the rings Z ¹ and Z ² form the above-mentioned ring assembly arene ring. Groups R ^3a and R
Types of ^3b may be the same or different in the same or different rings Z ¹ and Z ² .

The substitution numbers p1 and p2 can be appropriately selected according to the kind of the rings Z ¹ and Z ² etc.
To 8, preferably 0 to 4 (e.g. 0 to 2), more preferably 0 or 1 (e.g. 0)
It may be In particular, when p is 1, the rings Z ¹ and Z ² may be a benzene ring, a naphthalene ring or a biphenyl ring, and R ^3a and R ^3b may be a methyl group. In addition, groups R ^3a and R
The position of substitution of ^3b is not particularly limited, and on the rings Z ¹ and Z ² , the group [— (OR ^2a
It is good if it is except the position which _m1 -OH] and [-( ^OR2b ) _m2 -OH] substitute.

In the above formula (2-1), a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom and the like), an alkyl group (for example, a methyl group and an ethyl group) as the groups R ^4a and R ^4b
And C _1-6 alkyl groups such as propyl group, isopropyl group, butyl group and t-butyl group), aryl groups (eg, C _6-10 aryl group such as phenyl group), and the like. Among these groups R ^4a and R ^4b , a C _1-4 alkyl group (in particular, a methyl group) is preferable. The groups R ^4a and R ^4b may be the same or different, and when the substitution numbers k 1 and k 2 are 2 or more, each of the groups R ^4a and R ^4b is on the corresponding benzene ring in the fluorene structure , May be the same or different.

The substitution numbers k1 and k2 can be selected from the integers of 0 to 4, preferably 0 to 1, especially 0.
The substitution numbers k1 and k2 may be the same as or different from each other. Also, the substitution position of the groups R ^4a and R ^4b is not particularly limited. For example, the 2-position to the 7-position of the fluorene ring (2-
, 7-, 2- and 7-, etc.).

The representative compounds in the above formula (2-1) are 9,9-bis [hydroxy (mono or poly)
Alkoxyaryl] fluorene (eg, 9,9-bis [hydroxy (mono or poly)
C _2-6 alkoxy (mono or bi) C _6-10 aryl! Fluorene), 9, 9-bis [
Hydroxy (mono or poly) alkoxide severe Reel] fluorene (e.g., 9,9-bis [hydroxy (mono or _{poly) C 2-6} Arukokishibi _{C 6-10} aryl] fluorene)
, More preferably, 9,9-bis [hydroxy (mono or poly) C _2-3 alkoxy C _{6
And -10} aryl] fluorene, 9, 9-bis [hydroxy (mono or poly) C _2-3 alkoxy bi C _6-10 aryl] fluorene and the like.

Representative fluorenediol components include 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes, 9,9-bis (hydroxy (poly) alkoxyphenylnaphthyl) fluorenes, and the like.

As the 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes, in the above-mentioned formula (1-1), the rings Z ¹ and Z ² are substituted or unsubstituted benzene rings, R ^2a and R ^2b
A linear or branched _C2-4 alkylene group, a compound wherein m1 and m2 are 1, and each of k1 and k2 is 0, eg, (1) 9,9-bis [4- (2-hydroxyethoxy) 9,9-bis (hydroxy _C2-4 alkoxyphenyl) fluorene, such as phenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) phenyl] fluorene, (2) 9
, 9-Bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene, 9,
9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl) fluorene,
9,9-bis (4- (2-hydroxyethoxy) -3-isobutylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-t-butylphenyl) fluorene, 9,9- 9 such as bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-t-butyl-6-methylphenyl) fluorene , 9-bis (hydroxy _{C 2-4} alkoxy - mono- or _{di-C 1-4} alkyl phenyl) fluorene, (3) 9,9-bis (4- (2-hydroxyethoxy) -3-cyclohexyl phenyl) such as a fluorene 9,9-bis (hydroxy C
_2-4 alkoxy C _5-10 cycloalkylphenyl) fluorene, (4) 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-) 9,9 such as hydroxypropoxy) -3-phenylphenyl] fluorene
-Bis (hydroxy _C2-4 alkoxy _C6-10 arylphenyl) fluorene etc;
Rings Z ¹ and Z ² are substituted or unsubstituted benzene rings, R ^2a and R ^2b are linear or branched C _2-4 alkylene groups, m 1 and m 2 are 2 to 10, and k 1 and k 2 are each 0 A compound, that is, a compound in which m1 and m2 are 2 to 10 in the above compounds (2) to (4), for example, 9,9-bis (hydroxy _C2-4 alkoxy _C2-4 alkoxyphenyl) fluorene, 9,9-Bis (hydroxy _C2-4 alkoxy _C2-4 alkoxy-mono or di _C1-4 alkylphenyl) fluorene, 9,9-bis (hydroxy _C2-4 alkoxy _C2-4 alkoxy _{C6-6 10} arylphenyl) fluorene, 9, 9-bis (hydroxy _C2-4 alkoxy _C2-4 alkoxy _C6-10 arylphenyl) fluorene and the like are included .

As 9,9-bis (hydroxy (poly) alkoxynaphthyl) fluorenes, for example, ring Z ¹ and Z ² are substituted or unsubstituted naphthalene ring, and R ^2a and R ^2b are linear or branched C _{2 -4} alkylene group, compounds in which m1 and m2 are 1, and each of k1 and k2 is 0, for example, (5) 9,9-bis (hydroxyalkoxynaphthyl) fluorene [eg, 9,9-bis [6- (2) -Hydroxyethoxy) -2-naphthyl] fluorene, 9,9
-Bis [5- (2-hydroxyethoxy) -1-naphthyl] fluorene, 9,9-bis [
9,9-bis (hydroxy _C2-4 alkoxynaphthyl) fluorene such as 6- (2-hydroxypropoxy) -2-naphthyl] fluorene; and the like; Rings Z ¹ and Z ² are substituted or unsubstituted naphthalene rings, R ^2a And R ^2b is a linear or branched C 2 _-4 alkylene group, m 1
And m2 is 2 to 10, and each of k1 and k2 is 0, ie, a compound
5) include compounds in which m1 and m2 are 2 to 10, such as 9,9-bis (hydroxy _C2-4 alkoxy _C2-4 alkoxy naphthyl) fluorene and the like.

These fluorenediol components can be used alone or in combination of two or more. The preferred fluorenediol component is 9,9-bis (hydroxy _C2-4 alkoxyphenyl) fluorene such as 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4-) 9,9-Bis (C _1-4 alkyl-hydroxy C _2-4 alkoxyphenyl) fluorene such as (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) 9,9-Bis (hydroxy _C2-4 alkoxyphenylphenyl) fluorene such as -3-phenylphenyl) fluorene 9,9-bis (5- (2-hydroxyethoxy) -1-naphthyl) fluorene 9,
9,9- such as 9-bis (6- (2-hydroxyethoxy) -2-naphthyl) fluorene
Bis [hydroxy _C2-4 alkoxynaphthyl] fluorene, in particular 9,9-bis (4- (
2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (6- (2-hydroxyethoxy) -2-naphthyl) fluorene.

The diol component (A) may be composed of the fluorenzole component (A1) alone, or may be composed of the other diol component (A2) alone, and the diol component (A) is the fluorenediol component (A1) ) And the other diol component (A2) may be combined.

(Diol component (A2))
Other diol components (A2) include aliphatic diol components (A2-1) and alicyclic diol components (A2-).
2) and an aromatic diol component (A2-3). By using these diol components (A2), refractive index, flexibility and other properties (for example, optical properties such as birefringence, mechanical properties, thermal properties, etc.) in the cured product of polyester poly (meth) acrylate The balance of the handling properties of the polyester poly (meth) acrylate or the curable composition thereof can be adjusted.

