JP6487308B2 - Polyester poly (meth) acrylate having fluorene skeleton, curable composition and cured product thereof, and production method thereof - Google Patents

Description

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

  It is known that a material having a fluorene skeleton exhibits excellent properties in terms of refractive index and heat resistance. Polyfunctional (meth) acrylates having a fluorene skeleton have been proposed as representative examples of compounds that can be used for optical materials and the like by utilizing such excellent properties of the fluorene skeleton.

  For example, Japanese Unexamined Patent Application Publication No. 2007-91870 (Patent Document 1) includes a specific polyfunctional (meth) acrylate having a fluorene skeleton, a hydrolyzable condensable organosilicon compound having a polymerizable group, and a photoacid generator. In the examples, 9,9-bis (4-acryloyloxyethoxyphenyl) fluorene is described as the multifunctional (meth) acrylate. However, such a cured product of an acrylate having a fluorene skeleton has a high refractive index but is hard and lacks flexibility.

  In WO2013 / 022065 (Patent Document 2) and JP2013-53310A (Patent Document 3), two (meth) acryloyloxy groups are bonded to two phenyl groups bonded to the 9-position of fluorene, respectively. And / or polyfunctional (meth) acrylates with (meth) acryloyloxy (poly) alkoxy groups attached. In Examples and Reference Examples, an adduct diacrylate obtained by adding 6.6 to 16.0 mol of ethylene oxide on average to 1 mol of 9,9-bis (4-hydroxyphenyl) fluorene (BPF). Is described. However, such a cured product of diacrylate is derived from a soft polyoxyethylene unit and exhibits scratch recovery (flexibility) in a scratch resistance test, but is refracted as the number of ethylene oxide additions increases. The index decreases, and it is impossible to achieve both high refractive index and flexibility.

  JP-A-2008-285647 (Patent Document 4) describes a urethane acrylate that forms a cured product having both flexibility, heat resistance and high refractive index, and has excellent handling properties. 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 The urethane (meth) acrylate which the (meth) acrylic compound which has has reacted is disclosed. However, such a cured product of urethane acrylate exhibits flexibility derived from the polyol skeleton in the polyisocyanate compound, but cannot improve the refractive index.

  Japanese Patent Application Laid-Open No. 2013-227534 (Patent Document 5) discloses an acid that has a high refractive index, can be improved in alkali solubility and adhesion to a support, and has excellent optical properties, heat resistance, dimensional stability, and the like. An anhydride-modified fluorene-containing acrylic resin is disclosed. In the examples of this document, 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene was reacted with acrylic acid, and the resulting fluorene-containing epoxy acrylate was reacted with tetracarboxylic dianhydride. It is described that an 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 further, a pseudo crosslinking point due to a hydrogen bond between carboxyl groups is also formed.

  A polyester resin having a fluorene skeleton is also known as a thermoplastic resin that can be melt-molded utilizing the properties of the fluorene skeleton. For example, Japanese Patent Application Laid-Open No. 2012-144746 (Patent Document 6) discloses a diol component that is a polymerization component and a dicarboxylic acid as a polyester resin excellent in various properties such as heat resistance, refractive index, optical properties, and solvent solubility. A polyester resin in which both of the components include a compound having at least a fluorene skeleton is disclosed. In the examples, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -2-methylphenyl) fluorene, One diol component selected from 9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (2-chlorocarbonylethyl) fluorene, 2,7-di (chlorocarbonyl) -9,9-dimethyl A linear polyester resin obtained by polymerizing one dicarboxylic acid component selected from fluorene is described.

JP 2007-91870 A (Claim 1, paragraph [0007], Example) International Publication No. 2013/022065 (Claim 1, Example, Reference Example) JP2013-53310A (Claim 1, Examples, Reference Examples) JP 2008-285647 A (Claim 1, paragraphs [0009]-[0012], Examples) JP 2013-227534 A (Claim 1, paragraphs [0008]-[0012], Examples) JP 2012-144746 A (paragraphs [0006]-[0010], Examples)

  Accordingly, an object of the present invention is to provide a novel polyester poly (meth) acrylate having a cured product having flexibility and a fluorene skeleton, a curable composition containing the polyester poly (meth) acrylate, a cured product thereof, and the It is providing the manufacturing method of 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 capable of achieving both high refractive index and flexibility, and a curable composition containing the polyester poly (meth) acrylate. And a cured product thereof, and a method for producing the polyester poly (meth) acrylate.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have introduced a fluorene skeleton into the polyester poly (meth) acrylate, and a cured product having flexibility (flexibility), and further its flexibility and high refraction. The present invention was completed by finding that a cured product having both a good balance and a high rate was obtained.

  That is, the polyester poly (meth) acrylate (for example, bifunctional polyester (meth) acrylate) of the present invention is represented by 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 residues of the diol component (A) and the dicarboxylic acid component (B), respectively)
And 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).

(In the formula, Z ¹ and Z ² are each an aromatic hydrocarbon ring, R ^2a and R ^2b are each an alkylene group, m 1 and m 2 are each an integer of 0 or more, and R ^3a and R ^3b are substitutions that are inert to the reaction. Group, p1 and p2 are each an integer of 0 or more, R ^4a and R ^4b are each a substituent inert to the reaction, and k1 and k2 each represent an integer of 0 to 4).

The diol component represented by the formula (2-1) includes, for example, aromatic carbonization in which Z ¹ and Z ² are selected from C _6-14 aromatic hydrocarbon rings (for example, 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 groups), and m1 and m2 are integers of 0 to 10 (For example, an integer of 0 to 5), R ^3a and R ^3b are alkyl groups (for example, a methyl group), and p1 and p2 are integers of 0 to 4 (for example, an integer of 0 to 2), Also good.

The diol component (A) further comprises at least one diol component (A2) selected from the aliphatic diol component (A2-1), the alicyclic diol component (A2-2) and 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 the fluorene skeleton to the other diol component (A2) may be the former / the latter (molar ratio) = 10/90 to 100/0.

  The dicarboxylic acid component (B) is at least one selected from the aliphatic dicarboxylic acid component (B2-1), the alicyclic dicarboxylic acid component (B2-2), and the aromatic dicarboxylic acid component (B2-3). A dicarboxylic acid component may be included, and the aromatic dicarboxylic acid component (B2-3) may include a dicarboxylic acid component (B1) having a fluorene skeleton. The dicarboxylic acid component (B1) having a fluorene skeleton was 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. At least one dicarboxylic acid component may be included.

(Wherein, X ^1a and X ^1b are each a divalent hydrocarbon group which may have a substituent, q represents an integer of 0 to ^4, and R ^4a and R ^4b , k1 and k2 are the same as above. ).

The dicarboxylic acid component (B) is a compound 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 _5-10 cyclo It may be at least one component selected from alkane-dicarboxylic acids, C _6-24 arene-dicarboxylic acids and ester-forming derivatives thereof.

  The amount of the dicarboxylic acid component (B1) or other dicarboxylic acid component (B2) having a fluorene skeleton may be about 50 to 100 mol% with respect to the total dicarboxylic acid component (B).

  In the formula (1-1), the number of repeating units n 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 ) May be 50 mol% or more based on the total amount of residues (A and B).

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

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

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

  This invention also includes the curable composition containing the polyester poly (meth) acrylate mentioned above, and its hardened | cured material.

  In the present specification and claims, the term “dicarboxylic acid component” means not only dicarboxylic acids but also ester-forming derivatives of dicarboxylic acids (eg, lower alkyl esters, acid halides, acid anhydrides) unless otherwise specified. It is used to mean including things. “(Meth) acrylate” means both acrylate and methacrylate. Furthermore, “polyester poly (meth) acrylate” means an oligoester (meth) acrylate, and in the above formula (1-1), it may be an aggregate (or composition) of compounds having different repeating units n. Good. The “polyester polyol” means an oligoester polyol, and may be an aggregate (or composition) of compounds having different repeating units n in the formula (1-2).

