JP7362442B2 - Fluorene derivatives and their production methods and uses - Google Patents

Description

The present invention relates to a novel fluorene derivative (di(meth)acrylate) having a 9,9-bisarylfluorene skeleton, its production method and intermediate, and its uses, such as a curable composition containing the fluorene derivative and its curing. Concerning things, etc.

Compounds having a 9,9-bisarylfluorene skeleton are often used as optical members due to their excellent properties such as optical properties and thermal properties. For example, JP 2018-90560 A (Patent Document 1) describes 9,9-bis[4-hydroxy-3-phenyl-5-(phenyl C _1-4 alkyl) represented by the following formula (1). Compounds having a phenyl]fluorene skeleton and derivatives thereof, such as difunctional (meth)acrylate compounds corresponding to the above compounds, are disclosed.

(In the formula, R ₁ to R ₄ are the same or different and each represents an alkyl group, an aryl group, or a halogen atom, n ₁ and n ₂ are each the same or different and represent an integer of 1 to 4, and k ₁ to k ₄ are the same or different and represent 0 or an integer from 1 to 4. If at least one of k ₁ to k ₄ is 2 or more, the corresponding R ₁ to R ₄ may be the same or different. good).

Japanese Patent Application Publication No. 2018-90560

Patent Document 1 states that the compound represented by the above formula (1) has a uniquely low melting point and a high refractive index, and that the derivative (meth)acrylate compound has a high refractive index compared to conventional two. It is described that it exhibits a refractive index equal to or higher than that of functional (meth)acrylates, such as (meth)acrylate compounds having a fluorene skeleton or a binaphthyl skeleton. Furthermore, in the examples of Patent Document 1, 9,9-bis[4-hydroxy-3-phenyl-5-benzylphenyl]fluorene (Examples 1 and 2) and the difunctional (meth) The acrylate 9,9-bis[4-acryloyloxy-3-phenyl-5-benzylphenyl]fluorene (Example 5) has been synthesized.

However, although the bifunctional acrylate of Example 5 of Patent Document 1 exhibits a relatively high refractive index due to the fluorene skeleton, 9,9-bis[4 -Acryloyloxy-3-phenylphenyl]fluorene (Comparative Example 5), the refractive index nD at a wavelength of 589 nm is reduced by 0.011. That is, Patent Document 1 teaches that when a benzyl group is introduced into a conventional (meth)acrylate compound having a 9,9-bisarylfluorene skeleton as in Example 5, the refractive index is greatly reduced. Therefore, it may not be possible to use it for applications that require a higher refractive index.

Furthermore, in Patent Document 1, the resulting cured product tends to be brittle and has low scratch resistance (or flexibility), probably because the molecular structure is rigid.

Furthermore, the acrylate compound obtained in Example 5 of Patent Document 1 is difficult to handle because it is in powder form at room temperature, and dilution with a reactive diluent or solvent is required to form a cured product such as a photocured product. is essential, and it is difficult to form a cured product of the acrylate compound alone.

Therefore, an object of the present invention is to provide a novel fluorene derivative that has a high refractive index even when a molecular structure that is expected to lower the refractive index, a method for producing the same, an intermediate thereof, and uses thereof.

Another object of the present invention is to provide a diol compound (dihydroxy compound) that can impart high refractive index and heat resistance to a resin, a method for producing the same, and uses thereof.

As a result of intensive studies to achieve the above object, the present inventors have determined that a predetermined molecular structure having an alkylene group and an arene ring for the aryl group substituted at the 9,9-position in the 9,9-bisarylfluorene skeleton. The present invention was completed based on the discovery that a surprisingly high refractive index can be obtained by introducing ether through an ether bond.

That is, the novel compound of the present invention is represented by the following formula (1).

(In the formula,
R ¹ represents a substituent, k represents an integer of 0 to 8,
Z ^1a and Z ^1b are the same or different from each other and represent an arene ring,
R ^2a and R ^2b are the same or different from each other and represent a substituent, m1 and m2 are the same or different from each other and represent an integer of 0 or more,
A ^1a and A ^1b are the same or different from each other and represent a linear or branched alkylene group, n1 and n2 are the same or different from each other and represent an integer of 0 or more,
Z ^2a and Z ^2b are the same or different from each other and represent an arene ring,
R ^3a and R ^3b are the same or different from each other and represent a substituent, p1 and p2 are the same or different from each other and represent an integer of 0 or more,
A ^2a and A ^2b are the same or different from each other and represent a linear or branched alkylene group,
A ^3a and A ^3b are the same or different from each other and represent a linear or branched alkylene group, q1 and q2 are the same or different from each other and represent an integer of 0 or more,
R ^4a and R ^4b are the same or different and represent a hydrogen atom or a methyl group)

In the above formula (1),
Z ^1a and Z ^1b are the same or different from each other and represent a C _6-10 arene ring,
R ^2a and R ^2b are the same or different from each other and represent a hydrocarbon group, m1 and m2 are the same or different from each other and represent an integer from 0 to 4;
A ^1a and A ^1b are the same or different from each other and represent a linear or branched C _2-6 alkylene group, n1 and n2 are the same or different from each other and represent an integer from 0 to 10,
Z ^2a and Z ^2b are the same or different from each other and represent a C _6-10 arene ring,
R ^3a and R ^3b are the same or different from each other and represent a hydrocarbon group, p1 and p2 are the same or different from each other and represent an integer from 0 to 4,
A ^2a and A ^2b are the same or different from each other and represent a linear or branched C _1-4 alkylene group,
A ^3a and A ^3b are the same or different from each other and represent a linear or branched C _2-6 alkylene group, and q1 and q2 are the same or different from each other and represent an integer of 0 to 10; Good too.

Moreover, in the above formula (1),
Z ^1a and Z ^1b are the same or different from each other and represent a benzene ring or a naphthalene ring,
R ^2a and R ^2b are the same or different from each other and represent an alkyl group or an aryl group, m1 and m2 are the same or different from each other and represent an integer from 0 to 2,
A ^1a and A ^1b are the same or different from each other and represent a linear or branched C _2-4 alkylene group, n1 and n2 are the same or different from each other and represent 0 or 1,
Z ^2a and Z ^2b are the same or different from each other and represent a benzene ring,
R ^3a and R ^3b are the same or different from each other and represent an alkyl group or an aryl group, p1 and p2 are the same or different from each other and represent an integer from 0 to 2,
A ^2a and A ^2b are the same or different from each other and represent a C _1-2 alkylene group,
A ^3a and A ^3b are the same or different from each other and represent a linear or branched C _2-4 alkylene group, and q1 and q2 are the same or different from each other and may represent 0 or 1. .

The present invention includes a curable composition containing the above compound, and a cured product obtained by curing the curable composition.

The present invention also includes a novel compound represented by the following formula (2).

(In the formula,
R ¹ represents a substituent, k represents an integer of 0 to 8,
Z ^1a and Z ^1b are the same or different from each other and represent an arene ring,
R ^2a and R ^2b are the same or different from each other and represent a substituent, m1 and m2 are the same or different from each other and represent an integer of 0 or more,
A ^1a and A ^1b are the same or different from each other and represent a linear or branched alkylene group, n1 and n2 are the same or different from each other and represent an integer of 0 or more,
Z ^2a and Z ^2b are the same or different from each other and represent an arene ring,
R ^3a and R ^3b are the same or different from each other and represent a substituent, p1 and p2 are the same or different from each other and represent an integer of 0 or more,
A ^2a and A ^2b are the same or different from each other and represent a linear or branched alkylene group,
A ^3a and A ^3b are the same or different from each other and represent a linear or branched alkylene group, and q1 and q2 are the same or different from each other and represent an integer of 0 or more)

Furthermore, the present invention produces a compound represented by the formula (1) by reacting the compound represented by the formula (2) with the compounds represented by the following formulas (3a) and (3b). It also includes methods to do so.

(In the formula, R ^4a and R ^4b are the same as in formula (1) above, and R ^5a and R ^5b are the same or different and represent a hydroxyl group, an alkoxy group, or a halogen atom).

Note that in this specification and claims, the number of carbon atoms may be indicated as C ₁ , C ₆ , C ₁₀ , etc. For example, an alkyl group having 1 carbon number is represented by "C ₁ alkyl", and an aryl group having 6 to 10 carbon atoms is represented by "C _6-10 aryl".