As the aliphatic diol component (A2-1), for example, alkanediol (for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3-pentanediol,
1,4-pentanediol, 1,5-pentanediol, neopentyl glycol, 1,
_C2-10 alkane-diols such as 6-hexanediol, preferably _C2-6 alkane-diols, more preferably _C2-4 alkane-diols; polyalkane diols (e.g. diethylene glycol, dipropylene glycol, triethylene) Di or tri _C2-4 alkanediols, such as glycol, polytetramethylene ether glycol etc, etc. can be illustrated.

As the alicyclic diol component (A2-2), for example, cycloalkanediol (eg, C _5-8 cycloalkane-diol such as cyclohexanediol); di (hydroxyalkyl) cycloalkane (eg, cyclohexane dimethanol etc.) Di (hydroxy C _1-
4 alkyl) C _5-8 cycloalkane and the like); isosorbide and the like.

Examples of the aromatic diol component (A2-3) include dihydroxyarene (for example, hydroquinone, resorcinol and the like); dihydroxyalkylarene (for example, di (such as 1,3-benzenedimethanol and 1,4-benzenedimethanol) Hydroxy C _1-4 alkyl) C _6-10 arene etc.) Bisphenols (eg biphenol, bis (hydroxyphenyl) C _1-10 alkanes such as bisphenol A, bis such as 1,1-bis (hydroxyphenyl) cyclohexane (Hydroxyphenyl) C _4-10 cycloalkane and the like; and alkylene oxide adducts of the bisphenols (for example, C _2-3 alkylene oxide adducts such as ethylene oxide adducts of bisphenols and the like) and the like. These diol components (A2) may be used alone or in combination of two or more.

Aliphatic diol component (A2-1) or alicyclic diol component of the diol component (A2)
It is preferable to contain (A2-2), particularly, at least an aliphatic diol component (A2-1) (alkanediol such as C _2-6 alkanediol). By combining the diol component (A1) and the aliphatic diol component (A2-1), esterification can be efficiently performed, and polyester poly (meth) acrylate having a high refractive index and flexibility in a well-balanced manner You can get it.

The diol component (A) preferably contains at least a fluorenediole component (A1). The diol component (A) may further contain, as described above, an aliphatic diol component (A2-1) and / or an alicyclic diol component (A2-2) (for example, an alkane diol). Fluorenediol component (A1) and other diol components (A2) (for example, alkanediol (A2-)
1)) is the ratio of the former / the latter (molar ratio) = 10/90 to 100/0 (eg, 30/70)
/ 5 95/5), for example, 50/50 to 100/0 (eg, 75/2)
5 to 90/10), preferably 80/20 to 100/0 (e.g. 80/20 to 90/1)
0) It may be about. Depending on the composition of the dicarboxylic acid component (B) described later, when the amount of the diol component (A2) is too large, the high refractive index and the flexibility in the cured product of the curable composition containing the polyester poly (meth) acrylate are cured. And may not be compatible with each other.

The diol component (A) may be combined with the polyol component to introduce a branched structure into the polyester poly (meth) acrylate, as long as the effect of the present invention is not impaired.
As such a polyol component, for example, a polyol component having three or more hydroxyl groups [for example, an alkane polyol (for example, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol etc., etc.) and the like] can be mentioned, and the polyol component is You may use individually or in combination of 2 or more types. If necessary, these polyol components may be added in a small amount [e.g., 10 mol% or less (e.g., 0.1 to 8 mol%, preferably 0.2 to 10 mol%, based on the total amount of the diol component (A) and the polyol component 5 mol%) may be used.

The ratio of each component in the diol component (A) may correspond to the ratio of the residue A (residue of each component) in the above-mentioned formula (1-1), and the ratio (feed ratio) in the reaction system It may correspond (following, the same).

[Dicarboxylic acid component (B)]
The dicarboxylic acid component (B) may contain a dicarboxylic acid component (B1) having a fluorene skeleton (hereinafter sometimes referred to as a fluorenic carboxylic acid component (B1)).

(Fluorene carboxylic acid component (B1))
The dicarboxylic acid component (B1) is a fluorene carboxylic acid, for example, 2,4-dicarboxyfluorene, 2,4-dicarboxy-9,9-dimethylfluorene, 9,9-bis (carboxyaryl) capable of forming a cardo structure Fluorenes such as 9,9-bis (3-carboxyphenyl) fluorene, 9,9-bis (4-carboxyphenyl) fluorene,
9,9-bis (carboxy C _6-12 aryl) such as 9,9-bis (5-carboxy-1-naphthyl) fluorene, 9,9-bis (6-carboxy-2-naphthyl) fluorene
Fluorene and the like, and their ester-forming derivatives are included. Typically, the following formula
It may be a dicarboxylic acid represented by (3-1), a dicarboxylic acid represented by the following formula (3-2), and an ester-forming derivative thereof. These dicarboxylic acid components (B1) may be used alone or in combination
It can also be used in combination of species or more.

(Wherein, X ^1a and X ^1b each represent a divalent hydrocarbon group which may have a substituent, q represents an integer of 0 to ^4, and R ^4a and R ^4b , k 1 and k 2 each represent a preferred embodiment. Same as above including).

In the above formulas (3-1) and (3-2), as a hydrocarbon group represented by groups X ^1a and X ^1b , a linear or branched alkylene group, for example, a methylene group, an ethylene group, trimethylene group, propylene group, 2-ethyl ethylene group, such as 2-methyl-propane-1,3-diyl _{C 1-}
Examples thereof include ₈ alkylene groups (preferably, linear or branched C _1-6 alkylene groups).

As a substituent of an alkylene group, an aryl group (phenyl group etc.), a cycloalkyl group (cyclohexyl group etc.) etc. can be illustrated, for example.

X ^1a is a linear or branched C _2-6 alkylene group, preferably a linear or branched C
_In many cases, it is a _2-4 alkylene group (for example, an ethylene group, a propylene group), and X ^1b is a linear or branched C _1-6 alkylene group, preferably a linear or branched C _1-3 It is often an alkylene group (for example, a methylene group, an ethylene group). The alkylene group X ^1a having a substituent may be, for example, a 1-phenylethylene group, a 1-phenylpropane-1,2-diyl group or the like.

The coefficient q can be selected from the integers of 0 to 4, and may usually be 0 to 2, preferably 0 or 1.

Formula (3-1) and (3-2), groups ^{R 4a} and ^R 4b, k1 and k2, including preferred embodiments, the formula (2-1), wherein the ^{R 4a} and ^R 4b, k1 and k2 Is the same as

The representative compound represented by the above formula (3-1) is a compound wherein X ^1a is a C _2-6 alkylene group [eg, 9,9-bis (2-carboxyethyl) fluorene, 9,9-bis 9,9-bis (carboxy C _2-6 alkyl) fluorene etc., such as (2-carboxypropyl) fluorene], ester forming derivatives of these and the like. A representative compound represented by the above formula (3-2) is a compound wherein q = 0 and X ^1b is a C _1-6 alkylene group [eg, 9- (1-carboxy-2-carboxyethyl) ) Fluorene; q = 1 and X
Compounds in which 1 ^b is a C _1-6 alkylene group, such as 9- (dicarboxy C _2-6 alkyl) fluorenes such as 9- (2-carboxy-3-carboxypropyl) fluorene and ester forming derivatives thereof And so on.

These dicarboxylic acid components (B1) having a fluorene skeleton may be used alone or in combination of two or more.

Preferred examples of the dicarboxylic acid component (B1) include compounds represented by the above formula (3-1), for example, 9
, 9-bis (carboxyalkyl) fluorenes [eg, 9,9-bis (carboxy C)
_2-6 alkyl) fluorene etc.] and the like.