  In the present invention, the cured product obtained by curing the curable composition has high flexibility or flexibility because the novel polyester poly (meth) acrylate has a specific polyester structure having at least a fluorene skeleton. ing. Further, such a cured product can achieve both a 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 residues of the diol component (A) and the dicarboxylic acid component (B), respectively)
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 is cured, a cured product having flexibility or flexibility can be formed despite having a rigid fluorene skeleton. The reason is not clear, but there are (meth) acryloyl groups serving as crosslinking points at both ends of the polyester, and there is a fluorene skeleton or cardo structure between the crosslinking points, so that the crosslinked structure has a certain degree of freedom. Guessed. Furthermore, the (meth) acrylate and the cured product have a high refractive index 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 usually may be the same group (that is, a hydrogen atom or a methyl group).

  In the above formula (1-1), the number of repeating units n of the polyester structure can be selected from the range of about 1 to 100 (for example, 1 to 50), for example, an integer of about 1 to 30, preferably 1 to Even an integer of 20 (for example, an integer of 2 to 15), more preferably an integer of 1 to 10 (for example, an integer of 3 to 8), particularly an integer of 1 to 5 (for example, an integer of 1 to 3) Good. If the number of repeating units n is too large, the viscosity becomes high and the handling properties of the polyester poly (meth) acrylate and its curable composition may be reduced. In addition, n may mean the average value (arithmetic average value or arithmetic average value) as an aggregate of the polyester poly (meth) acrylates of the present invention, and the preferable range of the average value is within the range of the above integers. The same. The average value (arithmetic average value or arithmetic average value) can be calculated by a conventional method, and can be calculated from, for example, the area ratio in a 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))
The fluorenediol component (A1) is 9,9-bis (hydroxyalkyl) fluorene, such as 9,9-bis (hydroxymethyl) fluorene, 9,9-bis (2-hydroxyethyl) fluorene, 9,9- 9,9-bis (hydroxyC _1-10 alkyl) fluorene such as bis (2-hydroxypropyl) fluorene, 9,9-bis (3-hydroxypropyl) fluorene, 9,9-bis (6-hydroxyhexyl) fluorene (For example, 9,9-bis (hydroxyC _2-6 alkyl) fluorene) and the like, typically, may be a compound represented by the following formula (2-1). Moreover, these fluorenediol components (A1) can also be used individually or in combination of 2 or more types.

(In the formula, Z ¹ and Z ² are each an aromatic hydrocarbon ring, R ^2a and R ^2b are each an alkylene group, m 1 and m 2 are each an integer of 0 or more, and R ^3a and R ^3b are substitutions that are inert to the reaction. Group, p1 and p2 are each an integer of 0 or more, R ^4a and R ^4b are each a substituent inert to the reaction, and k1 and k2 each represent 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 a monocyclic aromatic hydrocarbon ring (monocyclic arene ring) such as a benzene ring, and a polycyclic ring. Aromatic hydrocarbon rings (polycyclic arene rings) and the like, and polycyclic aromatic hydrocarbon rings include condensed polycyclic aromatic hydrocarbon rings (condensed polycyclic arene rings), ring assembly aromatics A hydrocarbon ring (ring assembly arene ring) and the like are included.

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

Examples of the ring-assembled aromatic hydrocarbon ring include a bialene ring such as a bi-C _6-12 arene ring such as a biphenyl ring, a binaphthyl ring, and a phenylnaphthalene ring (such as a 1-phenylnaphthalene ring and a 2-phenylnaphthalene ring), and a telearene ring Examples thereof include a tel C _6-12 arene ring such as a terphenylene ring. Preferred ring-aggregated aromatic hydrocarbon rings include bi-C _6-10 arene rings, particularly biphenyl rings.

Preferred rings Z ¹ and Z ² include C _6-20 aromatic hydrocarbon rings (eg, C _6-14 aromatic hydrocarbon rings, particularly benzene ring, naphthalene ring and biphenyl ring). The two rings Z ¹ and Z ² may be the same or different rings, and may usually be the same ring.

In the above formula (2-1), examples of the alkylene group represented by the groups R ^2a and R ^2b include a linear or branched alkylene group. As the linear alkylene group, for example, a C _2-6 alkylene group such as an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, preferably a C _2-4 alkylene group, more preferably a C _2-3 alkylene group, In particular, an ethylene group can be exemplified. Examples of the branched alkylene group include C _3-6 alkylene groups such as a propylene group, 1,2-butanediyl group, and 1,3-butanediyl group, preferably a C _3-4 alkylene group, particularly a propylene group. In addition, when m1 and m2 are 2 or more, they may be composed of the same or different types of alkylene groups, and may usually 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 number of repeating units m1 and m2 of the groups OR ^2a and OR ^2b may be an integer of 0 or more, for example, about 0 to 10 (for example, 1 to 7), preferably an integer of 1 to 5 (for example, An integer of 1 to 4), more preferably an integer of 1 to 3 (for example, an integer of 1 to 2), particularly 1. In addition, m1 and m2 may be the same or different.

  The total amount (m1 + m2) of m1 and m2 is an average (arithmetic average or arithmetic average) with respect to the entire diol component (A1) (molecular aggregate of diols represented by the formula (2-1)). Can be selected from a range of about 20 (eg, 1-8), 1-15 (eg, 2-13), preferably 1-7 (eg, 1-6), more preferably 2-6 (eg, 2). To 4), particularly about 2 to 3, may be about 2 to 12 (for example, 2 to 10), and may be about 5 to 15 (for example, 9 to 12). If m1 or m2 (or m1 + m2) is too large, the flexibility of the cured product is improved, but there is a possibility that both high refractive index and flexibility cannot be achieved. In addition, the number of repeating units of the above average (arithmetic average or arithmetic average) can be easily calculated by a conventional method, for example, the method described in Patent Document 2 or 3.

In the formula (2-1), the groups [— (OR ^2a ) _m1 —OH] and [— (OR ^2b ) _m2 —OH] can be substituted at appropriate positions of the rings Z ¹ and Z ^2. when Z ¹ and ^{Z 2} is a benzene ring, the phenyl group 2-, 3-, 4-position (in particular, the 3-position or 4-position) often are substituted, ring ^{Z 1} and When Z ² is a naphthalene ring, it is often the 5th to 8th position of the naphthyl group, and any one of 1,5-position, 2,5-position, 1,6-position, 2,6-position, etc. For example, there are many cases such as the 1,5-position, 2,6-position, etc. (particularly, the 2,6-position). Further, in the ring assembly arene rings Z ¹ and Z ² , the substitution position is not particularly limited, and for example, the arene ring bonded to the 9-position of fluorene or the arene ring adjacent to the arene ring may be substituted. . For example, when the rings Z ¹ and Z ² are biphenyl rings, the 3-position or 4-position of the biphenyl rings Z ¹ and Z ² are often bonded to the 9-position of fluorene. , 5-position, 3,6-position, 3,3′-position, 3,4′-position, 4,2-position, 4,3′-position, 4,4′-position, etc. May be substituted, preferably 3,5-position, 3,6-position, 3,4'-position, 4,2-position, 4,4'-position, more preferably 3,6-position , May be substituted at the substitution position at the 4,2-position.

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

Among these groups R ^3a and R ^3b , typically, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an acyl group, a nitro group, a cyano group, a substituted amino group, and the like can be given. Preferred groups R ^3a and R ^3b include an alkyl group (such as a linear or branched C _1-6 alkyl group such as a methyl group), an aryl group, and an alkoxy group (such as a linear or branched chain such as a methoxy group). An alkyl group (for example, a methyl group) is particularly preferable, 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 form the ring assembly arene ring together with the rings Z ¹ and Z ² , respectively. The types of the radicals R ^3a and R ^3b may be the same or different in the same or different rings Z ¹ and Z ² .

Substituents which p1 and p2 may be selected appropriately in accordance with the type of ring ^{Z 1} and ^{Z 2,} for example, 0-8, preferably 0-4 (e.g., 0-2), more preferably 0 or 1 (e.g. , 0). 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. Incidentally, the substitution position of group ^{R 3a} and ^{R 3b} are not particularly limited, on the ring ^{Z 1} and ^{Z 2,} the group _{^{[- (OR 2a) m1 -OH}} ] and _{^{[- (OR 2b) m2 -OH}} ] May be other than the position to be replaced.