The novel fluorene derivative of the present invention has a 9,9-bisarylfluorene skeleton and a predetermined molecular structure having an alkylene group and an arene ring for the aryl group substituted at the 9,9-position of this skeleton, and an ether. Because it has a bonded structure, it surprisingly has a high refractive index despite the introduction of a molecular structure that is expected to lower the refractive index. In addition, even if a rigid arene ring skeleton is introduced, the cured product maintains scratch resistance (or flexibility) (or does not significantly decrease), and has a high refractive index and high heat resistance. The compound has an excellent balance of scratch resistance (flexibility), high refractive index, and high heat resistance. Furthermore, when Z ^1a and Z ^1b are benzene rings, the fluorene derivative is liquid (or viscous) at room temperature, for example, around 25°C, and therefore does not need to be diluted with a reactive diluent or solvent. Even if it is not heated to an excessively high temperature, for example, even if it is slightly heated to about 120° C., it has excellent handleability (fluidity) or moldability, and a cured product can be easily formed. Generally, when a reactive diluent is used, it becomes difficult to obtain a cured product exhibiting a high refractive index and high heat resistance, and when diluted with a solvent, the applications may be limited. Further, the diol compound (dihydroxy compound) which is an intermediate of the fluorene derivative can impart high refractive index and heat resistance to the resin or resin composition by using it as a resin or monomer raw material, a resin additive, etc.

[Fluorene derivative]
The novel fluorene derivative (first polyfunctional (meth)acrylate) of the present invention is a compound represented by the following formula (1).

(In the formula,
R ¹ represents a substituent, k represents an integer of 0 to 8,
Z ^1a and Z ^1b are the same or different from each other and represent an arene ring,
R ^2a and R ^2b are the same or different from each other and represent a substituent, m1 and m2 are the same or different from each other and represent an integer of 0 or more,
A ^1a and A ^1b are the same or different from each other and represent a linear or branched alkylene group, n1 and n2 are the same or different from each other and represent an integer of 0 or more,
Z ^2a and Z ^2b are the same or different from each other and represent an arene ring,
R ^3a and R ^3b are the same or different from each other and represent a substituent, p1 and p2 are the same or different from each other and represent an integer of 0 or more,
A ^2a and A ^2b are the same or different from each other and represent a linear or branched alkylene group,
A ^3a and A ^3b are the same or different from each other and represent a linear or branched alkylene group, q1 and q2 are the same or different from each other and represent an integer of 0 or more,
R ^4a and R ^4b are the same or different and represent a hydrogen atom or a methyl group)

In the formula (1), the substituent (non-reactive substituent or non-radically polymerizable substituent) represented by R ¹ is, for example, a hydrocarbon group, specifically an alkyl group, an aryl group, etc.; Cyano group; halogen atom, specifically, fluorine atom, chlorine atom, bromine atom, etc. Examples of the alkyl group include linear or branched C _1-6 groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, and t-butyl group. Examples include alkyl groups. Examples of the aryl group include C _6-10 aryl groups such as phenyl group.

When k is 1 or more, among these groups R ¹ , alkyl groups, cyano groups, and halogen atoms are preferable, and alkyl groups are more preferable, especially linear or branched C _1-4 alkyl groups, In particular, a linear or branched C _1-3 alkyl group such as a methyl group is preferred.

The number k of substitutions in the group R ¹ is, for example, an integer of about 0 to 6, preferably an integer of 0 to 4, more preferably 0 to 2, more preferably 0 or 1, and especially 0. In addition, when k is 2 or more, the types of groups R ¹ may be the same or different. Furthermore, when the two benzene rings forming the fluorene ring are each substituted with the group R ¹ , the number of substitutions on each benzene ring may be the same or different. Furthermore, the substitution position of the group R ¹ is not particularly limited, and may be, for example, any of the 2- to 7-positions of the fluorene ring, specifically, the 2-, 3-, and/or 7-positions. etc.

Examples of the substituent (non-reactive substituent or non-radically polymerizable substituent) represented by R ^2a and R ^2b include a halogen atom, specifically a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. ; Hydrocarbon group or group [-R ^a ], specifically, an alkyl group, cycloalkyl group, aryl group, aralkyl group, etc.; Group [-OR ^a ] (wherein R ^a represents the hydrocarbon group); ), specifically, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, etc.; a group [-SR ^a ] (wherein R ^a represents the hydrocarbon group), specifically, Alkylthio group, cycloalkylthio group, arylthio group, aralkylthio group, etc.; Acyl group, specifically C _1-6 alkyl-carbonyl group such as acetyl group; Nitro group; Cyano group; Mono- or di-substituted amino group, Specific examples include dialkylamino group and bis(alkylcarbonyl)amino group.

Examples of the alkyl group represented by R ^a include linear or branched groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, and t-butyl group. Examples include linear C _1-10 alkyl groups, preferably linear or branched C _1-6 alkyl groups, and more preferably linear or branched C _1-4 alkyl groups. Examples of the cycloalkyl group represented by R ^a include C _5-10 cycloalkyl groups such as cyclopentyl group and cyclohexyl group. Examples of the aryl group represented by R ^a include C _6-12 aryl groups such as phenyl group, alkylphenyl group, biphenylyl group, and naphthyl group. Examples of the alkylphenyl group include mono- to tri-C _1-4 alkyl-phenyl groups such as methylphenyl group (tolyl group) and dimethylphenyl group (xylyl group). Examples of the aralkyl group represented by R ^a include C _6-10 aryl-C _1-4 alkyl groups such as benzyl group and phenethyl group.

Specific examples of the group [-OR ^a ] include groups corresponding to the examples of the hydrocarbon group R ^a . Examples of the alkoxy group include linear or branched C _1-10 alkoxy groups such as methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, and t-butoxy. Examples of the cycloalkyloxy group include C _5-10 cycloalkyloxy groups such as cyclohexyloxy group. Examples of the aryloxy group include C _6-10 aryloxy groups such as phenoxy group. Examples of the aralkyloxy group include C _6-10 aryl-C _1-4 alkyloxy groups such as benzyloxy group.

Specific examples of the group [-SR ^a ] include groups corresponding to the examples of the hydrocarbon group R ^a . Examples of the alkylthio group include C _1-10 alkylthio groups such as methylthio group, ethylthio group, propylthio group, n-butylthio group, and t-butylthio group. Examples of the cycloalkylthio group include C _5-10 cycloalkylthio groups such as cyclohexylthio group. Examples of the arylthio group include C _6-10 arylthio groups such as a thiophenoxy group. Examples of the aralkylthio group include C _6-10 aryl-C _1-4 alkylthio groups such as benzylthio group.

In the mono- or di-substituted amino group, the dialkylamino group includes, for example, a di-C _1-4 alkylamino group such as a dimethylamino group. Examples of the bis(alkylcarbonyl)amino group include bis(C _1-4 alkyl-carbonyl)amino groups such as diacetylamino group.

Among these groups R ^2a and R ^2b , typically hydrocarbon groups such as halogen atoms, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups, acyl groups, nitro groups, cyano groups, substituted Examples include amino groups. When m1 and m2 are 1 or more, preferred groups R ^2a and R ^2b include alkyl groups, specifically linear or branched C _1-6 alkyl groups such as methyl groups; aryl groups, specifically Specific examples include C _6-14 aryl groups such as phenyl groups; alkoxy groups, specifically linear or branched C _1-4 alkoxy groups such as methoxy groups; among them, alkyl groups, Aryl groups are preferred, particularly linear or branched C _1-4 alkyl groups such as methyl groups, and C _6-10 aryl groups such as phenyl groups. Note that when the groups R ^2a and R ^2b are aryl groups, the groups R ^2a and R ^2b may form a ring assembly arene ring, which will be described later, together with the rings Z ^1a and Z ^1b . Note that the type of group R ^2a and the type of group R ^2b may be the same or different from each other. When the number of substitutions m1 or m2 is 2 or more, the types of the two or more groups R ^2a or R ^2b substituted on the same ring Z ^1a or Z ^1b may be the same or different in each ring.

The numbers m1 and m2 of substitution of the groups R ^2a and R ^2b may be, for example, an integer of about 0 to 8, preferably an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2. is an integer of, more preferably 0 or 1, especially 1. Note that the number of substitutions m1 and the number of substitutions m2 may be the same or different from each other. The substitution positions of the groups R ^2a and R ^2b are not particularly limited, and include the bonding positions between the rings Z ^1a and Z ^1b and the 9-position of the fluorene ring, and the bonding positions between the rings Z ^1a and Z ^1b and the (meth)acryloyl group-containing group (i.e. , the group [-O-(A ^1a O) _n1 -Z ^2a (R ^3a ) _p1 -A ^2a -O-(A ^3a O) _q1 -C(=O)-CR ^4a =CH ₂ ] or the group [-O Substitution at a position other than the bonding position with -(A ^1b O) _n2 -Z ^2b (R ^3b ) _p2 -A ^2b -O-(A ^3b O) _q2 -C(=O)-CR ^4b =CH ₂ ]) Usually, it is often substituted at a position adjacent to the substitution position (ortho position) of the (meth)acryloyl group-containing group.

Examples of the arene ring (aromatic hydrocarbon ring) represented by Z ^1a and Z ^1b include a monocyclic arene ring such as a benzene ring, a polycyclic arene ring (polycyclic aromatic hydrocarbon ring), and the like. Examples of the polycyclic arene ring include a fused polycyclic arene ring (fused polycyclic aromatic hydrocarbon ring), a ring-assembled arene ring (a ring-assembled aromatic hydrocarbon ring), and the like.