The dicarboxylic acid component (B) may be composed of the fluorene carboxylic acid component (B1) alone. Also, the dicarboxylic acid component (B) may be composed of another dicarboxylic acid component (B2) alone, or may be composed of a combination of the orange carbonic acid component (B1) and the other dicarboxylic acid component (B2). Good.

(Dicarboxylic acid component (B2))
Other dicarboxylic acid components (B2) include aliphatic dicarboxylic acid components (B2-1), alicyclic dicarboxylic acid components (B2-2) and aromatic dicarboxylic acid components (B2-3). Dicarboxylic acid component (B)
Contains these dicarboxylic acid components (B2), and the refractive index, flexibility and other properties of the cured product (eg, optical properties such as birefringence, handling properties, mechanical properties, thermal properties, etc.) You can adjust the balance of

Examples of the aliphatic dicarboxylic acid component (B2-1) include alkanedicarboxylic acids (eg, succinic acid, adipic acid, sebacic acid, C _2-12 alkane-dicarboxylic acids such as decanedicarboxylic acid, etc.); unsaturated aliphatic Examples thereof include dicarboxylic acids (eg, C _2-10 alkene-dicarboxylic acid such as maleic acid, fumaric acid, itaconic acid, etc.) and the like.

The alicyclic dicarboxylic acid component (B2-2), for example, cycloalkane carboxylic acids (e.g., C _5-10 cycloalkane such as 1,4-cyclohexanedicarboxylic acid - such as a dicarboxylic acid); di- or tri cycloalkane carboxylic acid (e.g., decalin dicarboxylic acid, norbornane carboxylic acid, adamantane dicarboxylic acids, such as tricyclodecane acid); cyclo alkene dicarboxylic acids (eg, C, such as cyclohexene dicarboxylic acid _5-
10 cycloalkene-dicarboxylic acid); di or tricycloalkene dicarboxylic acid (eg, norbornene dicarboxylic acid etc.) and the like.

Examples of the aromatic dicarboxylic acid component (B2-3) include polycyclic aromatic dicarboxylic acids and monocyclic aromatic dicarboxylic acids. As polycyclic aromatic dicarboxylic acid, for example, fused polycyclic aromatic dicarboxylic acid [eg, naphthalene dicarboxylic acid (eg, 1,5-naphthalene dicarboxylic acid, 1,6-naphthalene dicarboxylic acid, 1,7-naphthalene)] Dicarboxylic acid,
In different rings such as 1,8-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid
Naphthalene dicarboxylic acids having two carboxyl groups; Naphthalene dicarboxylic acids having two carboxyl groups in the same ring such as 1,2-naphthalene dicarboxylic acid and 1,4-naphthalene dicarboxylic acid), anthracene dicarboxylic acids, phenanthrene dicarboxylic acid, etc. Condensed polycyclic C _10-24 arene-dicarboxylic acid, preferably condensed polycyclic C _10-16
Arene-dicarboxylic acids, more preferably fused polycyclic C _10-14 arene-dicarboxylic acids, etc .; aryl aryl dicarboxylic acids [eg, biphenyl dicarboxylic acid (eg, 2,2′-biphenyl dicarboxylic acid, 4,4′-, C _6-10 aryl-C _6-10 arene-dicarboxylic acid etc. such as biphenyldicarboxylic acid etc.]; diarylalkanedicarboxylic acids [eg, diphenylalkanedicarboxylic acid such as 4,4'-diphenylmethanedicarboxylic acid etc. Di C _6-10 aryl-C _1-6 alkane-dicarboxylic acid and the like]; di aryl ketone dicarboxylic acid [eg, di C _6-10 such as diphenyl ketone dicarboxylic acid (eg, 4.4′-diphenyl ketone dicarboxylic acid and the like) Aryl-ketone-dicarboxylic acid) etc It can be exemplified. Moreover, as monocyclic aromatic dicarboxylic acid, for example, phthalic acid, terephthalic acid, isophthalic acid, alkyl isophthalic acid (eg,
C _6-10 such as C _1-4 alkyl-isophthalic acid such as 4-methylisophthalic acid
Arene-dicarboxylic acid etc. are mentioned. Further, ester forming derivatives of dicarboxylic acids exemplified above may also be mentioned. These dicarboxylic acid components (B2) may be used alone or in combination of two or more.

The dicarboxylic acid component (B2) is at least one selected from an aliphatic dicarboxylic acid component (B2-1), an alicyclic dicarboxylic acid component (B2-2) and an aromatic dicarboxylic acid component (B2-3) It can be used. As preferable components, for example, C _2-12 alkane-dicarboxylic acid (preferably C _2-8 alkane-dicarboxylic acid, more preferably C _2-4 alkane-dicarboxylic acid etc.), C _5-10 cycloalkane-dicarboxylic acid (Preferably C _5-8 cycloalkane-
Dicarboxylic acid, more preferably C _6-8 cycloalkane-dicarboxylic acid), C _6-24
There may be mentioned arene-dicarboxylic acids (preferably C _6-14 arene-dicarboxylic acids, more preferably C _6-10 arene-dicarboxylic acids). The dicarboxylic acid component (B2) is
Usually, at least an aliphatic dicarboxylic acid component (B2-1) and / or an alicyclic dicarboxylic acid component (B2-
2) may be included.

The ratio of the fluoro orange carboxylic acid component (B1) to the other dicarboxylic acid component (B2) is
It can be selected from the range of the former / the latter (molar ratio) = 0/100 to 100/0 (for example, 1/99 to 99/1), for example, 10/90 to 100/0 (for example, 30/70 to 90 /). 10),
Preferably, it may be about 50/50 to 100/0 (e.g., 60/40 to 85/15), and more preferably about 70/30 to 80/20.

The dicarboxylic acid component (B) is an aliphatic dicarboxylic acid component (B2-1), an alicyclic dicarboxylic acid component
It is preferable to contain at least one selected from (B2-2) and the aromatic dicarboxylic acid component (B2-3). The aromatic dicarboxylic acid component (B2-3) is a dicarboxylic acid component having a fluorene skeleton (
B1) may be included. In addition, only any one of a fluorene carboxylic acid component (B1) or another dicarboxylic acid component (B2) may be included, and both may be included.

The amount of the fluoro orange carboxylic acid component (B1) or the other dicarboxylic acid component (B2) to be used is 20 to 100% by mole (eg, 30 to 10 mol%) based on the total dicarboxylic acid component (B).
0 to 100 mol% (for example, 60 to 99 mol%).
It may be about 70 to 100 mol% (for example, 75 to 99 mol%), more preferably about 80 to 100 mol% (for example, 85 to 98 mol%). In other words, the ratio of the fluoro orange carboxylic acid component (B1) to the other dicarboxylic acid component (B2) is, for example, the former / the latter (molar ratio) = 100/0 to 0/100 (for example, 90/10 to 10) / 9
0) may be in the range of about 80/20 to 20/80 (eg, 75/25 to 25 /
75) It may be in the range of about.

The dicarboxylic acid component (B) may be combined with the polycarboxylic acid component to introduce a branched structure into the polyester poly (meth) acrylate as long as the effect of the present invention is not impaired. As such a polycarboxylic acid component, for example, a polycarboxylic acid component having three or more carboxyl groups (for example, aromatic polycarboxylic acids such as trimellitic acid and pyromellitic acid, and their ester-forming derivatives) Can be illustrated. If necessary, they may be added in a small amount [e.g., 10 mol% or less (e.g., 0.1 to 8 mol%, preferably 0.2 to 5 mol% based on the total amount of the dicarboxylic acid component (B) and the polycarboxylic acid component Mole%) may be used.