In the formula (2-1), as the groups R ^4a and R ^4b , a cyano group, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group (eg, a methyl group, an ethyl group, a propyl group, C _1-6 alkyl group such as isopropyl group, butyl group and t-butyl group), aryl group (for example, C _6-10 aryl group such as phenyl group) and the like. Of these groups R ^4a and R ^4b , C _1-4 alkyl groups (particularly methyl groups) are preferred. The groups R ^4a and R ^4b may be the same or different. When the number of substitutions k1 and k2 is 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 integers of 0 to 4, preferably 0 to 1, especially 0. The substitution numbers k1 and k2 may be the same or different from each other. Further, the substitution positions of the groups R ^4a and R ^4b are not particularly limited, and are, for example, 2-position to 7-position (2-position, 7-position, 2- and 7-position, etc.) of the fluorene ring. Also good.

A representative compound in the formula (2-1) is 9,9-bis [hydroxy (mono or poly) alkoxyaryl] fluorene (for example, 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) alkoxybiaryl] fluorene (eg, 9,9-bis [hydroxy (mono or poly) C _2-6 alkoxybi C _6-10 aryl] fluorene), more preferably 9,9-bis [hydroxy (mono or poly) C _2-3 alkoxyC _6-10 aryl] fluorene, 9,9-bis [hydroxy (mono or poly) C _2-3 alkoxybi C _6-10 aryl] fluorene and the like.

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

As 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes, in the formula (1-1), rings Z ¹ and Z ² are substituted or unsubstituted benzene rings, and R ^2a and R ^2b are linear Or branched C _2-4 alkylene group, compounds in which m1 and m2 are 1, and k1 and k2 are each 0, for example, (1) 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene 9,9-bis (hydroxyC _2-4 alkoxyphenyl) fluorene such as 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-hydroxy) Loxyethoxy) -3-isobutylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-t-butylphenyl) fluorene, 9,9-bis [4- (2-hydroxyethoxy)- 9,9-bis (hydroxy C _2-4 alkoxy such as 3,5-dimethylphenyl] fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butyl-6-methylphenyl) fluorene 9,9-bis (hydroxy C _2-4 such as mono- or di-C _1-4 alkylphenyl) fluorene, (3) 9,9-bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene alkoxy _{C 5-10} cycloalkyl phenyl) fluorene, (4) 9,9-bis [4- (2-hydroxyethoxy) -3-phenyl Fe Le] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -3-phenyl phenyl] 9,9-bis fluorene (hydroxy _{C 2-4} alkoxy _{C 6-10} aryl phenyl) fluorene; ring 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, m1 and m2 are 2 to 10, and k1 and k2 are 0, respectively. 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 (hydroxyC _2-4 alkoxyC _2-4 alkoxyphenyl) fluorene, 9 , 9-bis (hydroxy _{C 2-4} alkoxy _{C 2-4} alkoxy - mono- or _{di-C 1-4} alkyl phenyl) fluorene, 9,9-bis (hydroxy C _2-4 alkoxy C _2-4 alkoxy C _6-10 arylphenyl) fluorene, 9,9-bis (hydroxy C _2-4 alkoxy C _2-4 alkoxy C _6-10 arylphenyl) fluorene and the like are included.

As 9,9-bis (hydroxy (poly) alkoxynaphthyl) fluorenes, for example, rings Z ¹ and Z ² are substituted or unsubstituted naphthalene rings, and R ^2a and R ^2b are linear or branched C _{2. -4} alkylene group, a compound in which m1 and m2 are 1, and k1 and k2 are each 0, for example, (5) 9,9-bis (hydroxyalkoxynaphthyl) fluorene [for example, 9,9-bis [6- (2 -Hydroxyethoxy) -2-naphthyl] fluorene, 9,9-bis [5- (2-hydroxyethoxy) -1-naphthyl] fluorene, 9,9-bis [6- (2-hydroxypropoxy) -2-naphthyl ] fluorene such as 9,9-bis (hydroxy _{C 2-4} alkoxy naphthyl) fluorene; ring ^{Z 1} and ^{Z 2} are substituted or unsubstituted naphthalene ring, ^{R 2} And ^{R 2b} is linear or branched _{C 2-4} alkylene group, m1 and m2 is 2-10, Compound k1 and k2 are each 0, i.e., the compounds in (5), m1 and m2 are 2 -10, for example, 9,9-bis (hydroxy C _2-4 alkoxy C _2-4 alkoxynaphthyl) fluorene and the like.

These fluorenediol components can be used alone or in combination of two or more. Preferred fluorenediol components are 9,9-bis (hydroxyC _2-4 alkoxyphenyl) fluorene, such as 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene such as 9,9-bis _{(C 1-4} alkyl - hydroxy _{C 2-4} alkoxyphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy ) -3-phenylphenyl) fluorene such as 9,9-bis (hydroxy _{C 2-4} alkoxyphenyl phenyl) fluorene, 9,9-bis (5- (2-hydroxyethoxy) -1-naphthyl) fluorene, 9, 9- bis (6- (2-hydroxyethoxy) -2-naphthyl) fluorene such as 9,9-bis [hydroxy C _-4 alkoxy naphthyl] fluorene, in particular 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, a 9,9-bis (6- (2-hydroxyethoxy) -2-naphthyl) fluorene.

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

(Diol component (A2))
The other diol component (A2) includes an aliphatic diol component (A2-1), an alicyclic diol component (A2-2), and an aromatic diol component (A2-3). By using these diol components (A2), the 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 handleability of polyester poly (meth) acrylate or its curable composition can be adjusted.

Examples of the aliphatic diol component (A2-1) include alkane diols (for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, C _2-10 alkane-diols such as 1,4-butanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, preferably C _2-6 alkane-diol, more preferably C _2-4 alkane-diol); polyalkane diols (eg di- or tri-C _2-4 alkane diols such as diethylene glycol, dipropylene glycol, triethylene glycol, polytetramethylene) And ether glycol).

Examples of the alicyclic diol component (A2-2) include cycloalkanediol (eg, C _5-8 cycloalkane-diol such as cyclohexanediol); di (hydroxyalkyl) cycloalkane (eg, cyclohexanedimethanol). Di (hydroxyC _1-4 alkyl) C _5-8 cycloalkane and the like); isosorbide and the like.

Examples of the aromatic diol component (A2-3) include dihydroxyarene (eg, hydroquinone, resorcinol, etc.); dihydroxyalkylarene (eg, di (1,3-benzenedimethanol, 1,4-benzenedimethanol, etc.). hydroxy _{C 1-4 alkyl) C 6-10} arene); bisphenols (e.g., biphenol, bis (hydroxyphenyl such as bisphenol _{a) C 1-10} alkanes, 1,1-bis (bis such hydroxyphenyl) cyclohexane (Hydroxyphenyl) C _4-10 cycloalkane and the like); alkylene oxide adducts of the bisphenols (for example, C _2-3 alkylene oxide adducts such as ethylene oxide adducts of bisphenols) and the like. These diol components (A2) may be used alone or in combination of two or more.

Of the diol component (A2), the aliphatic diol component (A2-1) or the alicyclic diol component (A2-2), particularly at least the aliphatic diol component (A2-1) (C _2-6 alkanediol, etc.) Of alkanediols). When the diol component (A1) and the aliphatic diol component (A2-1) are combined, esterification can be performed efficiently, and polyester poly (meth) acrylate having a good balance between high refractive index and flexibility is obtained. Can be obtained.

  The diol component (A) preferably contains at least the fluorenediol component (A1). As described above, the diol component (A) may further contain an aliphatic diol component (A2-1) and / or an alicyclic diol component (A2-2) (for example, alkanediol). The ratio of the fluorenediol component (A1) and the other diol component (A2) (for example, alkanediol (A2-1)) is the former / the latter (molar ratio) = 10/90 to 100/0 (for example, 30/70 to 95/5), for example, 50/50 to 100/0 (for example, 75/25 to 90/10), preferably 80/20 to 100/0 (for example, 80/20). ~ 90/10). Although depending on the composition of the dicarboxylic acid component (B) described later, if the diol component (A2) is too much, a high refractive index and flexibility in a cured product obtained by curing a curable composition containing polyester poly (meth) acrylate. There is a risk that both cannot be achieved.