Examples of fused polycyclic arene rings include fused bicyclic arene rings, specifically fused bicyclic C _10-16 arene rings such as naphthalene rings; fused tricyclic arene rings, specifically , fused di- to tetracyclic arene rings such as anthracene ring and phenanthrene ring. Preferred fused polycyclic arene rings include fused polycyclic C _10-16 arene rings such as naphthalene rings and anthracene rings, more preferably fused polycyclic C _10-14 arene rings, and particularly, A naphthalene ring is preferred.

Examples of ring assembly arene rings include biarene rings, specifically biC _6-12 arene rings such as biphenyl rings, binaphthyl rings, and phenylnaphthalene rings; terarene rings, specifically terphenylene rings, etc. An example is a C _6-12 arene ring. Examples of the phenylnaphthalene ring include a 1-phenylnaphthalene ring and a 2-phenylnaphthalene ring. Preferred ring assembly arene rings include biC _6-10 arene rings such as biphenyl ring, binaphthyl ring, and phenylnaphthalene ring, with biphenyl ring being particularly preferred.

In this specification and claims, a ring-assembled arene ring containing a fused polycyclic arene ring skeleton such as a naphthalene ring skeleton is classified as a ring-assembled arene ring.

The type of ring Z ^1a and the type of ring Z ^1b bonded to the 9-position of fluorene may be the same or different, and are usually the same. Among rings Z ^1a and Z ^1b , C _6-12 arene rings such as benzene ring, naphthalene ring, and biphenyl ring are preferred, and C _6-10 arene rings such as benzene ring and naphthalene ring are more preferred. A benzene ring is particularly preferred from the viewpoint of being able to improve a high refractive index and heat resistance in a well-balanced manner without greatly reducing scratch resistance (or flexibility), and from the viewpoint of being able to highly improve the refractive index and heat resistance. Fused polycyclic arene rings such as naphthalene rings are particularly preferred.

The substitution positions of rings Z ^1a and Z ^1b bonded to the 9-position of fluorene are not particularly limited. For example, when the rings Z ^1a and Z ^1b are naphthalene rings, the groups corresponding to the rings Z ^1a and Z ^1b bonded to the 9-position of fluorene may be a 1-naphthyl group, a 2-naphthyl group, etc., and are usually , 2-naphthyl group. In addition, when rings Z ^1a and Z ^1b are biphenyl rings, the groups corresponding to rings Z ^1a and Z ^1b bonded to the 9-position of fluorene are 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, etc. It is usually a 3-biphenylyl group.

The (meth)acryloyl group-containing group can be substituted at appropriate positions of rings Z ^1a and Z ^1b . When rings Z ^1a and Z ^1b are benzene rings, the (meth)acryloyl group-containing group is, for example, at the 2nd to 4th positions, preferably at the 3rd or 4th positions, and more preferably at the 4th position. When rings Z ^1a and Z ^1b are naphthalene rings, the (meth)acryloyl group-containing group is the 5- to 8-position naphthyl group (1-naphthyl group or 2-naphthyl group) substituted at the 9-position of the fluorene ring. It is often substituted with one of the following, usually in the 1st and 5th positions, the 2nd and 6th positions, and especially in the 2nd and 6th positions. When rings Z ^1a and Z ^1b are biphenyl rings, the (meth)acryloyl group-containing group is a biphenylyl group substituted at the 9-position of the fluorene ring, such as a 3-biphenylyl group, a 4-biphenylyl group, etc. It may be substituted on the ring bonded to the 9-position of the ring, or may be substituted on the adjacent benzene ring. When the 3-position of the biphenyl ring as rings Z ^1a and Z ^1b is bonded to the 9-position of fluorene, the (meth)acryloyl group-containing group is attached to the 2-position, 4-position, 5-position, 6-position, 2-position of the biphenyl ring. Substitution may be at any of the ', 3', and 4' positions, usually the 6, 3', and 4' positions, preferably the 6 or 4' positions, particularly the 6 position. There are many.

Examples of the linear alkylene group represented by A ^1a and A ^1b include linear C _2-6 alkylene groups such as ethylene group, trimethylene group, and tetramethylene group, preferably linear C _{2 -4} alkylene group, more preferably a linear C _2-3 alkylene group, especially ethylene group, and examples of branched alkylene group include propylene group, 1,2-butanediyl group, 1,3-butanediyl group Examples include branched C _3-6 alkylene groups such as, branched C _3-4 alkylene groups are preferred, and propylene groups are particularly preferred. Among these alkylene groups A ^1a and A ^1b , preferably, in the following steps, a linear or branched C _2-6 alkylene group, a linear or branched C _2-4 alkylene group, a linear or a branched C _2-3 alkylene group, of which ethylene and propylene groups are preferred, with ethylene group being particularly preferred.

In addition, in the two (poly)oxyalkylene groups [-(OA ^1a ) _n1 -] and [-(OA ^1b ) _n2 -] substituted on rings Z ^1a and Z ^1b , the type of group A ^1a and the group A ^1b are The types may be the same or different, and are usually the same. Further, when the repeating numbers n1 and n2 are each 2 or more, the types of the two or more groups A ^1a or A ^1b forming the same polyoxyalkylene group may be different from each other, but they are the same. There are many things.

The repeating numbers n1 and n2 of the oxyalkylene group (OA ^1a ) and the oxyalkylene group (OA ^1b ) may be selected, for example, from integers in the range of about 0 to 20, respectively, and the preferable ranges are as follows: , 0-15, 0-10, 0-8, 0-5, 0-3, 0-2, 0-1, and is often 0.

Further, in each of the (poly)oxyalkylene groups substituted on the rings Z ^1a and Z ^1b , n1 and n2 may be the same or different from each other. Note that the repeating numbers n1 and n2 may be an average value (or an arithmetic average value, an arithmetic average value), that is, an average number of added moles, and the range thereof is the same as the range of the above-mentioned integer including preferred embodiments. be.

In addition, the total number of repeating numbers n1 and n2 means the total number of oxyalkylene groups (or the average value of the total number of added moles) in one molecule of the fluorene derivative represented by the above formula (1), and is simply referred to as n1+n2. There are cases. n1+n2 can be selected from a range of about 0 to 30, for example, and preferable ranges are 0 to 25, 0 to 20, 0 to 15, 0 to 10, 0 to 6, and 0 to 4 in the following steps. , usually 0 to 2, especially 0. Further, n1+n2 may be an integer as described above, but may also be an average value of the total number of added moles, and its range is the same as the range of the above-mentioned integer, including preferred embodiments.

If the value of n1 and n2 or n1+n2 is too large, there is a risk that properties such as high refractive index and high heat resistance will deteriorate.

Note that n1+n2 can be measured by a conventional method, for example, in the preparation of raw materials for fluorene derivatives represented by the above formula (1) such as 9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes. , when forming a (poly)alkyleneoxy group by the addition reaction of an alkylene oxide (alkylene carbonate or haloalkanol) to a given hydroxy compound, the amount of the hydroxy compound (or hydroxyl value) and the alkylene oxide ( It can be measured by a method of calculating the arithmetic mean or arithmetic mean value from the ratio with the amount of (alkylene carbonate or haloalkanol), for example, the method described in JP-A-2013-53310.

Examples of the arene rings represented by Z ^2a and Z ^2b include the same rings as the arene rings exemplified above for Z ^1a and Z ^1b . The type of ring Z ^2a and the type of ring Z ^2b may be the same or different, and are usually the same. Among rings Z ^2a and Z ^2b , C _6-12 arene rings such as benzene ring, naphthalene ring, and biphenyl ring are preferred, and C _6-10 arene rings such as benzene ring and naphthalene ring are more preferred. A benzene ring is particularly preferred from the viewpoint of being able to improve a high refractive index and heat resistance in a well-balanced manner without greatly reducing scratch resistance (flexibility).

The substitution positions of the rings Z ^2a and Z ^2b bonded to the oxygen atom [or the oxyalkylene group (-A ^1a O-) and the oxyalkylene group (-A ^1b O-)] are not particularly limited. For example, when the rings Z ^2a and Z ^2b are naphthalene rings, the groups corresponding to the rings Z ^2a and Z ^2b bonded to the oxygen atom may be 1-naphthyl group, 2-naphthyl group, etc., and usually, It is often a 2-naphthyl group. Furthermore, when the rings Z ^2a and Z ^2b are biphenyl rings, the groups corresponding to the rings Z ^2a and Z ^2b bonded to the oxygen atom include a 2-biphenylyl group, a 3-biphenylyl group, a 4-biphenylyl group, etc. Good too.