The proportion of each component in the dicarboxylic acid component (B) is the same as in the diol component (A),
It may correspond to the ratio of residue B (residue of each component) in the above formula (1-1), or may correspond to the ratio (feed ratio) in the reaction system (the same applies hereinafter).

In the present invention, at least one of the diol component (A) and the dicarboxylic acid component (B) may be a component having a fluorene skeleton, and in the diol component (A) and the dicarboxylic acid component (B), The total amount of the component (A1) and the flour orange carboxylic acid component (B1) is, for example, 10 mol% or more (eg, 30 mol% or more) with respect to the total amount of the diol component (A) and the dicarboxylic acid component (B) Preferably 50 mol% or more (
For example, it may be about 70 mol% or more, more preferably about 75 mol% or more (for example, 90 mol% or more). When the component having a fluorene skeleton is too small, there is a possibility that the high refractive index and the flexibility in the cured product can not be compatible.

In a preferred embodiment, the diol component (A) comprises at least a fluorenicol component (A1)
And the dicarboxylic acid component (B) includes the fluorene carboxylic acid component (B1), the aliphatic dicarboxylic acid component (B2-1), the alicyclic dicarboxylic acid component (B2-2) and the aromatic dicarboxylic acid component (B2-3) And at least one dicarboxylic acid component selected from The dicarboxylic acid component (B) may contain a dicarboxylic acid component having at least one aromatic hydrocarbon ring selected from fluorene carboxylic acid component (B1) and aromatic dicarboxylic acid component (B2-3). At least one of the diol component (A) and the dicarboxylic acid component (B) may contain an aliphatic component. For example, the diol component (A) further contains an alkanediol as an aliphatic diol component A2-1) may be contained, and the dicarboxylic acid component (B) may contain the fluorene carboxylic acid component (B1) and / or the aliphatic dicarboxylic acid component (B2-1). A compound having a high refractive index can be prepared by using esterification of a diol component (A) containing at least a fluorenzole component (A1) and a dicarboxylic acid component (B) containing at least a fluorene carboxylic acid component (B1) . In addition, when the aromatic dicarboxylic acid component (B2-3) is used, the decrease in refractive index can be suppressed, and the heat resistance can be improved.

[Production Method and Properties of Polyester Poly (Meth) Acrylate]
The polyester polyol is formed by the reaction of the diol component (A) with the dicarboxylic acid component (B). A representative polyester polyol is a polyester diol represented by the following formula (1-2) and having a hydroxyl group at the end.

(Wherein n, A and B are as defined above).

In addition, the polyester polyol (or polyester polyol composition) represented by said Formula (1-2) can be utilized as various polyol components (especially diol component), for example, polyester resin, polyurethane resin (polyurethane (meth)) It may be used as a diol component of a polycarbonate resin, including an oligopolyurethane resin such as acrylate, etc., to produce a resin of high refractive index. In a preferred embodiment, it is useful to prepare polyester poly (meth) acrylates utilizing hydroxyl groups.

The polyester poly (meth) acrylate of the present invention represented by the above formula (1-1) comprises a diol component (A), a dicarboxylic acid component (B), (meth) acrylic acid or an ester-forming derivative thereof (hereinafter referred to as And (meth) acrylic acid component (C)) may be mixed and prepared in a one-step reaction in which a diol component (A) and a dicarboxylic acid component (B) are reacted (1st step) Step reaction), a polyester having a hydroxyl group at the end generated and represented by the above formula (1-2) (hereinafter sometimes referred to as polyester polyol or polyester polyol composition) and (meth) acrylic acid component (C) And may be prepared stepwise (reaction of the second stage).

When the esterification reaction of all the components is carried out simultaneously (in a single step reaction), di (meth) acrylate (compound of n = 0 in the above formula (1-1)) not containing the dicarboxylic acid component (B) is also simultaneously produced. It is preferable in that it has few steps. Usually, it may be prepared stepwise. In the staged reaction, the reaction of the second stage may be carried out without isolating or purifying the reaction product of the first stage. Moreover, if it carries out in steps, since reaction control is easy, molecular weight distribution will be narrow and it is preferable at the point which can obtain the target polyester poly (meth) acrylate in high yield.

The (meth) acrylic acid or its ester-forming derivative ((meth) acrylic acid component (C
(Meth) acrylic acid and (meth) acrylic acid lower alkyl esters (specific examples of
For example, (meth) acrylic acid C _1-4 alkyl (meth) acrylate such as methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid halide (eg, (meth) acrylic acid chloride, (meth) acrylic acid Bromide etc., di (meth) acrylic acid anhydride etc. are mentioned. These may be used alone or in combination of two or more.

In the esterification reaction, diol component (A) to 1 mol of dicarboxylic acid component (B)
The ratio of is preferably about 1 to 5 moles, preferably excess moles, for example 1.1 to 4 moles (eg 1
. 2 to 3 moles, preferably 1.3 to 2.5 moles (eg, 1.4 to 2 moles), and more preferably 1.5 to 2 moles (eg, 1.5 to 1.8 moles) May be, usually 1
. It may be about 3 to 3 moles (e.g., 1.5 to 2.5 moles). Diol component (A)
If the amount is too small, it may be difficult to form a polyester having a terminal hydroxyl group. On the contrary, if it is too large, many unreacted diol components (A) tend to remain.

In addition, the amount of the (meth) acrylic acid component (C) used is 0.8 to 10 moles, preferably equivalent moles or more, for example, 1 mole with respect to 1 mole of hydroxyl groups of the produced polyester polyol.
To 5 moles, usually excess moles, such as 1.1 to 3 moles (eg 1.2 to 2 moles, in particular
It may be about 1.2 to 1.5 mol).

In addition, according to the ratio of the diol component (A) to the dicarboxylic acid component (B) [eg,
When the amount of diol component (A) used is small], the polyester poly (meth) acrylate may have a free carboxyl group derived from the dicarboxylic acid component (B). Also,
Not all the hydroxyl groups of the polyester polyol need to be esterified with the (meth) acrylic acid component (C), and the polyester poly (meth) acrylate is a diol component (A)
It may have a free hydroxyl group derived from Furthermore, the polyester poly (meth) acrylate may have free carboxyl groups and free hydroxyl groups.
The acid value (or hydroxyl value) of the polyester poly (meth) acrylate is, for example, 0 to 50 m.
gKOH / g, preferably 1 to 25 mg KOH / g, more preferably 3 to 10 mg KO
It may be about H / g.

A catalyst may be used for the esterification reaction. The catalyst may be an acid catalyst, a base catalyst, or an alkoxide, for example, a titanium (IV) alkoxide such as titanium (IV) tetraisopropoxide. For example, in particular, when the dicarboxylic acid component (B) and / or the (meth) acrylic acid component (C) is an "acid component", when the acid component is a dicarboxylic acid, a dicarboxylic acid lower alkyl ester or a dicarboxylic acid anhydride An acid catalyst can be suitably used. The acid catalyst is not particularly limited, and examples thereof include strong acids (eg, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid etc.), homo or heteropoly acids (eg, tungstophosphoric acid, molybdophosphoric acid, tungstosilicic acid, molybdosilicic acid etc.) Organic acids such as inorganic acids, sulfonic acids (alkanesulfonic acids such as methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, arenesulfonic acids such as p-toluenesulfonic acid, etc.), Lewis acids (eg, boron trifluoride) And solid acid catalysts such as etherates, tin tetrachloride, etc., cation exchange resins. The acid catalysts may be used alone or in combination of two or more.