  In addition, if a diol component (A) is a range which does not impair the effect of this invention, you may introduce | transduce a branched structure into polyester poly (meth) acrylate in combination with a polyol component. Examples of such a polyol component include a polyol component having 3 or more hydroxyl groups [eg, alkane polyol (eg, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, etc.)], You may use individually or in combination of 2 or more types. These polyol components may be added in small amounts [for example, 10 mol% or less (for example, 0.1 to 8 mol%, preferably 0.2 to 0.1% based on the total amount of the diol component (A) and the polyol component). About 5 mol%)] may be used.

  The proportion of each component in the diol component (A) may correspond to the proportion of the residue A (residue of each component) in the formula (1-1), and is the proportion in the reaction system (feeding ratio). It may correspond (hereinafter 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 fluorene carboxylic acid component (B1)).

(Full orange carboxylic acid component (B1))
The dicarboxylic acid component (B1) is a fluorenedicarboxylic acid such as 2,4-dicarboxyfluorene, 2,4-dicarboxy-9,9-dimethylfluorene, and 9,9-bis (carboxyaryl) capable of forming a cardo structure. Fluorene, for example, 9,9-bis (3-carboxyphenyl) fluorene, 9,9-bis (4-carboxyphenyl) fluorene, 9,9-bis (5-carboxy-1-naphthyl) fluorene, 9,9- Examples include 9,9-bis (carboxy C _6-12 aryl) fluorene such as bis (6-carboxy-2-naphthyl) fluorene, and ester-forming derivatives thereof. Typically, it may be a dicarboxylic acid represented by the following formula (3-1), a dicarboxylic acid represented by the following formula (3-2), and ester-forming derivatives thereof. These dicarboxylic acid components (B1) can be used alone or in combination of two or more.

(Wherein, X ^1a and X ^1b are each a divalent hydrocarbon group which may have a substituent, q represents an integer of 0 to ^4, and R ^4a and R ^4b , k1 and k2 are preferred embodiments. Including the same as above).

In the above formulas (3-1) and (3-2), the hydrocarbon group represented by the groups X ^1a and X ^1b is a linear or branched alkylene group such as a methylene group, an ethylene group, or trimethylene. C _1-8 alkylene groups (preferably linear or branched C _1-6 alkylene groups) such as a group, propylene group, 2-ethylethylene group, 2-methylpropane-1,3-diyl group it can.

  Examples of the substituent of the alkylene group include an aryl group (such as a phenyl group) and a cycloalkyl group (such as a cyclohexyl group).

X ^1a is often a linear or branched C _2-6 alkylene group, preferably a linear or branched C _2-4 alkylene group (eg, ethylene group, propylene group), and X ^1b is It is often a linear or branched C _1-6 alkylene group, preferably a linear or branched C _1-3 alkylene group (eg, methylene group, 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 an integer of 0 to 4, and may be usually 0 to 2, preferably 0 or 1.

In the formulas (3-1) and (3-2), the groups R ^4a and R ^4b , k1 and k2 include R ^4a and R ^4b , k1 and k2 described in the formula (2-1) including preferred embodiments. Is the same.

A typical compound represented by the formula (3-1) is a compound in which X ^1a is a C _2-6 alkylene group [for example, 9,9-bis (2-carboxyethyl) fluorene, 9,9-bis 9,9-bis (carboxy C _2-6 alkyl) fluorene etc. such as (2-carboxypropyl) fluorene etc.] and ester-forming derivatives thereof. A typical compound represented by the formula (3-2) is a compound in which q = 0 and X ^1b is a C _1-6 alkylene group [for example, 9- (1-carboxy-2-carboxyethyl) ) Fluorene; a compound in which q = 1 and X ^1b is a C _1-6 alkylene group, for example, 9- (dicarboxy C _2-6 alkyl) such as 9- (2-carboxy-3-carboxypropyl) fluorene ) Fluorene etc.] and their ester-forming derivatives.

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

Preferred dicarboxylic acid component (B1) includes compounds represented by the above formula (3-1), such as 9,9-bis (carboxyalkyl) fluorenes [for example, 9,9-bis (carboxy C _2-6). Alkyl) fluorene etc.] and the like.

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

(Dicarboxylic acid component (B2))
The other dicarboxylic acid component (B2) includes an aliphatic dicarboxylic acid component (B2-1), an alicyclic dicarboxylic acid component (B2-2), and an aromatic dicarboxylic acid component (B2-3). The dicarboxylic acid component (B) contains these dicarboxylic acid components (B2), so that the refractive index, flexibility and other properties (for example, optical properties such as birefringence, handling properties, mechanical properties) in the cured product. The balance of thermal properties, etc.).

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

Examples of the alicyclic dicarboxylic acid component (B2-2) include cycloalkane dicarboxylic acids (for example, C _5-10 cycloalkane-dicarboxylic acids such as 1.4-cyclohexanedicarboxylic acid); di- or tricycloalkanedicarboxylic acids Acids (eg, decalin dicarboxylic acid, norbornane dicarboxylic acid, adamantane dicarboxylic acid, tricyclodecane dicarboxylic acid, etc.); cycloalkene dicarboxylic acids (eg, C _5-10 cycloalkene-dicarboxylic acids such as cyclohexene dicarboxylic acid); Examples thereof include cycloalkene dicarboxylic acids (eg, norbornene dicarboxylic acid).

Examples of the aromatic dicarboxylic acid component (B2-3) include polycyclic aromatic dicarboxylic acids and monocyclic aromatic dicarboxylic acids. Examples of the polycyclic aromatic dicarboxylic acid include condensed polycyclic aromatic dicarboxylic acid [for example, naphthalenedicarboxylic acid (for example, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalene). Naphthalene dicarboxylic acid having two carboxyl groups in different rings such as dicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid; 1,2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, etc. Condensed polycyclic C _10-24 arene-dicarboxylic acid such as naphthalenedicarboxylic acid having two carboxyl groups in the same ring), anthracene dicarboxylic acid, phenanthrene dicarboxylic acid, etc., preferably condensed polycyclic C _10-16 arene- dicarboxylic acid, more preferably fused polycyclic C _{10 14} arene - such as dicarboxylic acid]; aryl array Nji carboxylic acid [e.g., biphenyl dicarboxylic acid (e.g., 2,2'-biphenyl dicarboxylic acid, 4,4'-biphenyl and di-carboxylic acids) _{C 6-10} aryl -C such _{6 -10} arene - such as dicarboxylic acid]; diaryl alkane dicarboxylic acid [for example, _{di-C 6-10} aryl _{-C 1-6} alkane such as diphenyl alkane dicarboxylic acids (e.g., such as 4,4'-diphenylmethane dicarboxylic acid) - dicarboxylic acid Etc.]; diaryl ketone dicarboxylic acids [for example, diC _6-10 aryl-ketone-dicarboxylic acids such as diphenyl ketone dicarboxylic acid (eg, 4.4′-diphenyl ketone dicarboxylic acid)] and the like. Examples of the monocyclic aromatic dicarboxylic acid include C ₆ such as phthalic acid, terephthalic acid, isophthalic acid, and alkyl isophthalic acid (for example, C _1-4 alkyl-isophthalic acid such as 4-methylisophthalic acid). _-10 arene-dicarboxylic acid and the like. Moreover, the ester-forming derivative of the dicarboxylic acid illustrated above is also 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). Can be used. Preferable components include, 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 arene-dicarboxylic acid (preferably C _6-14 arene-dicarboxylic acid, more preferably C _6-10 arene-dicarboxylic acid). The dicarboxylic acid component (B2) may usually contain at least an aliphatic dicarboxylic acid component (B2-1) and / or an alicyclic dicarboxylic acid component (B2-2).

  The ratio of the full orange carboxylic acid component (B1) to the other dicarboxylic acid component (B2) is in 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 50/50 to 100/0 (for example, 60/40 to 85/15), and more preferably 70. It may be about / 30 to 80/20.