As the substituents represented by R ^3a and R ^3b , the same groups as the substituents (non-reactive substituents or non-radically polymerizable substituents) exemplified in the section of R ^2a and R ^2b can be exemplified, and preferred embodiments include The same applies to When R ^3a and R ^3b are aryl groups, they may form the ring assembly arene ring together with Z ^2a and Z ^2b .

Further, the numbers p1 and p2 of substitution of the groups R ^3a and R ^3b may be, for example, an integer of about 0 to 8, preferably an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 3, and an integer of 0 to 3. It is an integer of ˜2, more preferably 0 or 1, particularly 0. Note that the number of substitutions p1 and the number of substitutions p2 may be the same or different from each other, and the type of group R ^3a and the type of group R ^3b may be the same or different from each other. Further, when p1 and p2 are each 2 or more, the types of the two or more groups R ^3a and R ^3b in the same ring Z ^2a or Z ^2b may be the same or different from each other.

The substitution positions of the groups R ^3a and R ^3b are not particularly limited, and between the rings Z ^2a and Z ^2b and the oxygen atom [or the oxyalkylene group (-A ^1a O-) and the oxyalkylene group (-A ^1b O-)] The substitution may be made at a position other than the bonding position of , or the bonding position of the rings Z ^2a and Z ^2b and the alkylene groups A ^2a and A ^2b .

The linear or branched alkylene groups represented by A ^2a and A ^2b include, for example, methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, 1,2-butanediyl group, 1,3- Examples include straight chain or branched C _1-6 alkylene groups such as butanediyl group. The type of alkylene group A ^2a and the type of alkylene group A ^2b may be different from each other, but are usually the same in many cases. Preferred alkylene groups A ^2a and A ^2b include linear or branched C _1-4 alkylene groups, more preferably linear or branched C _1-3 alkylene groups, even more preferably C _{1 -2} alkylene groups, particularly methylene groups, are preferred. If the number of carbon atoms in the alkylene groups A ^2a and A ^2b is too large, the refractive index and heat resistance may decrease.

The substitution positions of the alkylene groups A ^2a and A ^2b in the rings Z ^2a and Z ^2b are not particularly limited, but when the rings Z ^2a and Z ^2b are benzene rings, from the viewpoint of productivity, the substitution positions of the alkylene groups A ^2a and A ^2b are Alkylene groups A 2a and A ^2b are often substituted at the meta ^position relative to the bonding position with the oxygen atom [or oxyalkylene group (-A ^1a O-) and oxyalkylene group (-A ^1b O-)] .

Examples of the alkylene groups A ^3a and A ^3b include the same groups as the alkylene groups exemplified above for A ^1a and A ^1b , including preferred embodiments. Note that (poly)oxyalkylene groups [-(OA ^3a ) _q1 -] and [-(OA ^3b ) _q2 -] substituted for two different alkyleneoxy groups (-A ^2a O-) and (-A ^2b O-) ], the types of groups A ^3a and A ^3b may be the same or different, and are usually the same. Further, when the repeating numbers q1 and q2 are each 2 or more, the types of the two or more groups A ^3a or A ^3b forming the same polyoxyalkylene group may be different from each other, but are the same. There are many things.

The repeating numbers (or average number of added moles) q1 and q2 of the oxyalkylene groups (OA ^3a ) and (OA ^3b ) are the same as n1 and n2 above, including preferred embodiments. Moreover, q1 and q2 may be the same or different from each other. The total number of repetitions q1 and q2 (or the average value of the total number of added moles; sometimes simply referred to as q1+q2) is the same as n1+n2, including preferred embodiments.

If the value of q1 and q2 or q1+q2 is too large, properties such as high refractive index and high heat resistance may deteriorate. Note that q1+q2 can be measured by a conventional method, for example, a method similar to the method for measuring n1+n2 described above.

Although R ^4a and R ^4b may be either a hydrogen atom or a methyl group, a hydrogen atom is preferred from the standpoint of improving reactivity (or curability) and refractive index. The type of group R ^4a and the type of group R ^4b may be the same or different from each other, and are usually the same.

As a preferable fluorene derivative represented by the above formula (1), R ¹ is a hydrocarbon group, a cyano group, or a halogen atom, more preferably an alkyl group, a cyano group, or a halogen atom, and still more preferably an alkyl group; is 0 to 2, more preferably 0 or 1, still more preferably 0; Z ^1a and Z ^1b are C _6-12 arene rings such as benzene ring, naphthalene ring, biphenyl ring, more preferably benzene ring, naphthalene ring A C _6-10 arene ring such as, more preferably a benzene ring or a naphthalene ring, most preferably a naphthalene ring; R ^2a and R ^2b are a hydrocarbon group, more preferably an alkyl group such as a methyl group, a phenyl group, etc. An aryl group, more preferably a C _1-4 alkyl group such as a methyl group; m1 and m2 are integers of 0 to 2, more preferably 0 or 1; A ^1a and A ^1b are linear or branched. a C _2-4 alkylene group, more preferably a linear or branched C _2-3 alkylene group such as an ethylene group or a propylene group, even more preferably an ethylene group; n1 and n2 are 0 to 6, more preferably is 0 to 3, more preferably 0 or 1; Z ^2a and Z ^2b are a C _6-12 arene ring such as a benzene ring, a naphthalene ring or a biphenyl ring, more preferably a C 6-12 arene ring such as a benzene ring or a _naphthalene ring; ₁₀ arene ring, more preferably a benzene ring; R ^3a and R ^3b are a hydrocarbon group, more preferably an alkyl group such as a methyl group, an aryl group such as a phenyl group, and even more preferably a C _1-4 group such as a methyl group. is an alkyl group; p1 and p2 are 0 to 2, more preferably 0 or 1, even more preferably 0; A ^2a and A ^2b are linear or branched C _1-3 alkylene groups, more preferably A C _1-2 alkylene group, more preferably a methylene group; A ^3a and A ^3b are a linear or branched C _2-4 alkylene group, more preferably a linear or branched chain such as an ethylene group or a propylene group. a chain C _2-3 alkylene group, more preferably an ethylene group; q1 and q2 are 0 to 6, more preferably 0 to 3, even more preferably 0 or 1; R ^4a and R ^4b are hydrogen atoms; One example is a compound. These preferred fluorene derivatives include compounds in which the ranges described in stages in each specific item are appropriately combined.

Among these fluorene derivatives, R ¹ in formula (1) has a particularly excellent balance of high refractive index, high heat resistance, and scratch resistance, high productivity, and low skin irritation (high safety). is an alkyl group; k is 0 to 2; Z ^1a and Z ^1b are a benzene ring or naphthalene ring; R ^2a and R ^2b are an alkyl group such as a methyl group; m1 and m2 are 1 to 2 A ^1a and A ^1b are linear or branched C _2-3 alkylene groups such as ethylene group or propylene group; n1 and n2 are 0 or 1; Z ^2a and Z ^2b are benzene rings R ^3a and R ^3b are alkyl groups such as a methyl group; p1 and p2 are 0 or 1; A ^2a and A ^2b are C _1-2 alkylene groups such as a methylene group and an ethylene group; A compound in which A ^3a and A ^3b are linear or branched C _2-3 alkylene groups such as ethylene group or propylene group; q1 and q2 are 0 or 1; and R ^4a and R ^4b are hydrogen atoms. is preferable; in particular, k is 0; Z ^1a and Z ^1b are benzene rings or naphthalene rings; R ^2a and R ^2b are C _1-4 alkyl groups such as methyl groups; m1 and m2 are 1 to 2; A ^1a and A ^1b are ethylene groups; n1 and n2 are 0 or 1; Z ^2a and Z ^2b are benzene rings; R ^3a and R ^3b are C _1-4 such as methyl groups is an alkyl group; p1 and p2 are 0 or 1; A ^2a and A ^2b are methylene groups; A ^3a and A ^3b are ethylene groups; q1 and q2 are 0 or 1; R ^4a and Compounds in which R ^4b is a hydrogen atom are preferred.

The fluorene derivative represented by the formula (1) has a high refractive index. The refractive index (refractive index before curing) of the fluorene derivative represented by the above formula (1) can be selected from a range of, for example, about 1.6 to 1.7 at a temperature of 25° C. and a wavelength of 589 nm, and a preferable range is , in the following stepwise order: 1.605 to 1.63, 1.61 to 1.625, more preferably 1.615 to 1.62. In applications requiring a high refractive index, the refractive index of the fluorene derivative at a temperature of 25° C. and a wavelength of 589 nm is, for example, 1.63 to 1.7, preferably 1.64 to 1.69, more preferably 1. .65 to 1.68, most preferably 1.66 to 1.67.

In addition, the refractive index before curing can be measured by the method described in Examples described later.

[Production method of fluorene derivative represented by formula (1) and intermediate represented by formula (2)]
The method for producing the fluorene derivative represented by the formula (1) is not particularly limited, but may be produced, for example, according to the reaction scheme shown below.