The proportion of the catalyst is not particularly limited, and may be, for example, 0 with respect to 1 mol of the diol component (A).
. It may be about 001 mole to 1 mole, preferably about 0.01 to 0.5 mole.

When an acid halide (particularly, acid chloride) is used as the acid component, the reaction may be performed in the presence of a base in order to trap hydrogen halide generated in the reaction. As a base,
For example, metal hydroxides (alkali metal hydroxides such as sodium hydroxide and calcium hydroxide or alkaline earth metal hydroxides), metal carbonates (alkali metal carbonates such as sodium carbonate and sodium hydrogencarbonate or alkaline earths) Inorganic bases such as metalloid salts, amines (
Trialkylamines such as triethylamine, aromatic thirds such as benzyldimethylamine
And organic bases such as heterocyclic tertiary amines such as pyridine, etc.). The bases may be used alone or in combination of two or more.

The amount of the base used is not particularly limited, but, for example, per 1 mol of acid halide, for example,
It may be about 0.8 to 20 mol (e.g., 1 to 10 mol), preferably about 1.2 to 5 mol, and more preferably about 1.5 to 3 mol.

The reaction may be carried out in the presence of a thermal polymerization inhibitor. As a thermal polymerization inhibitor, benzoquinone, hydroquinones (eg, hydroquinone, hydroquinone monomethyl ether, p-te
rt-Butyl hydroquinone, p-benzoquinone etc., catechols (eg p-te)
rt-Butyl catechol and the like), amines (for example, N, N-diethylhydroxylamine and the like), 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 0.01 to 1 part by weight with respect to 100 parts by weight of the (meth) acrylic acid component (C).

The reaction may be carried out in the presence of a solvent. As the solvent, for example, hydrocarbons (aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene), halogenated hydrocarbons (methylene chloride, chloroform, carbon tetrachloride) Such),
Ethers (dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran), ketones (acetone, methyl ethyl ketone etc.), sulfoxides
Dimethyl sulfoxide and the like), nitriles (for example, acetonitrile and the like) and the like can be mentioned. The solvents may be used alone or in combination of two or more.

The reaction temperature and the reaction time can be appropriately selected according to the type of the raw material used, and in the reaction system containing the (meth) acrylic acid component (C), the reaction can be carried out at a relatively low temperature. The reaction temperature is not particularly limited. For example, in the first step reaction of stepwise esterification reaction (reaction not containing (meth) acrylic acid component (C)), the reaction temperature is about 50 to 300 ° C., preferably about 70 to 250 ° C. In order to suppress the polymerization of the (meth) acrylic acid component (C) in the second-stage reaction, which is carried out at a temperature, for example,
The temperature may be about 0 to 130 ° C. (eg, 0 to 120 ° C.), preferably about 25 to 100 ° C., and more preferably about 50 to 80 ° C.

The reaction may be carried out at reflux temperature. The reaction can be carried out with stirring in air or an inert atmosphere (nitrogen, noble gas, etc.), and may be carried out under normal pressure, under pressure or under reduced pressure. Moreover, in order to prevent unexpected polymerization at the time of reaction, you may carry out, blowing air in a reaction liquid.

In addition, the produced | generated compound (The polyester which has a hydroxyl group at the terminal represented by said Formula (1-2), or polyester poly (meth) acrylate of this invention represented by said Formula (1-1))
May be separated and purified by conventional means, for example, separation means such as filtration, reprecipitation with an antisolvent, concentration, extraction, crystallization, recrystallization, column chromatography, or a combination of these.

The weight average molecular weight (Mw) of the obtained polyester poly (meth) acrylate of the present invention measured using polystyrene by gel permeation chromatography (GPC) is, for example, 400 to 15000 (for example, 600 to 12000) You can choose from the range of 800 ~
It may be about 10000 (e.g., 1000 to 7500), more preferably about 1200 to 6000 (e.g., 1500 to 5000).

The molecular weight distribution (Mw / Mn) of the polyester poly (meth) acrylate of the present invention can be selected, for example, from the range of 1.0 to 10 (e.g., 1.1 to 7).

The glass transition temperature (Tg) of the polyester poly (meth) acrylate of the present invention can be selected, for example, from the range of -60 ° C to 300 ° C, preferably -40, as measured using a differential scanning calorimeter (DSC). It may be about -250 ° C, more preferably about -200C.

Usually, at room temperature, the polyester poly (meth) acrylate of the present invention is high in viscosity or solid and may not be able to be measured by a B-type viscometer. The viscosity (temperature 25 ° C.) of a mixture obtained by diluting 50 parts by weight of polyester poly (meth) acrylate with 50 parts by weight of 2-phenoxyethyl acrylate is, for example, 1000 to 300000 mPa · s (for example, 2000 to 9)
000 mPa · s), preferably 3000 to 8500 mPa · s (eg, 4000 to 8000 mPa · s), more preferably 5000 to 7500 mPa · s.
It may be about s (e.g., 6000 to 7000 mPa · s).

Also, the refractive index (temperature 25) of the polyester poly (meth) acrylate (uncured product) of the present invention
° C, wavelength 589 nm) is, for example, 1.55 to 1.73 (eg, 1.56 to 1.65)
And may be selected from the range of 1.57 to 1.64 (eg, 1.58 to 1.63), preferably 1.585 to 1.62 (eg, 1.59 to 1.61). Well, 1.55 to
It may be about 1.7 (e.g., 1.57 to 1.63). In particular, compounds in which rings Z ¹ and Z ² are fused polycyclic hydrocarbon rings (polyester poly (meth) acrylates) exhibit high refractive index, and the refractive index can be reduced by increasing m1 + m2 and introducing an aliphatic component . Therefore, the refractive index may be adjusted, for example, in the range of 1.53 to 1.75 (for example, 1.56 to 1.72), or 1.56 to 1.73 (for example, 1.57 to 1.73). 1.68), preferably 1
. 62 to 1.70 (for example, 1.63 to 1.67), more preferably 1.63 to 1.7
It may be about 0 (e.g., 1.64 to 1.67).

[Curable composition]
The curable composition of the present invention may consist of the polyester poly (meth) acrylate alone, and may further contain other polymerizable compounds such as (meth) acrylate (monofunctional (meth)).
Acrylate, multifunctional (meth) acrylate) and the like may be included.

The polymerizable compound may be N-vinyl pyrrolidone and the like, and as monofunctional (meth) acrylate, for example, alkyl (meth) acrylate [eg methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) And C _1-20 alkyl (meth) acrylates such as acrylate), hydroxyalkyl (meth) acrylates, alkoxyalkyl (meth) acrylates, cyclohexyl (meth) acrylates, aryl (
Meta) acrylate (eg, phenyl (meth) acrylate etc.), aryloxyalkyl (meth) acrylate (eg, phenoxyethyl (meth) acrylate etc.),
Aralkyl (meth) acrylate (eg, benzyl (meth) acrylate etc.), aryloxy ((poly) alkoxy) alkyl (meth) acrylate (eg, phenoxyethoxyethyl (meth) acrylate etc.), alkyl aryloxy ((poly) alkoxy ) Alkyl (meth) acrylate (eg, nonyl phenoxy (poly) ethoxyethyl (meth) acrylate etc.), aryl aryl (oxy ((poly) alkoxy) alkyl) (meth) acrylate (eg, 2- (o-phenyl phenoxy)) Ethyl (Meta)
Acrylate, phenyl phenoxy (poly) ethoxyethyl (meth) acrylate etc)
(Meth) acrylates having a sulfur atom [eg alkylthio (meth) acrylates (eg methylthio (meth) acrylate etc.), arylthio (meth) acrylates (eg phenylthio (meth) acrylate etc.), aralkylthio (meth) acrylates (Eg, benzylthio (meth) acrylate and the like), arylthioalkyl (meth) acrylate (eg, phenylthioethyl (meth) acrylate and the like); N, N-
Dialkyl (meth) acrylamide (for example, N, N- dimethyl (meth) acrylamide etc.), N, N- dialkyl aminoalkyl (meth) acrylate (for example, N, N- dimethylaminoethyl (meth) acrylate etc.), bisphenols Or mono (meth) acrylates of alkylene oxide adducts thereof (eg, mono (meth) acrylates of ethylene oxide adducts of bisphenol A), (meth) acrylates having a fluorene skeleton (eg, 9- (meth) acryloyloxymethyl fluorene) Etc. can be illustrated.