  The dicarboxylic acid component (B) includes at least one selected from the aliphatic dicarboxylic acid component (B2-1), the alicyclic dicarboxylic acid component (B2-2), and the aromatic dicarboxylic acid component (B2-3). Is preferred. The aromatic dicarboxylic acid component (B2-3) may contain a dicarboxylic acid component (B1) having a fluorene skeleton. In addition, only one of the full orange carboxylic acid component (B1) or the other dicarboxylic acid component (B2) may be included, or both may be included.

  The amount of the full orange carboxylic acid component (B1) or other dicarboxylic acid component (B2) used is in the range of about 20 to 100 mol% (for example, 30 to 100 mol%) with respect to the total dicarboxylic acid component (B). For example, 50 to 100 mol% (eg 60 to 99 mol%), preferably 70 to 100 mol% (eg 75 to 99 mol%), more preferably 80 to 100 mol% (eg 85 (About -98 mol%) may be sufficient. In other words, the ratio of the full 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). / 90) or a range of about 80/20 to 20/80 (for example, 75/25 to 25/75).

  In addition, as long as the dicarboxylic acid component (B) is a range which does not impair the effect of this invention, it may combine with a polycarboxylic acid component and introduce | transduce a branched structure into polyester poly (meth) acrylate. Examples of such polycarboxylic acid components include polycarboxylic acid components having three or more carboxyl groups (for example, aromatic polycarboxylic acids such as trimellitic acid and pyromellitic acid, and ester-forming derivatives thereof). Can be illustrated. These may be added in small amounts [for example, 10 mol% or less (for example, 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). May be used.

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

  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 the diol component (A) and the dicarboxylic acid component (B) The total amount of the component (A1) and the full orange carboxylic acid component (B1) is, for example, 10 mol% or more (for example, 30 mol% or more) with respect to the total amount of the diol component (A) and the dicarboxylic acid component (B), Preferably, it may be about 50 mol% or more (for example, 70 mol% or more), more preferably about 75 mol% or more (for example, 90 mol% or more). When there are too few components which have a fluorene skeleton, there exists a possibility that it may become impossible to make high refractive index and a softness | flexibility in cured | curing material compatible.

  In a preferred embodiment, the diol component (A) includes at least a fluorenediol component (A1), and the dicarboxylic acid component (B) includes a fluorenedicarboxylic carboxylic acid component (B1), an aliphatic dicarboxylic acid component (B2-1), and an alicyclic group. It contains at least one dicarboxylic acid component selected from the dicarboxylic acid component (B2-2) and the aromatic dicarboxylic acid component (B2-3). The dicarboxylic acid component (B) may contain a dicarboxylic acid component having at least one aromatic hydrocarbon ring selected from the full orange carboxylic acid component (B1) and the 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 ( A2-1) may be contained, and the dicarboxylic acid component (B) may contain a fluorenedicarboxylic acid component (B1) and / or an aliphatic dicarboxylic acid component (B2-1). A compound having a high refractive index can be prepared by utilizing esterification of a diol component (A) containing at least a fluorenediol component (A1) and a dicarboxylic acid component (B) containing at least a fluorenedicarboxylic carboxylic acid component (B1). . In addition, when the aromatic dicarboxylic acid component (B2-3) is used, a decrease in refractive index can be suppressed and heat resistance can be improved.

[Production method and characteristics of polyester poly (meth) acrylate]
A polyester polyol is produced by the reaction of the diol component (A) and the dicarboxylic acid component (B). A typical polyester polyol is a polyester diol represented by the following formula (1-2) and having a hydroxyl group at the terminal.

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

  The polyester polyol (or polyester polyol composition) represented by the formula (1-2) can be used as various polyol components (particularly, diol components). For example, polyester resins, polyurethane resins (polyurethane (meta)) (Including oligopolyurethane resins such as acrylates), diol components of polycarbonate resins, etc., and high refractive index resins may be produced. In a preferred embodiment, it is useful for preparing polyester poly (meth) acrylates utilizing hydroxyl groups.

  The polyester poly (meth) acrylate of the present invention represented by the above formula (1-1) includes a diol component (A), a dicarboxylic acid component (B), (meth) acrylic acid or an ester-forming derivative thereof (hereinafter referred to as “formula”). , (Meth) acrylic acid component (C)) and may be prepared by a one-step reaction in which the diol component (A) and the dicarboxylic acid component (B) are reacted (first). Stage reaction), a polyester having a hydroxyl group at the generated terminal represented by the above formula (1-2) (hereinafter sometimes referred to as polyester polyol or polyester polyol composition) and (meth) acrylic acid component (C) May be prepared (step 2 reaction) and prepared stepwise.

  When the esterification reaction of all components is carried out simultaneously (in a one-step reaction), di (meth) acrylate (compound with n = 0 in the formula (1-1)) not containing the dicarboxylic acid component (B) is also produced at the same time. , Which is preferable in terms of fewer steps. Usually, it may be prepared stepwise. In the stepwise reaction, the second stage reaction may be performed without isolating or purifying the first stage reaction product. Moreover, it is preferable to carry out stepwise because the reaction control is easy and the molecular weight distribution is narrow and the desired polyester poly (meth) acrylate can be obtained in high yield.

Specific examples of the (meth) acrylic acid or its ester-forming derivative ((meth) acrylic acid component (C)) include (meth) acrylic acid, (meth) acrylic acid lower alkyl ester (for example, (meth) acrylic acid (Meth) acrylic acid C _1-4 alkyl) such as methyl, ethyl (meth) acrylate), (meth) acrylic acid halide (for example, (meth) acrylic acid chloride, (meth) acrylic acid bromide, etc.), di (meth) ) Acrylic anhydride and the like. These may be used alone or in combination of two or more.

  In the esterification reaction, the ratio of the diol component (A) to 1 mol of the dicarboxylic acid component (B) is about 1 to 5 mol, preferably an excess mol, for example, 1.1 to 4 mol (for example, 1.2 to 3). Mol), preferably 1.3 to 2.5 mol (for example, 1.4 to 2 mol), more preferably about 1.5 to 2 mol (for example, 1.5 to 1.8 mol). Usually, it may be about 1.3 to 3 mol (for example, 1.5 to 2.5 mol). If the amount of the diol component (A) is too small, it may be difficult to produce a polyester having a terminal hydroxyl group. If the amount is too large, a large amount of unreacted diol component (A) tends to remain.

  Moreover, the usage-amount of a (meth) acrylic-acid component (C) is 0.8-10 mol with respect to 1 mol of hydroxyl groups of the produced | generated polyester polyol, Preferably it is an equimolar or more, for example, 1-5 mol, Usually , Excess moles, for example, about 1.1 to 3 moles (for example, 1.2 to 2 moles, particularly 1.2 to 1.5 moles) may be sufficient.

  In addition, according to the ratio of the diol component (A) to the dicarboxylic acid component (B) [for example, when the amount of the diol component (A) used is small], the polyester poly (meth) acrylate is added to the dicarboxylic acid component (B). It may have a free carboxyl group derived from it. Further, it is not necessary to esterify all the hydroxyl groups of the polyester polyol with the (meth) acrylic acid component (C), and the polyester poly (meth) acrylate has a free hydroxyl group derived from the diol component (A). It may be. Furthermore, the polyester poly (meth) acrylate may have a free carboxyl group and a free hydroxyl group. The acid value (or hydroxyl value) of the polyester poly (meth) acrylate may be, for example, about 0 to 50 mgKOH / g, preferably about 1 to 25 mgKOH / g, and more preferably about 3 to 10 mgKOH / g.

  A catalyst may be used for the esterification reaction. In addition to an acid catalyst and a base catalyst, the catalyst may be 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”, the acid component is a dicarboxylic acid, a dicarboxylic acid lower alkyl ester, or a dicarboxylic acid anhydride. Can use an acid catalyst suitably. The acid catalyst is not particularly limited, and examples thereof include strong acids (for example, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid), homo- or heteropoly acids (for example, tungstophosphoric acid, molybdophosphoric acid, tungstosilicic acid, molybdosilicic acid, etc.) Inorganic acids, organic acids such as sulfonic acids (alkanesulfonic acids such as methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, and arenesulfonic acids such as p-toluenesulfonic acid), Lewis acids (for example, boron trifluoride) Solid acid catalysts such as etherate and tin tetrachloride) and cation exchange resins. The acid catalysts may be used alone or in combination of two or more.