(In the formula, Z ^1a , Z ^1b , Z 2a , Z ^2b , R ¹ , R ^2a , R ^2b , R ^3a , R ^3b , R ^4a , R ^4b , A ^1a , A ^1b , ^{A 2a ,} A ^2b , A ^3a , A ^3b , k, m1, m2, n1, n2, p1, p2, q1 and q2 are the same as the above formula (1), including preferred embodiments, and X ¹ and X ² are the same or Differently, the halogen atoms R ^5a and R ^5b are the same or different from each other and represent a hydroxyl group, an alkoxy group or a halogen atom).

(Preparation method of dihydroxy compound represented by the above formula (2) and its properties)
The first dihydroxy compound represented by the formula (2) is a new compound, for example, the second dihydroxy compound represented by the formula (4) and the compound represented by the formula (5a). It can be synthesized by reacting with the compound represented by the formula (5b).

Examples of the second dihydroxy compound represented by the formula (4) include compounds corresponding to the preferred fluorene derivatives exemplified as the fluorene derivatives represented by the formula (1). Specifically, in the formula (4), 9,9-bis(hydroxyaryl)fluorenes where n1 and n2 are 0; 9,9-bis[hydroxy(poly)alkoxy where n1 and n2 are 1 or more; [aryl]fluorenes, etc. In addition, in this specification and the claims, "(poly)alkoxy" is used to include both an alkoxy group and a polyalkoxy group.

Examples of the 9,9-bis(hydroxyaryl)fluorenes include 9,9-bis(hydroxyaryl)fluorene, specifically 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(hydroxyaryl)fluorene. 9,9-bis(hydroxyC _6-10 aryl)fluorene such as (6-hydroxy-2-naphthyl)fluorene, 9,9-bis(5-hydroxy-1-naphthyl)fluorene; -alkylaryl)fluorene, specifically 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, etc. 9-bis(hydroxy-mono- or diC _1-4 alkylC _6-10 aryl)fluorene; 9,9-bis(hydroxy-arylaryl)fluorene, specifically 9,9-bis(4-hydroxy- Examples include 9,9-bis(hydroxy-C _6-10 arylC _6-10 aryl)fluorene such as 3-phenylphenyl)fluorene.

Examples of the 9,9-bis[hydroxy(poly)alkoxyaryl]fluorenes include 9,9-bis[hydroxy(poly)alkoxyaryl]fluorene, specifically 9,9-bis[4-(2 -hydroxyethoxy)phenyl]fluorene, 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene, 9,9-bis[5-(2-hydroxyethoxy)-1-naphthyl]fluorene, 9,9-bis[hydroxy(poly) _C2 such as 9,9-bis[4-(2-hydroxypropoxy)phenyl]fluorene, 9,9-bis[4-(hydroxypenta- or hexaethoxy)phenyl]fluorene _-3 alkoxy C _6-10 aryl]fluorene; 9,9-bis[hydroxy(poly)alkoxy-alkylaryl]fluorene, specifically 9,9-bis[4-(2-hydroxyethoxy)-3- 9,9-bis[hydroxy(poly)C _2-3 alkoxy-mono- or di-C such as methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3,5-dimethylphenyl]fluorene _1-4 alkyl C _6-10 aryl]fluorene; 9,9-bis(hydroxy-arylaryl)fluorene, specifically 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl] Examples include 9,9-bis[hydroxy(poly)C _2-3 alkoxy-C _6-10 arylC _6-10 aryl]fluorene such as fluorene.

Among these, from the viewpoint of productivity, 9,9-bis(hydroxyaryl)fluorenes in which n1 and n2 are 0 are often used, and they have a good balance of high refractive index, high heat resistance, and scratch resistance. From the viewpoint of excellent properties, 9,9-bis(hydroxyphenyl)fluorene and 9,9-bis(hydroxy-alkylphenyl)fluorene are preferable, and from the viewpoint of low skin irritation and excellent handling properties, 9,9-bis( Preferred are 9,9-bis(hydroxy-mono- or diC _1-4 alkylphenyl)fluorenes, such as 4-hydroxy-3-methylphenyl)fluorene. Furthermore, 9,9-bis(hydroxynaphthyl)fluorene such as 9,9-bis(6-hydroxy-2-naphthyl)fluorene is preferred because of its particularly high refractive index and heat resistance.

These second dihydroxy compounds represented by formula (4) may be commercially available products, and can be prepared by a conventional method, for example, by combining 9-fluorenones such as 9-fluorenone with phenol, o-cresol, It may be prepared by a method in which a hydroxy(poly)alkoxyarene such as 2-naphthol is reacted in the presence of an acid catalyst such as sulfuric acid and a co-catalyst such as β-mercaptopropionic acid.

In the formulas (5a) and (5b), examples of the halogen atoms represented by X ¹ and X ² include a chlorine atom, a bromine atom, an iodine atom, and the like. The type of group X ¹ and the type of group X ² may be different, but are usually the same. Preferred examples of X ¹ and X ² are a bromine atom and an iodine atom, usually a bromine atom. ^{Further , the} substitution ^{position of} X ¹ and .

The repeating numbers q1 and q2 of the alkoxy groups (-A ^3a O-) and (-A ^3b O-) correspond to q1 and q2 in the above formula (2), and are the same including preferred embodiments, and usually, It is often 0. In addition, in formula (1) or (2), the compound in which q1 and q2 are 1 or more is the compound obtained after synthesis using the compound in which q1 and q2 are 0 in formula (5a) and (5b). A compound (a compound in which q1 and q2 are 0 in formula (2)) and an alkylene oxide (or alkylene carbonate or haloalkanol) corresponding to the alkoxy group (-A ^3a O-) and (-A ^3b O-) It may also be prepared by reacting.

Examples of the compounds represented by formulas (5a) and (5b) include halobenzyl alcohols such as m-chlorobenzyl alcohol, m-bromobenzyl alcohol, and m-iodobenzyl alcohol; alkyl-halobenzyl alcohols; phenyl- Aryl-halobenzyl alcohols such as halobenzyl alcohol; halonaphthalene methanols such as chloronaphthalene methanol, bromonaphthalene methanol, iodonaphthalene methanol; alkyl-halonaphthalene methanols; and alkylene oxide (or alkylene carbonate or haloalkanol) additions of these compounds Examples include ethylene oxide adducts. The type of compound represented by the above formula (5a) and the type of the compound represented by the above (5b) may be different, but are usually the same. Among these compounds represented by formulas (5a) and (5b), halobenzyl alcohols such as m-bromobenzyl alcohol are often used.

The total proportion of the compounds represented by formulas (5a) and (5b) is, for example, 2 to 5 mol, preferably 2.1 to 3 mol, per 1 mol of the compound represented by formula (4). , more preferably 2.2 to 2.5 mol.

The reaction may be carried out in the presence of a base. Typical bases include inorganic bases, such as metal hydroxides, specifically alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; metal carbonates, specifically sodium carbonate, Examples include alkali metal carbonates such as potassium carbonate; metal hydrogen carbonates, specifically alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate. These bases can be used alone or in combination of two or more. Among these bases, metal carbonates such as potassium carbonate are often used. The proportion of the base is, for example, about 1 to 3 equivalents, preferably 1 to 2 equivalents, and more preferably 1.2 to 1.8 equivalents, relative to the hydroxyl group of the compound represented by formula (4). .

The reaction may be carried out in the presence of a catalyst. Examples of the catalyst include copper or its derivatives. Examples of copper include simple copper such as copper powder. Examples of copper derivatives include copper halides such as copper (I) chloride, copper (I) bromide, and copper (I) iodide, copper oxides such as copper (I) oxide, copper carbonate, and copper methoxide (I). ) and other copper alkoxides (I). These catalysts can be used alone or in combination of two or more. Among these catalysts, copper powder, copper (I) halides, and copper alkoxides (I) are often used, and among them, copper (I) halides such as copper (I) chloride are often used. The proportion of the catalyst is, for example, 0.001 to 0.2 mol, preferably 0.01 to 0.15 mol, per 1 mol of the compound represented by formula (4).

Further, the catalyst, for example, copper (I) halide such as copper (I) chloride, may be used alone, but is usually used in the form of a complex with a ligand. Examples of the ligand include 8-quinolinol (8-oxyquinoline or 8-quinolinolato). The proportion of the ligand is, for example, 0.5 to 3 mol, preferably 0.8 to 2 mol, more preferably 0.9 to 1.1 mol, per mol of the catalyst.

The reaction may be carried out in a solvent. Typically, the solvent is an aprotic polar solvent, such as amides, specifically N,N'-dimethyl-2-imidazolidinone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and the like; sulfoxides, specifically dimethyl sulfoxide, etc.; sulfones, specifically sulfolane, etc.; phosphoramides, specifically hexamethylphosphoramide and the like. These solvents can be used alone or in combination of two or more. Among these solvents, amides such as N,N'-dimethyl-2-imidazolidinone are often used. The proportion of the solvent is not particularly limited, and is, for example, 10 to 500 parts by mass based on 100 parts by mass of the compound represented by the formula (4) and the compounds represented by the formulas (5a) and (5b). It may be a degree.