As polyfunctional (meth) acrylates, difunctional (meth) acrylates [for example, C _2-10 alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, diethylene glycol Di (
Polyalkylene glycol di (meth) acrylates such as meta) acrylate, di (meth) acrylate of bisphenol A (or its alkylene oxide adduct), trifunctional or higher (meth) acrylates [eg trimethylolpropane tri (meth) acrylate ) Triol or tetraol such as acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tri or tetra (meth) acrylate of tetraol, oligo (meth) acrylate [urethane (meth) acrylate, epoxy (meth) Acrylates, polyester (meth) acrylates not belonging to the category of polyester poly (meth) acrylates of the present invention, etc.], (meth) acrylates having a fluorene skeleton {
For example, 9, 9-bis [4- (2- (meth) acryloyloxy (poly) ethoxy) phenyl] fluorene etc} etc. are mentioned. These monofunctional and polyfunctional (meth) acrylates can be used alone or in combination of two or more.

The curable composition may contain a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator (heat radical generator) or a photopolymerization initiator (photo radical generator).

As a thermal polymerization initiator, organic peroxides [dialkyl peroxides (for example, di-t
ert-butyl peroxide, etc.), diacyl peroxides (eg, lauroyl peroxide, benzoyl peroxide, etc.), peracids (or peresters) (eg, tert-butyl hydroperoxide, cumene hydroperoxide, peracetic acid tert) -
Butyl, etc.) ketone peroxides, peroxycarbonates, peroxyketals], azo compounds [eg, azonitrile compounds such as 2,2'-azobis (isobutyronitrile), azoamide compounds, azoamidine compounds, etc. It can be illustrated. These thermal polymerization initiators can be used alone or in combination of two or more.

Examples of photopolymerization initiators include benzoins (benzoin, benzoin alkyl ethers such as benzoin ethyl ether, etc.), acetophenones (acetophenone, 2
-Hydroxy-2-methyl-1-phenylpropan-1-one etc.), aminoacetophenones {2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoaminopropanone etc}, anthraquinones (Anthraquinone, 2-methylanthraquinone, etc.), Thioxanthones (2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, etc.) Ketals (acetophenone dimethyl ketal, benzyl dimethyl ketal), benzophenones Benzophenone and the like), xanthones and the like can be exemplified. You may use these photoinitiators individually or in combination of 2 or more types.

The amount of polymerization initiator (heat or photopolymerization initiator) used is the total of 10 (meth) acrylate components.
0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight (eg, 1 to 8 parts by weight) based on 0 parts by weight
Parts by weight), more preferably about 2 to 5 parts by weight.

The photoinitiator may be combined with a photosensitizer. Photosensitizers include tertiary amines {eg, trialkylamines, trialkanolamines (such as triethanolamine)
And dialkylaminobenzoic acids such as ethyl N, N-dimethylaminobenzoate [such as ethyl p- (dimethylamino) benzoate], amyl N, N-dimethylaminobenzoate [such as amyl p- (dimethylamino) benzoate], etc. Conventional photosensitizers such as alkyl esters, bis (dialkylamino) benzophenones such as 4, 4- bis (diethylamino) benzophenone, dialkylamino benzophenones such as 4- (dimethylamino) benzophenone, etc., and the like can be mentioned. These photosensitizers may be used alone or in combination of two or more.

The amount of the photosensitizer used may be about 1 to 200 parts by weight, preferably 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 polymerization initiator.

The curable composition may also contain a solvent. The solvent is not particularly limited.
In addition to the solvents exemplified in the esterification reaction, esters (eg, ethyl acetate etc.) can be exemplified. These solvents may be used alone or in combination of two or more.

Furthermore, the curable composition may be a conventional additive such as a colorant, a stabilizer (a heat stabilizer, an antioxidant, an ultraviolet absorber, etc.), a filler, an antistatic agent, a flame retardant, a surfactant, It may contain a plasticizer and the like. These additives may be used alone or in combination of two or more.

[Cured product]
The curable composition of the present invention is easily cured by applying active energy (active energy ray) to form a cured product. As the activation energy, thermal energy and / or light energy (ultraviolet light, X-ray, electron beam, etc.) is useful.

When thermal energy is used, the heating temperature may be, for example, about 50 to 200 ° C., preferably 60 to 150 ° C., and more preferably about 70 to 120 ° C.

In the case of light irradiation (for example, ultraviolet irradiation), the light irradiation energy amount can be appropriately selected according to the application, and is, for example, 50 to 10000 mJ / cm ² , preferably 70 to 8000 mJ.
/ Cm ² , more preferably 100 to 5000 mJ / cm ² (eg, 500 to 3000)
It may be about mJ / cm ² ).

  Curing may be carried out in air or in an inert gas atmosphere (eg, nitrogen, noble gases, etc.).

The cured product is excellent in flexibility, probably because the polyester poly (meth) acrylate has a predetermined polyester structure, and also has high optical properties such as high refractive index derived from a fluorene skeleton. ing.

100 parts by weight of the polyester poly (meth) acrylate of the present invention and Irgacure 184 (manufactured by BASF Japan Ltd.) (3 parts by weight) as a photopolymerization initiator are mixed to form a curable composition, and ultraviolet irradiation (500 mJ refractive index of / cm ²⁾ four times a cured product was prepared (
The temperature 25 ° C., the wavelength 589 nm) is, for example, 1.5 to 1.75 (eg, 1.55 to 1.1).
65) can be selected from the range of about 1.57 to 1.70 (eg, 1.57 to 1.64),
Preferably, 1.58 to 1.68 (eg, 1.58 to 1.64), more preferably 1.
It may be about 6 to 1.67 (e.g., 1.6 to 1.63), or 1.61 to 1.73 (
For example, 1.61 to 1.62), preferably 1.62 to 1.72 (eg, 1.62 to 1).
. 665), and more preferably about 1.63 to 1.70 (e.g., about 1.64 to 1.68).

The Shore D hardness (the measurement method according to JIS K 7215) of the cured product is, for example,
It may be selected from the range of about 20 to 80 (e.g., 25 to 75), preferably about 30 to 70 (e.g., 40 to 67), and more preferably about 50 to 65 (e.g., 60 to 63).

Also, the glass transition temperature (T of the cured product) measured using a differential scanning calorimeter (DSC)
g) can be selected from the range of, for example, -60 ° C to 150 ° C (eg, -60 ° C to 120 ° C), -40 ° C to 130 ° C (eg, -40 ° C to 80 ° C), preferably -20 ° C ~ 120 ° C
(Eg, -20 ° C. to 40 ° C.), and may usually be 10 to 150 ° C. (eg, 3)
0 to 130 ° C., preferably 40 to 125 ° C. (eg, 50 to 120 ° C.), more preferably 60 to 120 ° C. (eg, 70 to 115 ° C.), particularly 70 to 120 ° C. (eg, 80)
It may be about 115 ° C.). The cured product of polyester poly (meth) acrylate in which the rings Z ¹ and Z ² are fused polycyclic hydrocarbon rings has a high glass transition temperature (Tg), for example, 90 to 130 ° C. (eg, 95 to 120 ° C.) ) Show a degree of Tg. Despite exhibiting such a high glass transition temperature, the cured product is rich in flexibility or flexibility (flexibility).