  The ratio of the catalyst is not particularly limited, and may be, for example, about 0.001 mol to 1 mol, preferably about 0.01 to 0.5 mol, with respect to 1 mol of the diol component (A).

  Moreover, when using an acid halide (especially acid chloride) for an acid component, in order to trap the hydrogen halide produced | generated by reaction, you may make it react in presence of a base. Examples of the base include metal hydroxides (alkali metal hydroxides such as sodium hydroxide and calcium hydroxide or alkaline earth metal hydroxides), metal carbonates (alkali carbonates such as sodium carbonate and sodium hydrogen carbonate). Inorganic bases such as metal or alkaline earth metal salts), amines (trialkylamines such as triethylamine, aromatic tertiary amines such as benzyldimethylamine, heterocyclic tertiary amines such as pyridine), etc. An organic base etc. are mentioned. The bases may be used alone or in combination of two or more.

  Although the usage-amount of a base is not specifically limited, For example, with respect to 1 mol of acid halides, for example, 0.8-20 mol (for example, 1-10 mol), Preferably it is 1.2-5 mol, More preferably About 1.5-3 mol may be sufficient.

  The reaction may be performed in the presence of a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include benzoquinone, hydroquinones (eg, hydroquinone, hydroquinone monomethyl ether, p-tert-butylhydroquinone, p-benzoquinone, etc.), catechols (eg, p-tert-butylcatechol etc.), amines ( Examples thereof include 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 0.01 to 1 part by weight with respect to 100 parts by weight of the (meth) acrylic acid component (C).

  The reaction may be performed in the presence of a solvent. Examples of the solvent include hydrocarbons (aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene, toluene, and xylene), halogenated hydrocarbons (methylene chloride, chloroform, carbon tetrachloride). Etc.), ethers (dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran), ketones (acetone, methyl ethyl ketone, etc.), sulfoxides (dimethyl sulfoxide, etc.), nitriles (eg acetonitrile, etc.), etc. It is done. The solvents may be used alone or in combination of two or more.

  The reaction temperature and reaction time can be appropriately selected according to the type of raw material used, and the reaction system containing the (meth) acrylic acid component (C) can be carried out at a relatively low temperature. The reaction temperature is not particularly limited. For example, in the first-stage reaction of the stepwise esterification reaction (reaction not including the (meth) acrylic acid component (C)), it 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, the temperature is slightly low, for example, 0 to 130 ° C. (for example, 0 to 120 ° C.), preferably 25 to 100. C., more preferably about 50 to 80.degree.

  The reaction may be performed at the reflux temperature. The reaction can be performed in air or in an inert atmosphere (nitrogen, rare gas, etc.) with stirring, and may be performed under normal pressure, increased pressure, or reduced pressure. Further, in order to effectively prevent unexpected polymerization during the reaction, the reaction may be performed while blowing air into the reaction solution.

  The produced compound (polyester having a hydroxyl group at the end represented by the formula (1-2) or the polyester poly (meth) acrylate of the present invention represented by the formula (1-1)) is commonly used. For example, it may be separated and purified by separation means such as filtration, reprecipitation with a poor solvent, concentration, extraction, crystallization, recrystallization, column chromatography, etc., or a separation means combining these.

  The weight average molecular weight (Mw) of the obtained polyester poly (meth) acrylate of the present invention measured by gel permeation chromatography (GPC) in terms of polystyrene is, for example, 400 to 15000 (for example, 600 to 12000). It may be selected from the range of 800 to 10,000 (for example, 1000 to 7500), more preferably about 1200 to 6000 (for example, 1500 to 5000).

  Moreover, molecular weight distribution (Mw / Mn) of the polyester poly (meth) acrylate of this invention can be selected from the range of 1.0-10 (for example, 1.1-7), for example.

  When measured using a differential scanning calorimeter (DSC), the glass transition temperature (Tg) of the polyester poly (meth) acrylate of the present invention can be selected from the range of −60 ° C. to 300 ° C., preferably −40. -250 degreeC, More preferably, about -20-200 degreeC may be sufficient.

  Usually, at room temperature, the polyester poly (meth) acrylate of the present invention is highly viscous or solid and may not be measured with 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, in the range of 1000 to 30000 mPa · s (for example, 2000 to 9000 mPa · s). Preferably, it is 3000-8500 mPa * s (for example, 4000-8000 mPa * s), More preferably, it may be about 5000-7500 mPa * s (for example, 6000-7000 mPa * s).

Moreover, the refractive index (temperature 25 degreeC, wavelength 589nm) of the polyester poly (meth) acrylate (unhardened | cured material) of this invention is 1.55-1.73 (for example, 1.56-1.65), for example. It can be selected from a range, and may be about 1.57 to 1.64 (for example, 1.58 to 1.63), preferably about 1.585 to 1.62 (for example, 1.59 to 1.61). 1.55 to 1.7 (for example, 1.57 to 1.63). In particular, a compound in which rings Z ¹ and Z ² are condensed polycyclic hydrocarbon rings (polyester poly (meth) acrylate) exhibits a 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 in the range of 1.53 to 1.75 (for example, 1.56 to 1.72), for example, 1.56 to 1.73 (for example, 1.57 to 1.72). 1.68), preferably 1.62 to 1.70 (for example, 1.63 to 1.67), more preferably about 1.63 to 1.70 (for example, 1.64 to 1.67). May be.

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

The polymerizable compound may be N-vinylpyrrolidone or the like, and examples of the monofunctional (meth) acrylate include alkyl (meth) acrylate [for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) ) _C1-20 alkyl (meth) acrylate such as acrylate], hydroxyalkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, cyclohexyl (meth) acrylate, aryl (meth) 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, etc. B) Alkyl (meth) acrylate (for example, phenoxyethoxyethyl (meth) acrylate), alkylaryloxy ((poly) alkoxy) alkyl (meth) acrylate (for example, nonylphenoxy (poly) ethoxyethyl (meth) acrylate) , Arylaryl (oxy ((poly) alkoxy) alkyl) (meth) acrylate (for example, 2- (o-phenylphenoxy) ethyl (meth) acrylate, phenylphenoxy (poly) ethoxyethyl (meth) acrylate, etc.); sulfur atom (Meth) acrylates [eg, alkylthio (meth) acrylates (eg, methylthio (meth) acrylates, etc.), arylthio (meth) acrylates (eg, phenylthio (meth) acrylates, etc.), arals Kirthio (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, etc.), N, N-dialkylaminoalkyl (meth) acrylate (eg, N, N-dimethylaminoethyl (meth) acrylate etc.), bisphenols or their monooxides of alkylene oxide adducts ( Examples include (meth) acrylate (eg, mono (meth) acrylate of ethylene oxide adduct of bisphenol A), (meth) acrylate having a fluorene skeleton (eg, 9- (meth) acryloyloxymethylfluorene), and the like. .

As the polyfunctional (meth) acrylate, bifunctional (meth) acrylate [for example, C _2-10 alkylene glycol di (meth) acrylate such as ethylene glycol di (meth) acrylate and butanediol di (meth) acrylate, diethylene glycol Poly (alkylene glycol) di (meth) acrylate such as di (meth) acrylate, di (meth) acrylate of bisphenol A (or its alkylene oxide adduct), trifunctional or higher (meth) acrylate [for example, trimethylolpropane tri (Meth) acrylate, pentaerythritol tri (meth) acrylate, triol such as pentaerythritol tetra (meth) acrylate or tetraol tri or tetra (meth) acrylate], oligo (meth) acrylate Rate [urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate not belonging to the category of the polyester poly (meth) acrylate of the present invention], etc.], (meth) acrylate having a fluorene skeleton {for example, 9,9 -Bis [4- (2- (meth) acryloyloxy (poly) ethoxy) phenyl] fluorene etc.} and the like. 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. This polymerization initiator may be a thermal polymerization initiator (thermal radical generator) or a photopolymerization initiator (photo radical generator).