The reaction temperature is, for example, 80 to 200°C, preferably 120 to 160°C, more preferably 130 to 150°C. The reaction time is not particularly limited, and is, for example, 1 to 144 hours, preferably 48 to 96 hours.

The reaction may be carried out in air or in an inert atmosphere such as nitrogen gas or rare gas. Moreover, the reaction may be carried out under normal pressure, increased pressure or reduced pressure.

After completion of the reaction, the generated compound represented by the formula (2) can be processed by conventional methods such as neutralization, washing, dehydration, filtration, concentration, extraction, crystallization, recrystallization, reprecipitation, centrifugation, column Separation and purification may be performed by means of separation and purification such as chromatography, or by a combination of these means.

Note that the first dihydroxy compound (diol compound) represented by the formula (2) is a new compound and has a high refractive index and high heat resistance. The refractive index of the dihydroxy compound represented by the formula (2) can be selected, for example, from a range of about 1.6 to 1.7 at a temperature of 25° C. and a wavelength of 589 nm, and the preferable range is as follows, step by step: 1.605 to 1.65, 1.61 to 1.64, 1.615 to 1.635, 1.62 to 1.63, more preferably 1.622 to 1.628. In applications requiring a high refractive index, the refractive index of the dihydroxy compound at a temperature of 25° C. and a wavelength of 589 nm is, for example, 1.63 to 1.7, preferably 1.64 to 1.69, more preferably 1. .65 to 1.68, most preferably 1.66 to 1.67.

Further, the temperature at which the dihydroxy compound represented by the formula (2) decreases by 5% by mass may be, for example, about 300 to 500°C, particularly about 300 to 450°C, and the preferable range is as follows, step by step: The temperature is 330-430°C, 350-410°C, 360-400°C, and more preferably 370-390°C. In applications requiring high heat resistance, the 5% reduction temperature of the dihydroxy compound is, for example, 400 to 480°C, preferably 430 to 470°C, more preferably 440 to 460°C.

Note that the refractive index and the 5% mass reduction temperature can be measured by the method described in Examples described later.

Since the first dihydroxy compound has such excellent properties, it can be used not only as a fluorene derivative (acrylate compound) represented by formula (1) but also as a raw material for other resins or monomers, such as epoxy It can be used as a raw material for curable resins such as resins, thermoplastic resins such as polyester resins, polycarbonate resins, and polyurethane resins; and as resin additives such as refractive index improvers and heat resistance improvers, to give resins a high refractive index. It can provide high heat resistance and heat resistance.

(Preparation of fluorene derivative represented by the above formula (1))
The fluorene derivative represented by the formula (1) (or the first polyfunctional (meth)acrylate) is composed of the first dihydroxy compound represented by the formula (2) and the formulas (3a) and (3b). ) can be produced by reacting with (meth)acrylic acid or its ester-forming derivative. In this specification and claims, unless otherwise specified, "ester-forming derivatives" refer to alkyl esters (or lower alkyl esters), specifically C _1-4 methyl esters, ethyl esters, etc. Alkyl ester; acid halide such as acid chloride; acid anhydride, etc.

The first dihydroxy compound represented by the formula (2) is, for example, a fluorene derivative represented by the formula (1) (or the second dihydroxy compound represented by the formula (4)). Examples include compounds corresponding to the compounds exemplified in .

In formulas (3a) and (3b), examples of the halogen atom represented by R ^5a and R ^5b include a chlorine atom, a bromine atom, an iodine atom, and preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom or a bromine atom. is a chlorine atom. The alkoxy group represented by R ^5a and R ^5b includes a lower alkoxy group, such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a s-butoxy group, and a t-butoxy group. Examples include straight-chain or branched C _1-4 alkoxy groups such as, and preferred are C _1-2 alkoxy groups such as methoxy. The type of group R ^5a and the type of group R ^5b may be different, but are usually the same. Usually, R ^5a and R ^5b are often hydroxyl groups.

Examples of the compounds represented by formulas (3a) and (3b) include (meth)acrylic acid or its anhydride; (meth)acrylic acid halides such as (meth)acrylic acid chloride and (meth)acrylic acid bromide; (meth)acrylic acid alkyl esters, specifically (meth)acrylic acid C _1-4 alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, t-butyl (meth)acrylate, etc. can be mentioned. These compounds represented by the formula (3) can be commercially available products. The type of compound represented by the above formula (3a) and the type of the compound represented by the above (3b) may be different, but are usually the same. Among the compounds represented by formulas (3a) and (3b), (meth)acrylic acid is usually often used.

The total proportion of the compounds represented by the formulas (3a) and (3b) is, for example, 1 to 10 mol per mol of the hydroxyl group of the first dihydroxy compound represented by the formula (2), The amount is preferably 1.1 to 5 mol, more preferably 1.2 to 2 mol, and still more preferably 1.3 to 1.5 mol.

In the above formulas (3a) and (3b), when R ^5a and R ^5b are halogen atoms [when the compound represented by the above formulas (3a) and (3b) is a (meth)acrylic acid halide], the reaction The reaction may be carried out in the presence of a base in order to trap the hydrogen halide produced. Bases can be broadly classified into, for example, inorganic bases and organic bases.

Examples of inorganic bases include metal hydroxides, specifically hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide and calcium hydroxide; metal carbonates, specifically sodium carbonate. , carbonates of alkali metals or alkaline earth metals such as calcium carbonate; and metal hydrogencarbonates, specifically, hydrogencarbonates of alkali metals or alkaline earth metals such as sodium hydrogencarbonate.

Examples of the organic base include amines, specifically trialkylamines such as triethylamine, aromatic tertiary amines such as benzyldimethylamine, and heterocyclic amines such as pyridine and N-methylmorpholine. . The bases may be used alone or in combination of two or more.

Among these bases, amines such as trialkylamines such as triethylamine are often used. The amount of the base to be used is not particularly limited, but for example, 1 to 2 mol, preferably 1.05 to 1.5 mol, more preferably 1.1 to 1.5 mol, per 1 mol of (meth)acrylic acid halide. It is 1.2 mol.

In addition, in the above formulas (3a) and (3b), when R ⁵ is a hydroxyl group or an alkoxy group [the compound represented by the above formulas (3a) and (3b) is (meth)acrylic acid (or its anhydride) ) or (meth)acrylic acid alkyl ester], the reaction may use a conventional esterification catalyst. Examples of the catalyst include acid catalysts, base catalysts, and metal catalysts such as metal alkoxides, specifically titanium (IV) alkoxides such as titanium (IV) tetraisopropoxide. Among these catalysts, acid catalysts can be preferably used.

The acid catalyst is not particularly limited, and includes inorganic acids; organic acids; Lewis acids such as boron trifluoride etherate and tin tetrachloride; solid acid catalysts such as cation exchange resins, and the like. These acid catalysts may be used alone or in combination of two or more. Moreover, these acid catalysts may be hydrates.

Examples of the inorganic acids include strong acids, specifically sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, etc.; homo- or heteropolyacids, specifically tungstophosphoric acid, molybdophosphoric acid, tungstosilicic acid, molybdosilicic acid, etc. It will be done.

Examples of the organic acids include sulfonic acids, specifically alkanesulfonic acids such as methanesulfonic acid and ethanesulfonic acid, fluorinated alkanesulfonic acids such as trifluoromethanesulfonic acid, and arenesulfonic acids such as p-toluenesulfonic acid. Examples include acids. As the acid catalyst, arenesulfonic acids such as p-toluenesulfonic acid monohydrate are often used.

The proportion of the catalyst is not particularly limited, and is, for example, 0.001 to 1 mol, preferably 0.01 to 0.5 mol, per 1 mol of the first dihydroxy compound represented by formula (2). be.

The reaction may be carried out in the presence of a thermal polymerization inhibitor, and/or the thermal polymerization inhibitor may be added after the reaction is completed. Examples of thermal polymerization inhibitors include benzoquinone; hydroquinones such as hydroquinone, hydroquinone monomethyl ether (MEHQ), t-butylhydroquinone, and p-benzoquinone; catechols such as pt-butylcatechol and 2-methoxyphenol; , N-diethylhydroxylamine; 1,1-diphenyl-2-picrylhydrazyl; tri-p-nitrophenylmethyl; and phenothiazine. Thermal polymerization inhibitors may be used alone or in combination of two or more. Among these thermal polymerization inhibitors, catechols such as 2-methoxyphenol are often used.