The form of the cured product may be a cured product of a one-dimensional structure, a cured product of a two-dimensional structure, such as a cured film (for example, a film etc), and a cured product of a three-dimensional structure (for example, a lens , Prism, etc.).

The cured product can be formed by various methods, and the method for forming the cured product is not particularly limited. For example, the cured film can be formed by using the curable composition as a substrate or a substrate [eg, metal (such as aluminum), ceramics (silicon, titania , Coating on inorganic materials such as glass, quartz etc., organic materials such as plastics (polypropylene, cyclic olefin resin, polycarbonate etc), porous materials such as wood] to form a coating (or thin film) and curing You may form by processing. In addition, a cured product having a tertiary structure may be produced by curing (heating and / or light irradiation) after molding or pouring (injecting) the curable composition into a predetermined mold.

The present invention will be described in more detail based on examples given below, but the present invention is not limited by these examples. The evaluation method is shown below.

(Average molecular weight, molecular weight distribution, number of repeating units n)
Gel Permeation Chromatography (GPC) (Tosoh Corp. HLC-8120 GPC)
The sample was dissolved in chloroform, and the average molecular weight and the molecular weight distribution were measured in terms of polystyrene at a temperature of 30 ° C. (flow rate: 0.085 mL / min). Repeating unit number n
Was calculated from the area ratio of the obtained GPC chart.

(Glass transition temperature (Tg))
Using a differential scanning calorimeter (DSC 6220, manufactured by Seiko Instruments Inc.), put the sample (cured product) in an aluminum pan, and under a nitrogen flow of 50 ml / min, under a temperature rising condition of 10 ° C./min, -50
The Tg was measured in the range of ° C to 200 ° C.

The sample (cured product) is polyester poly (meth) acrylate (100 parts by weight) and Irgacure 184 (manufactured by BASF Japan Ltd.) as a photopolymerization initiator (3 parts by weight)
And a mixture of them to prepare a curable composition, and a coating film of this curable composition is irradiated with ultraviolet light (500 mJ / cm).
² ) Repeatedly irradiated 4 times to cure, and a cured film as a sample was prepared.

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

(Flexibility or flexibility)
The cured film was applied to an end portion at an angle of 90 ° and bent to an angle of 90 ° to observe whether the cured film cracked or not, and the flexibility or flexibility of the cured film was evaluated based on the following criteria.

○: no cracks in the cured film ×: cracks in the cured film

Example 1
(1) Preparation of polyester diol 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (hereinafter referred to as BPEF) (155 mmol) and 9,9-bis (2-carboxyethyl) fluorene (hereinafter referred to as , FDP) (103 mmol) in toluene (solvent) (270 mL),
Paratoluenesulfonic acid (catalyst) (31 mmol) was added, and the reaction temperature was 115 under nitrogen atmosphere.
The reaction was allowed to proceed at 5 ° C for 5 hours. The completion of the reaction was confirmed by high performance liquid chromatography (HPLC).

(2) Preparation of polyester diacrylate Acrylic acid (438 mmol) was added to the obtained polyester diol composition, methoquinone (polymerization inhibitor) (48 mmol) was added, and reaction was carried out at a reaction temperature of 115 ° C. for 6 hours. After completion of the reaction was confirmed by high performance liquid chromatography (HPLC), the reaction solution was neutralized and then purified by washing with water to obtain 48.5 g of a transparent viscous polyester diacrylate.

The weight average molecular weight (Mw) of the obtained polyester diacrylate is 2317, the molecular weight distribution (Mw / Mn) is 1.45, the average value of the number n of repeating units is 2.3, the refractive index (25 ° C., wavelength 589 nm) is It was 1.625.

(Example 2)
The step of Example 1 was carried out using 168 mmol of BPEF in step (1) of Example 1.
In the same manner as in Example 1 except that 84 mmol of acrylic acid was used in 2), 49.7 g of a transparent viscous polyester diacrylate was obtained.

The weight average molecular weight (Mw) of the obtained polyester diacrylate is 1579, the molecular weight distribution (Mw / Mn) is 1.25, the average number of repeating units n is 1.6, and the refractive index (25 ° C., wavelength 589 nm) It was 1.621.

(Example 3)
Using 177 millimoles of BPEF in step (1) of Example 1;
A clear and viscous polyester diacrylate was obtained in the same manner as in Example 1 except that 71 mmol of acrylic acid was used in 2).

The weight average molecular weight (Mw) of the obtained polyester diacrylate is 1582, the molecular weight distribution (Mw / Mn) is 1.16, the average number of repeating units n is 1.5, and the refractive index (25 ° C., wavelength 589 nm) It was 1.617.

(Example 4)
An adduct in which 9 moles of ethylene oxide is added to 1 mole of BPEF (hereinafter referred to as BP)
EF-9 EO) was prepared by the method described in Patent Document 3.

90 mmol of BPEF-9EO instead of BPEF in step (1) of Example 1; FD
A clear and viscous polyester diacrylate was obtained in the same manner as in Example 1 except that 50 mmol of P was used and 110 mmol of acrylic acid was used in step (2) of Example 1.

The weight average molecular weight (Mw) of the obtained polyester diacrylate was 4235, and the molecular weight distribution (Mw / Mn) was 1.93.

(Example 5)
100 mmol of BPEF-9EO in place of BPEF in step (1) of Example 1;
A transparent viscous polyester diacrylate was obtained in the same manner as in Example 1 except that 56 mmol of adipic acid was used instead of DP and 123 mmol of acrylic acid was used in step (2) of Example 1.

The weight average molecular weight (Mw) of the obtained polyester diacrylate was 3968, and the molecular weight distribution (Mw / Mn) was 2.12.

(Example 6)
Same as Example 1 except using 100 mmol of BPEF in step (1) of Example 1, using 55 mmol of adipic acid instead of FDP, and using 123 mmol of acrylic acid in step (2) of Example 1. A clear and viscous polyester diacrylate was obtained.

The weight average molecular weight (Mw) of the obtained polyester diacrylate was 1791 and the molecular weight distribution (Mw / Mn) was 2.22.

(Example 7)
(Synthesis of BNEF)
In a 1 L separable flask, 45 g of 9-fluorenone (0.25 mol, made by Osaka Gas Chemical Co., Ltd.), 188 g (1 mol) of ethylene glycol mono (2-naphthyl) ether
Then, 1 g of 3-mercaptopropionic acid was added, and the mixture was heated to 60 ° C. to completely dissolve it. 54 g of sulfuric acid was gradually added to the formed mixture and stirred for 5 hours while maintaining 60 ° C., and it was confirmed by HPLC (high performance liquid chromatography) that the conversion of 9-fluorenone was 99% or more did. The reaction solution obtained was neutralized with 48% aqueous sodium hydroxide solution, 400 g of xylene was added, and the reaction solution was washed several times with distilled water and cooled to precipitate crystals. Furthermore, when it filtered and dried, 87 g (yield 67%) of the target 9, 9- bis [6- (2-hydroxy ethoxy) -2- naphthyl] fluorenes (BNEF) were obtained as a crystal.
The HPLC purity of the obtained crystals was measured to be 98.3%. The obtained crystals were confirmed to be 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene (BNEF) by ¹ H-NMR and mass spectrum.

100 mmol of BNEF is used instead of 155 mmol of BPEF in step (1) of Example 1, and 55 mmol of FDP is used, and acrylic acid 122 is used in step (2) of Example 1.
A clear, viscous polyester diacrylate was obtained as in Example 1, but using millimoles.