  Examples of the thermal polymerization initiator include organic peroxides [dialkyl peroxides (for example, di-tert-butyl peroxide), diacyl peroxides (for example, lauroyl peroxide, benzoyl peroxide, etc.), peracids (or Peracid esters) (eg, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peracetate, etc.) ketone peroxides, peroxycarbonates, peroxyketals], azo compounds [eg, 2,2 ′ -Azonitrile compounds such as 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 include benzoins (benzoin alkyl ethers such as benzoin and benzoin ethyl ether), acetophenones (acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, etc.), Aminoacetophenones {2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoaminopropanone-1 etc.}, anthraquinones (anthraquinone, 2-methylanthraquinone etc.), thioxanthones (2,4-dimethyl) Examples include thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone), ketals (acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.), benzophenones (benzophenone, etc.), xanthones, and the like. These photopolymerization initiators may be used alone or in combination of two or more.

  The amount of the polymerization initiator (heat or photopolymerization initiator) used is 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight (for example, 1) with respect to 100 parts by weight of the total amount of the (meth) acrylate component. ~ 8 parts by weight), more preferably about 2-5 parts by weight.

  The photopolymerization initiator may be combined with a photosensitizer. As photosensitizers, tertiary amines {eg, trialkylamines, trialkanolamines (such as triethanolamine), ethyl N, N-dimethylaminobenzoate [such as ethyl p- (dimethylamino) benzoate] Dialkylaminobenzoic acid alkyl esters such as amyl N, N-dimethylaminobenzoate [amyl amyl p- (dimethylamino) benzoate], and bis (dialkylamino) benzophenones such as 4,4-bis (diethylamino) benzophenone, 4 Conventional photosensitizers such as dialkylaminobenzophenone such as-(dimethylamino) benzophenone} and the like. These photosensitizers may be used alone or in combination of two or more.

  The use amount of the photosensitizer may be 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 contain a solvent. It does not specifically limit as a solvent, In addition to the solvent illustrated in the said esterification reaction, ester (for example, ethyl acetate etc.) etc. can be illustrated. These solvents can be used alone or in combination of two or more.

  Furthermore, the curable composition may be prepared by using conventional additives such as colorants, stabilizers (thermal stabilizers, antioxidants, ultraviolet absorbers, etc.), fillers, antistatic agents, flame retardants, surfactants, A plasticizer or the like may be included. These additives can be used alone or in combination of two or more.

[Cured product]
The curable composition of this invention hardens | cures easily by providing active energy (active energy ray), and produces | generates hardened | cured material. As the activation energy, thermal energy and / or light energy (ultraviolet ray, X-ray, electron beam, etc.) is useful.

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

Moreover, when irradiating light (for example, 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 is 100-. It may be about 5000 mJ / cm ² (for example, 500 to 3000 mJ / cm ² ).

  Curing may be performed in air or in an inert gas atmosphere (for example, nitrogen, rare gas, etc.).

  The cured product is excellent in flexibility because the polyester poly (meth) acrylate has a predetermined polyester structure, and also has high optical properties such as a high refractive index derived from the 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 obtain a curable composition, which is irradiated with ultraviolet rays (500 mJ). / cm ² ) 4 times, the refractive index (temperature 25 ° C., wavelength 589 nm) of the prepared cured product is, for example, in the range of about 1.5 to 1.75 (eg, 1.55 to 1.65). 1.57-1.70 (e.g., 1.57-1.64), preferably 1.58-1.68 (e.g., 1.58-1.64), more preferably 1.6- It may be about 1.67 (for example, 1.6 to 1.63), 1.61 to 1.73 (for example, 1.61 to 1.62), preferably 1.62 to 1.72 ( For example, 1.62-1.665), more preferably .63～1.70 (e.g., 1.64 to 1.68) may be about.

  The Shore D hardness (measurement method based on JIS K7215) of the said hardened | cured material can be selected from the range of about 20-80 (for example, 25-75), for example, Preferably it is 30-70 (for example, 40-67). More preferably, it may be about 50 to 65 (for example, 60 to 63).

Moreover, the glass transition temperature (Tg) of the said hardened | cured material measured using the differential scanning calorimeter (DSC) can be selected from the range of -60 degreeC-150 degreeC (for example, -60 degreeC-120 degreeC), for example. -40 ° C to 130 ° C (eg, -40 ° C to 80 ° C), preferably -20 ° C to 120 ° C (eg, -20 ° C to 40 ° C), and usually 10 to 150 ° C ( For example, 30-130 ° C), preferably 40-125 ° C (eg, 50-120 ° C), more preferably 60-120 ° C (eg, 70-115 ° C), particularly 70-120 ° C (eg, 80-120 ° C). 115 ° C.). Incidentally, the cured product of the polyester poly (meth) acrylate ring ^{Z 1} and ^{Z 2} is a fused polycyclic hydrocarbon ring, high glass transition temperature (Tg), for example, 90 to 130 ° C. (e.g., 95-120 ° C. ) Degree Tg. Despite 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 having a one-dimensional structure, a cured product having a two-dimensional structure, for example, a cured film (for example, a film), or the like, and a cured product having a three-dimensional structure (for example, a lens). Or prism).

  The cured product can be formed by various methods, and the forming method is not particularly limited. For example, the cured film is formed by using the curable composition as a base material or a substrate [for example, metal (such as aluminum), ceramics (silicon, titania). It is applied to inorganic materials such as glass, quartz, 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 then cured You may form by giving a process. Further, the cured product having the tertiary 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. In addition, the evaluation method is shown below.

(Average molecular weight, molecular weight distribution, number of repeating units n)
Using gel permeation chromatography (GPC) (manufactured by Tosoh Corporation, HLC-8120GPC), the sample was dissolved in chloroform, and the average molecular weight and polystyrene conversion were performed under the conditions of a temperature of 30 ° C. (flow rate: 0.085 mL / min). Its molecular weight distribution was measured. The number of repeating units n was calculated from the area ratio of the obtained GPC chart.

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

The sample (cured product) was curable by mixing polyester poly (meth) acrylate (100 parts by weight) and Irgacure 184 (manufactured by BASF Japan Ltd.) (3 parts by weight) as a photopolymerization initiator. A composition was prepared, and the coating film of this curable composition was cured by repeatedly irradiating ultraviolet rays (500 mJ / cm ² ) four times to prepare a cured film as a sample.

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

(Flexibility or flexibility)
The cured film was bent at an angle of 90 ° against the end of the angle of 90 °, and whether the cured film was cracked or not was observed, and the flexibility or flexibility of the cured film was evaluated according to the following criteria.

○: Cracks do not occur in the cured film ×: Cracks occur in the cured film

( Reference 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 BPEF) , FDP) (103 mmol) is dissolved in toluene (solvent) (270 mL), paratoluenesulfonic acid (catalyst) (31 mmol) is added, and the mixture is reacted at a reaction temperature of 115 ° C. for 5 hours under a nitrogen atmosphere. It was. 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 the mixture was reacted at a reaction temperature of 115 ° C. for 6 hours. After the completion of the reaction was confirmed by high performance liquid chromatography (HPLC), the reaction solution was neutralized and purified by washing with water to obtain 48.5 g of a transparent and viscous polyester diacrylate.

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

( Reference Example 2)
Reference Example BPEF using 168 mmol in 1 step (1), except that 84 mmol use acrylic acid in the step of Reference Example 1 (2), in the same manner as in Reference Example 1, a transparent viscous polyester diacrylates 49.7 g was obtained.

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

( Reference Example 3)
Reference Example BPEF using 177 mmol in 1 step (1), except that 71 mmol use acrylic acid in the step of Reference Example 1 (2), in the same manner as in Reference Example 1, a transparent viscous polyester diacrylates Got.

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

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

90 mmol of BPEF-9EO instead of BPEF in step (1) of Reference Example 1, using 50 mmol of FDP, except that 110 mmol use acrylic acid in Step (2) of Reference Example 1, the same manner as in Reference Example 1 Thus, a transparent and viscous polyester diacrylate was obtained.

  The obtained polyester diacrylate had a weight average molecular weight (Mw) of 4235 and a molecular weight distribution (Mw / Mn) of 1.93.