The proportion of the thermal polymerization inhibitor may be, for example, about 0.001 to 10 parts by mass with respect to 100 parts by mass of the compounds represented by formulas (3a) and (3b), and the For example, the amount may be about 0.0001 to 0.1 part by mass with respect to 100 parts by mass of the fluorene derivative represented by formula (1).

The reaction may be carried out in the presence of a solvent. Examples of solvents include hydrocarbons, specifically aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene; halogenated Hydrocarbons, specifically methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, etc.; Ethers, specifically dialkyl ethers such as diethyl ether, tetrahydrofuran (THF), 1,4-dioxane, etc. cyclic ethers, etc.; Ketones, specifically, acetone, methyl ethyl ketone, etc.; Sulfoxides, specifically, dimethyl sulfoxide, etc.; Amides, specifically, N,N-dimethylformamide, N,N- Examples include dimethylacetamide, N-methyl-2-pyrrolidone, and nitriles such as acetonitrile. The solvents may be used alone or in combination of two or more. Among these solvents, aromatic hydrocarbons such as toluene are often used. The proportion of the solvent is not particularly limited, and is, for example, 10 to 1000 parts by mass based on 100 parts by mass of the compound represented by the formula (2) and the compounds represented by the formulas (3a) and (3b). The amount may be approximately 100 to 150 parts by mass.

The reaction temperature and reaction time can be appropriately selected depending on the type of raw materials used, and when the compounds represented by formulas (3a) and (3b) are (meth)acrylic acid halides, the reaction temperature is, for example, -10°C to 30°C, preferably 0 to 20°C, more preferably 2 to 10°C. When the compounds represented by formulas (3a) and (3b) are (meth)acrylic acid (or its anhydride) or (meth)acrylic acid alkyl ester, the reaction temperature is, for example, 50 to 150°C, preferably is 80 to 130°C, more preferably 100 to 120°C. Note that the reaction may be performed at reflux temperature. The reaction time is not particularly limited, and may be, for example, about 1 to 24 hours.

The reaction can be carried out with stirring in air or in an inert atmosphere such as nitrogen gas or rare gas, and may be carried out under normal pressure, increased pressure, or reduced pressure. Furthermore, in order to effectively prevent unexpected polymerization during the reaction, the reaction may be carried out while blowing air into the reaction solution.

After the completion of the reaction, the produced fluorene derivative represented by the formula (1) can be processed by conventional methods such as neutralization, washing, dehydration, filtration, adsorption, concentration, extraction, crystallization, recrystallization, reprecipitation, and centrifugation. Separation and purification may be carried out by separation and purification means such as separation and column chromatography, or by a combination of these means.

[Curable composition and cured product thereof]
The present invention includes a curable composition containing the fluorene derivative (or first polyfunctional (meth)acrylate) represented by formula (1) above, and a cured product thereof. The curable composition may contain at least a first polyfunctional (meth)acrylate, and the first polyfunctional (meth)acrylate may be contained alone or in combination of two or more. good. Further, the curable composition may contain other polymeric components such as a second polyfunctional (meth)acrylate and a monofunctional (meth)acrylate different from the formula (1).

The second polyfunctional (meth)acrylate is not particularly limited as long as it is a compound having a plurality of (two or more) (meth)acryloyl groups. The number of (meth)acryloyl groups per molecule is, for example, 2 to 10, preferably 2 to 6, more preferably 2 to 4, especially 2 to 3, particularly 2.

Examples of the second polyfunctional (meth)acrylate include aliphatic epoxy (meth)acrylate, alicyclic epoxy (meth)acrylate, aromatic epoxy (meth)acrylate, and poly(meth)acrylate of novolac type epoxy resin. Epoxy (meth)acrylates (vinyl ester resins) such as; urethane (meth)acrylates; polyester (meth)acrylates (poly(meth)acrylates of polyester polyols having two or more hydroxyl groups); alkylene glycol di(meth)acrylates; Polyalkylene glycol di(meth)acrylate; di(meth)acrylate of alicyclic diol; di(meth)acrylate of biphenols or bisphenols or their alkylene oxide (alkylene carbonate or haloalkanol) adducts; 3 to 6 Examples include low molecular weight polyol compounds having a certain degree of hydroxyl group or poly(meth)acrylates of alkylene oxide (alkylene carbonate or haloalkanol) adducts thereof. These second polyfunctional (meth)acrylates may be used alone or in combination of two or more. Commercially available products may be used as these second polyfunctional (meth)acrylates.

Examples of the aliphatic epoxy (meth)acrylates include (poly)alkylene glycol diglycidyl ethers such as di(meth)acrylate of 1,6-hexanediol diglycidyl ether and di(meth)acrylate of polypropylene glycol diglycidyl ether. Examples include di(meth)acrylates.

Examples of the alicyclic epoxy (meth)acrylates include cyclohexanediol, cyclohexanedimethanol, dicyclopentadienedimethanol, norbornanediol, norbornenedimethanol, adamantanediol, adamantane dimethanol, tricyclodecanediol, and tricyclodecanediol. Di(meth)acrylate of an epoxy compound (diglycidyl ether) corresponding to a diol having a _C5-15 aliphatic hydrocarbon ring such as methanol; Aromatics described below such as di(meth)acrylate of hydrogenated bisphenol A diglycidyl ether Examples include di(meth)acrylates of diglycidyl ethers of bisphenols or biphenols or hydrogenated products of alkylene oxide (alkylene carbonate or haloalkanol) adducts thereof described in the group epoxy(meth)acrylates.

Examples of the aromatic epoxy (meth)acrylate include diglycidyl ethers of bisphenols or biphenols or their alkylene oxide (alkylene carbonate or haloalkanol) adducts, such as di(meth)acrylate of bisphenol A diglycidyl ether. Examples include di(meth)acrylates. Examples of bisphenols include bisphenol A, bisphenol F, bisphenol AD, and bisphenol S. Examples of biphenols include p,p'-biphenol, m,m'-biphenol, and o,o'-biphenol.

Examples of the alkylene glycol di(meth)acrylates include C _2-10 alkylene glycol di(meth)acrylates such as ethylene glycol di(meth)acrylate and butanediol di(meth)acrylate.

Examples of the polyalkylene glycol di(meth)acrylate include di- to hexaC _2-10 alkylene glycol di(meth)acrylate such as diethylene glycol di(meth)acrylate.

Examples of the di(meth)acrylate of the alicyclic diol include cyclohexanediol, cyclohexanedimethanol, dicyclopentadienedimethanol, norbornanediol, norbornenedimethanol, adamantanediol, adamantane dimethanol, tricyclodecanediol, and tricyclodiol. Di(meth)acrylates corresponding to diols having a _C5-15 aliphatic hydrocarbon ring such as decanedimethanol; bisphenols described in the aromatic epoxy(meth)acrylates such as di(meth)acrylate of hydrogenated bisphenol A; and di(meth)acrylates of hydrogenated products of biphenols or alkylene oxide (alkylene carbonate or haloalkanol) adducts thereof.

Examples of the poly(meth)acrylate of the low molecular weight polyol compound having about 3 to 6 hydroxyl groups or its alkylene oxide (alkylene carbonate or haloalkanol) adduct include glycerin tri(meth)acrylate, diglycerin tetra( meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol Examples include hexa(meth)acrylate, sorbitol tri-hexa(meth)acrylate.

The proportion of the first polyfunctional (meth)acrylate represented by the formula (1) is, for example, 10% by mass or more with respect to the total amount of the first and second polyfunctional (meth)acrylates, can be selected from the range of about 30 to 100% by mass, and the preferred ranges are 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, and more preferably It is preferably 90% by mass or more, particularly substantially 100% by mass, that is, the polyfunctional polymerization component is only the first polyfunctional (meth)acrylate. Note that the ratio may be selected from a range of, for example, about 60 to 99% by mass, and specifically, may be 80 to 97% by mass.

The monofunctional polymerization component (or reactive diluent) includes one polymerizable group (or polymerizable unsaturated bond), for example, an alkenyl group such as a vinyl group or an allyl group, a (meth)acryloyl group, etc. Specific examples include monofunctional vinyl monomers; monofunctional (meth)acrylic monomers. Examples of monofunctional vinyl monomers include α-olefin monomers such as ethylene and propylene; styrene monomers such as styrene, α-methylstyrene, and vinyltoluene; vinyl ester monomers such as vinyl acetate; N-vinylpyrrolidone. Examples include. Monofunctional (meth)acrylic monomers include (meth)acrylic acid; (meth)acrylamide; N-substituted (meth)acrylamide such as N-methylol (meth)acrylamide and N,N-dimethyl (meth)acrylamide; (Meth)acrylonitrile; includes monofunctional (meth)acrylates.

These monofunctional polymerization components can be used alone or in combination of two or more. Among these monofunctional polymerization components, monofunctional (meth)acrylic monomers, especially monofunctional (meth)acrylates, are often used.