The weight average molecular weight (Mw) of the obtained polyester diacrylate was 2253, and the molecular weight distribution (Mw / Mn) was 2.23.

(Example 8)
100 mmol of BNEF is used in place of 155 mmol of BPEF in the step (1) of Example 1 and 55 mmol of adipic acid is used in place of 103 mmol of FDP in the step (2) of Example 1; A clear and viscous polyester diacrylate was obtained in the same manner as in Example 1 except that it was used.

The weight average molecular weight (Mw) of the obtained polyester diacrylate was 1759, and the molecular weight distribution (Mw / Mn) was 2.07.

(Comparative example 1)
As a comparative example, 9,9-bis (4- (2-acryloyloxyethoxy) phenyl) fluorene [refractive index (25 ° C., wavelength 589 nm) 1.616] was used.

  The evaluation results are shown in Table 1 below.

As shown in Table 1, novel flexible or flexible polyester polyester poly (high refractive index)
Meta) acrylate was obtained.

The polyester poly (meth) acrylate of the present invention is excellent in properties such as high refractive index and flexibility, so that it can be used in various applications, for example, light emitting materials (eg, light emitting materials for organic EL), organic semiconductors, graphitization Precursor, gas separation membrane (eg, CO ₂ gas separation membrane etc.), ink material,
Paint, printing ink, coating agent (eg optical overcoat or hard coating agent such as coating agent for LED (light emitting diode) element), lens [for DVD lens (eg digital versatile disc) Pickup lens etc.)
, Micro lenses (for example, micro lenses for liquid crystal projectors), spectacle lenses, etc.], polarizing films (for example, polarizing films for liquid crystal displays), antireflective films (or antireflective films, for example, antireflective films for display devices, etc.) ), Films for touch panels, films for flexible substrates, films for displays (for example, PDP (plasma display), LCD (liquid crystal display), VFD (vacuum fluorescent display), SED (surface conduction electron-emitting device display), FED (electric field) Films (filters, protective films, etc.) for displays (especially thin displays) such as NEDs (nano-emissive displays), CRTs, etc., membranes for fuel cells, optical fibers, optical waveguides, holo Ram, can be suitably used in a wide range of applications such as UV-curable CFRP, the power semiconductor encapsulation. In particular, the polyester poly (meth) acrylates of the invention are
It can be suitably used as an optical material, and examples of the shape of such an optical material include a film or sheet, a plate, a lens, a tube, and the like.

Claims (14)

Following formula (1-1)

(Wherein, R ^1a and R ^1b are each a hydrogen atom or a methyl group, n is an integer of 1 or more, and A and B are each a residue of a diol component (A) and a dicarboxylic acid component (B))
Wherein the diol component (A) contains a diol component (A1) having a fluorene skeleton in the formula (1-1), and the dicarboxylic acid component (B) has a fluorene skeleton Containing a dicarboxylic acid component (B1) having a total amount of residues of the diol component (A1) and the dicarboxylic acid component (B1) of the residues of the diol component (A) and the dicarboxylic acid component (B) Polyester poly (meth) acrylate which is 70 mol% or more with respect to the total amount. The polyester poly (meth) acrylate according to claim 1, wherein the diol component (A1) having a fluorene skeleton contains at least a diol component represented by the following formula (2-1).

(Wherein, Z ¹ and Z ² each represent an aromatic hydrocarbon ring, R ^2a and R ^2b each represent an alkylene group, m 1 and m 2 each represent an integer of 0 or more, and R ^3a and R ^3b each represent an inactive substitution in the reaction Each of the groups p1 and p2 is an integer of 0 or more, each of R ^4a and R ^4b is a substituent inert to the reaction, and each of k 1 and k 2 is an integer of 0 to 4). In equation (2-1),
Z ¹ and Z ² are a C _6-14 aromatic hydrocarbon ring,
R ^2a and R ^2b are linear or branched alkylene groups,
m1 and m2 are integers of 0 to 10,
R ^3a and R ^3b are alkyl groups,
The polyester poly (meth) acrylate according to claim 2, wherein p1 and p2 are integers of 0-4. In equation (2-1),
Z ¹ and Z ² are aromatic hydrocarbon rings selected from benzene ring, naphthalene ring and biphenyl ring,
R ^2a and R ^2b are linear or branched C _2-6 alkylene groups,
m1 and m2 are integers of 0 to 5,
R ^3a and R ^3b are methyl groups,
The polyester poly (meth) acrylate according to claim 2 or 3, wherein p1 and p2 are integers of 0-2.   The diol component (A) further comprises at least one diol component (A2) selected from an aliphatic diol component (A2-1), an alicyclic diol component (A2-2) and an aromatic diol component (A2-3). The polyester poly (meth) acrylate according to any one of claims 1 to 4, which comprises The dicarboxylic acid component (B) is at least one dicarboxylic acid selected from aliphatic dicarboxylic acid component (B2-1), alicyclic dicarboxylic acid component (B2-2) and aromatic dicarboxylic acid component (B2-3) Contains the ingredients,
The dicarboxylic acid component (B1) having a fluorene skeleton is selected from a dicarboxylic acid represented by the following formula (3-1), a dicarboxylic acid represented by the following formula (3-2) and an ester-forming derivative thereof The polyester poly (meth) acrylate according to any one of claims 1 to 5, which contains at least one.

(Wherein, X ^1a and X ^1b each represent a divalent hydrocarbon group which may have a substituent, q represents an integer of 0 to ^4, and R ^4a and R ^4b , and k 1 and k 2 are the same as above) ). A dicarboxylic acid component (B) is a dicarboxylic acid in which X ^1a is a linear or branched C _1-6 alkylene group in the above formula (3-1), C _2-12 alkane-dicarboxylic acid, C _5- The polyester poly (meth) acrylate according to any one of claims 1 to 6, which comprises at least one dicarboxylic acid component selected from ₁₀ cycloalkane-dicarboxylic acids, C _6-24 arene-dicarboxylic acids and their ester-forming derivatives. .   The amount of use of the dicarboxylic acid component (B1) having a fluorene skeleton or the other dicarboxylic acid component (B2) is 50 to 100% by mole based on all dicarboxylic acid components (B). Polyester poly (meth) acrylate as described in.   The polyester poly (meth) acrylate according to any one of claims 1 to 8, wherein in the formula (1-1), the number n of repeating units is 1 to 10.   The total amount of residues of the diol component (A1) having a fluorene skeleton and the dicarboxylic acid component (B1) having a fluorene skeleton is 90 moles relative to the total amount of residues of the diol component (A) and the dicarboxylic acid component (B) The polyester poly (meth) acrylate according to any one of claims 1 to 9, which is at least%. Following formula (1-2)

(Wherein n, A and B are the same as described in claim 1)
Wherein, in the formula (1-2), the diol component (A) contains a diol component (A1) having a fluorene skeleton, and the dicarboxylic acid component (B) is a dicarboxylic acid having a fluorene skeleton The total of residues of the diol component (A1) and the dicarboxylic acid component (B1) including the component (B1) is relative to the total amount of residues of the diol component (A) and the dicarboxylic acid component (B) 70% by weight or more of polyester polyol.   A diol component (A) and a dicarboxylic acid component (B) are reacted to form a polyester having a hydroxyl group at an end, and the produced polyester is reacted with (meth) acrylic acid or its ester-forming derivative, A method of producing the polyester poly (meth) acrylate according to any one of claims 1 to 10.   A curable composition comprising the polyester poly (meth) acrylate according to any one of claims 1 to 10.   The hardened | cured material which the curable composition of Claim 13 hardened | cured.