( Reference Example 5)
Step (1) in place of BPEF in BPEF-9EO 100 mmol Reference Example 1, adipic acid using 56 mmol instead of FDP, except that 123 mmol use acrylic acid in the step of Reference Example 1 (2), In the same manner as in Reference Example 1, a transparent and viscous polyester diacrylate was obtained.

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

( Reference Example 6)
Same as Reference Example 1, except that 100 mmol of BPEF was used in Step (1) of Reference Example 1, 55 mmol of adipic acid was used instead of FDP, and 123 mmol of acrylic acid was used in Step (2) of Reference Example 1. Thus, a transparent and viscous polyester diacrylate was obtained.

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

(Example 7)
(Synthesis of BNEF)
Into a 1 L separable flask, 45 g of 9-fluorenone (0.25 mol, manufactured by Osaka Gas Chemical Co., Ltd.), 188 g (1 mol) of ethylene glycol mono (2-naphthyl) ether, and 1 g of 3-mercaptopropionic acid are charged. The solution was heated to 60 ° C. and completely dissolved. When 54 g of sulfuric acid was gradually added to the resulting mixture and stirred for 5 hours while maintaining 60 ° C., it was confirmed by HPLC (high performance liquid chromatography) that the conversion of 9-fluorenone was 99% or more. did. The obtained reaction solution was neutralized by adding 48% aqueous sodium hydroxide, then 400 g of xylene was added, 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-hydroxyethoxy) -2-naphthyl] fluorene (BNEF) was obtained as crystals. When the HPLC purity of the obtained crystal was measured, the purity was 98.3%. The obtained crystal was confirmed to be 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene (BNEF) by ¹ H-NMR and mass spectrum.

Reference Example 1 except that 100 mmol of BNEF was used instead of 155 mmol of BPEF in Step (1) of Reference Example 1, 55 mmol of FDP was used, and 122 mmol of acrylic acid was used in Step (2) of Reference Example 1. Similarly, a transparent and viscous polyester diacrylate was obtained.

  The obtained polyester diacrylate had a weight average molecular weight (Mw) of 2253 and a molecular weight distribution (Mw / Mn) of 2.23.

(Example 8)
In step (1) of Reference Example 1, BPEF was changed to 155 mmol, BNEF was used at 100 mmol, FDP was added at 103 mmol, and adipic acid was added at 55 mmol, and in Reference Example 1 step (2), 122 mmol of acrylic acid was added. A transparent and viscous polyester diacrylate was obtained in the same manner as in Reference Example 1 except that it was used.

  The obtained polyester diacrylate had a weight average molecular weight (Mw) of 1759 and a molecular weight distribution (Mw / Mn) of 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, a novel polyester poly (meth) acrylate having excellent flexibility or flexibility and a high refractive index was obtained.

Since the polyester poly (meth) acrylate of the present invention is excellent in properties such as high refractive index and flexibility, it can be used in various applications such as light emitting materials (for example, light emitting materials for organic EL), organic semiconductors, graphitization. Precursors, gas separation membranes (for example, CO ₂ gas separation membranes), ink materials, paints, printing inks, coating agents (for example, coating agents for LED (light emitting diode) elements, optical overcoat agents or hard coats) Agent), lens [pickup lens (eg, pickup lens for DVD (digital versatile disc)), microlens (eg, microlens for liquid crystal projector), spectacle lens, etc.), polarizing film (eg, liquid crystal display) Polarizing film), antireflection film (or antireflection film, for example, display device) Anti-reflection film), touch panel film, flexible substrate film, display film [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), cathode ray tube, film for electronic paper (particularly thin display) (filter, protective film, etc.)], fuel cell membrane, optical fiber, optical It can be suitably used for a wide range of applications such as waveguides, holograms, UV curable CFRP, and power semiconductor encapsulation. In particular, the polyester poly (meth) acrylate of the present invention can be suitably used as an optical material. Examples of the shape of such an optical material include a film or sheet shape, a plate shape, a lens shape, and a tubular shape.

Claims (13)

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 residues of the diol component (A) and the dicarboxylic acid component (B), respectively)
A in the polyester poly (meth) acrylate represented, the diol component (A) comprises a diol component (A1) having a fluorene skeleton, the diol component (A1) is, at least the following formula (2-1) Polyester poly (meth) acrylate containing a diol component represented .

( Wherein Z ¹ and Z ² are each a polycyclic aromatic hydrocarbon ring, R ^2a and R ^2b are each an alkylene group, m 1 and m 2 are each an integer of 0 or more, and R ^3a and R ^3b are each not reactive. Active substituents, p1 and p2 are each an integer of 0 or more, R ^4a and R ^4b are each an inert substituent for the reaction, and k1 and k2 each are an integer of 0 to 4. In formula (2-1),
Z ¹ and Z ² are fused polycyclic aromatic hydrocarbon rings,
R ^2a and R ^2b are linear or branched alkylene groups,
m1 and m2 are integers from 0 to 10,
R ^3a and R ^3b are alkyl groups,
polyester poly (meth) acrylate according to claim 1, wherein p1 and p2 is an integer of 0-4. In formula (2-1),
A Z ¹ and Z ² Gana Futaren ring and aromatic hydrocarbon ring selected from a biphenyl ring,
R ^2a and R ^2b are linear or branched C _2-6 alkylene groups,
m1 and m2 are integers from 0 to 5,
R ^3a and R ^3b are methyl groups,
polyester poly (meth) acrylate according to claim 1, wherein p1 and p2 is an integer of 0 to 2. The diol component (A) further comprises at least one diol component (A2) selected from the aliphatic diol component (A2-1), the alicyclic diol component (A2-2) and the aromatic diol component (A2-3). 4) The polyester poly (meth) acrylate according to any one of claims 1 to 3 . At least one dicarboxylic acid in which the dicarboxylic acid component (B) is selected from the aliphatic dicarboxylic acid component (B2-1), the alicyclic dicarboxylic acid component (B2-2), and the aromatic dicarboxylic acid component (B2-3) And the aromatic dicarboxylic acid component (B2-3) includes a dicarboxylic acid component (B1) having a fluorene skeleton,
The dicarboxylic acid component (B1) is at least one 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. The polyester poly (meth) acrylate according to any one of claims 1 to 4 .

(Wherein, X ^1a and X ^1b are each a divalent hydrocarbon group which may have a substituent, q represents an integer of 0 to ^4, and R ^4a and R ^4b , k1 and k2 are the same as above. ). Dicarboxylic acid component (B), the formula ^(3-1), the dicarboxylic acid ^{X 1a} is a linear or branched _{C 1-6} alkylene _{group, C 2-12} alkanoic - dicarboxylic _{acids, C 5- 10} cycloalkane - dicarboxylic acids, C _6-24 arene - dicarboxylic acids and polyester poly (meth) acrylates according to any one of claims 1 to 5 including at least one dicarboxylic acid component selected from ester-forming derivatives thereof . The amount of the dicarboxylic acid component having a fluorene skeleton (B1) or another dicarboxylic acid component (B2) is, relative to the total dicarboxylic acid component (B), claim 1-6 which is 50 to 100 mol% Polyester poly (meth) acrylate described in 1. The polyester poly (meth) acrylate according to any one of claims 1 to 7 , wherein in the formula (1-1), the number of repeating units n 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 50 moles relative to the total amount of residues of the diol component (A) and the dicarboxylic acid component (B). polyester poly (meth) acrylates according to any of claims 1-8 or more percent. Following formula (1-2)

(Wherein n, A and B are the same as described in claim 1)
In a polyester polyol represented, the diol component (A) comprises a diol component (A1) having a fluorene skeleton, the diol component (A1) is, at least according to claim 1, wherein in formula (2-1) The polyester polyol containing the diol component represented . The diol component (A) and the dicarboxylic acid component (B) are reacted to form a polyester having a hydroxyl group at the terminal, the produced polyester is reacted with (meth) acrylic acid or an ester-forming derivative thereof, method of producing a polyester poly (meth) acrylates according to any of claims 1-9. Curable composition comprising a polyester poly (meth) acrylates according to any of claims 1-9. A cured product obtained by curing the curable composition according to claim 12 .