Monofunctional (meth)acrylates include, for example, aliphatic monofunctional (meth)acrylates; alicyclic monofunctional (meth)acrylates; aromatic monofunctional (meth)acrylates; monofunctional containing sulfur atoms. (meth)acrylates. These monofunctional (meth)acrylates can be used alone or in combination of two or more.

Examples of aliphatic monofunctional (meth)acrylates include C _1-20 alkyl (meth)acrylates such as methyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

Examples of alicyclic monofunctional (meth)acrylates include bridged C _5-10 cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and isobornyl (meth)acrylate. Examples include cyclic (meth)acrylates.

Aromatic monofunctional (meth)acrylates include, for example, aryl (meth)acrylates such as phenyl (meth)acrylate; aralkyl (meth)acrylates such as benzyl (meth)acrylate; aryloxyalkyl (meth)acrylates; Examples include C _6-12 aryloxy C _2-4 such as 2-phenoxyethyl (meth)acrylate, 2-(2-naphthoxy)ethyl (meth)acrylate, and 2-(o-phenylphenoxy)ethyl (meth)acrylate. Alkyl (meth)acrylates, etc.; Mono(meth)acrylates of bisphenols or biphenols (or their alkylene oxide adducts), such as mono(meth)acrylates of ethylene oxide adducts of bisphenol A; 9-(meth)acryloyloxymethylfluorene Examples include (meth)acrylates having a fluorene skeleton such as.

Examples of the monofunctional (meth)acrylate containing a sulfur atom include alkylthio(meth)acrylate, arylthio(meth)acrylate, aralkylthio(meth)acrylate, and arylthioalkyl(meth)acrylate. Examples of alkylthio(meth)acrylates include C _1-6 alkylthio(meth)acrylates such as methylthio(meth)acrylate. Examples of arylthio(meth)acrylates include C _6-10 arylthio(meth)acrylates such as phenylthio(meth)acrylate. Examples of aralkylthio(meth)acrylates include C _6-10 arylC _1-6 alkylthio(meth)acrylates such as benzylthio(meth)acrylate. Examples of arylthioalkyl (meth)acrylates include C _6-10 arylthioC _2-4 alkyl (meth)acrylates such as phenylthioethyl (meth)acrylate.

(components other than polymerization components)
The curable composition may further contain a polymerization initiator, a solvent, an additive, etc. in addition to the polymerization component (or monomer component).

The polymerization initiator may be a thermal polymerization initiator (thermal radical generator) or a photopolymerization initiator (photoradical generator).

Examples of the thermal polymerization initiator include organic peroxides and azo compounds. Examples of organic peroxides include dialkyl peroxides such as di-t-butyl peroxide; diacyl peroxides such as lauroyl peroxide and benzoyl peroxide; t-butyl hydroperoxide, cumene hydroperoxide, and peroxide. Examples include peracids (or peracid esters) such as t-butyl acetate; ketone peroxides; peroxycarbonates; and peroxyketals. Examples of the azo compound include azonitrile compounds such as 2,2'-azobis(isobutyronitrile), azoamide compounds, and azoamidine compounds. These thermal polymerization initiators can be used alone or in combination of two or more.

Examples of photopolymerization initiators include benzoins, specifically benzoin, benzoin alkyl ethers such as benzoin ethyl ether; acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, etc. Acetophenones; Aminoacetophenones such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoaminopropanone-1; Anthraquinones such as anthraquinone and 2-methylanthraquinone; 2,4-dimethylthioxanthone; Examples include thioxanthone such as 2,4-diethylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; and xanthone. These photopolymerization initiators may be used alone or in combination of two or more.

The proportion of the polymerization initiator (thermal and/or photopolymerization initiator) is 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the total amount of polymerization components. The amount is 8 parts by weight, more preferably 2 to 5 parts by weight.

Moreover, the photoinitiator may be combined with a photosensitizer. Typically, photosensitizers include tertiary amines such as trialkylamines; trialkanolamines such as triethanolamine; dialkylaminobenzoic acid alkyl esters, specifically p-(dimethylamino)benzoic acid; ethyl N,N-dimethylaminobenzoate such as ethyl acid; amyl N,N-dimethylaminobenzoate such as amyl p-(dimethylamino)benzoate; bis( such as 4,4-bis(diethylamino)benzophenone); Dialkylamino)benzophenones; conventional photosensitizers such as dialkylaminobenzophenones such as 4-(dimethylamino)benzophenone; These photosensitizers may be used alone or in combination of two or more.

The proportion of the photosensitizer is 1 to 200 parts by weight, preferably 5 to 150 parts by weight, and more preferably 10 to 100 parts by weight, based on 100 parts by weight of the polymerization initiator.

The curable composition does not need to contain a solvent, but may contain a solvent as necessary to adjust the handleability. The solvent is not particularly limited, and examples include hydrocarbons, specifically aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as toluene and xylene. halogenated hydrocarbons, specifically methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, etc.; ethers, specifically chain ethers such as diethyl ether, tetrahydrofuran, 1,4 - Cyclic ethers such as dioxane; Ketones, specifically dialkyl ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; cyclic ketones such as cyclohexanone; Esters, specifically methyl acetate, acetic acid Acetate esters such as ethyl and butyl acetate; glycol ether acetates, specifically (poly)alkylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and diethylene glycol monobutyl ether acetate; sulfoxides, specifically Examples include dimethyl sulfoxide and the like; amides, specifically, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, etc.; and nitriles, specifically, acetonitrile. These solvents can be used alone or as a mixed solvent in combination of two or more.

The proportion of the solvent is not particularly limited, and it may be contained so that the concentration of solid content (components other than the solvent) is, for example, about 0.1 to 50% by mass based on the entire curable composition.

The curable compositions may contain conventional additives such as colorants, stabilizers, fillers, antistatic agents, flame retardants, surfactants, plasticizers, curing agents, polymerization inhibitors, and the like. Examples of the stabilizer include heat stabilizers, antioxidants, and ultraviolet absorbers. These additives can be used alone or in combination of two or more.

The total proportion of the additives is, for example, 30% by mass or less, and the preferable range is 20% by mass or less, 10% by mass or less, and 5% by mass or less, based on the entire curable composition. Note that the ratio may be 0.001 to 15% by mass, specifically 0.01 to 3% by mass.

(cured product)
The curable composition of the present invention is easily cured by applying active energy (or active energy rays) to produce a cured product. Thermal energy and/or light energy, such as ultraviolet rays and X-rays, are useful as the activation energy.

In the case of heat treatment using thermal energy, the heating temperature is, for example, 50 to 200°C, preferably 60 to 150°C, and more preferably 70 to 120°C.

Further, when irradiating light using light energy (for example, ultraviolet rays, etc.), the amount of light irradiation energy can be appropriately selected depending on the application, and is, for example, 50 to 10,000 mJ/cm ² , preferably 70 to 8,000 mJ/cm ² , more preferably 100 to 5000 mJ/cm ² , particularly 500 to 3000 mJ/cm ² .

The shape of the cured product is not particularly limited, and may be a cured product with a three-dimensional structure such as a lens shape or a tube shape, or a cured product (or cured film) with a two-dimensional structure such as a film shape, sheet shape, or plate shape. The cured product may have a linear, fibrous, or rod-like one-dimensional structure.

The method for producing the cured product is not particularly limited, and for example, depending on the shape of the cured product, the curable composition may be molded or cast (injected) into a predetermined mold, and then cured (heated and/or (light irradiation)). In the case of a cured product with a two-dimensional structure, for example, the curable composition may be used as a base material or substrate, such as metal such as aluminum; inorganic material or ceramics such as titanium oxide, glass, or quartz; cyclic olefin resin, polycarbonate. It may be manufactured by coating an organic material such as a resin-based resin or a porous body such as a plastic, or a porous body such as wood to form a film-like coating (or thin film), and then subjecting it to a curing treatment.

Since the cured product of the present invention is formed from the fluorene derivative represented by the above formula (1), it exhibits a high refractive index and high heat resistance.

The refractive index (refractive index after curing) of the cured product can be selected, for example, from the range of about 1.61 to 1.7 at a temperature of 25° C. and a wavelength of 589 nm, and the preferable range is 1. 62 to 1.65, 1.625 to 1.64, more preferably 1.63 to 1.635. In applications requiring a high refractive index, the cured product has a refractive index of, for example, 1.63 to 1.7, preferably 1.64 to 1.69, more preferably 1.64 to 1.69 at a temperature of 25° C. and a wavelength of 589 nm. 1.65 to 1.68, most preferably 1.66 to 1.67.

Further, the glass transition temperature Tg of the cured product is, for example, about 150 to 250°C, preferably 180 to 220°C, and more preferably 190 to 210°C. In applications requiring high heat resistance, the cured product has a Tg of, for example, 180 to 250°C, preferably 190 to 230°C, and more preferably 200 to 220°C.

The 5% mass reduction temperature of the cured product is, for example, about 350 to 500°C, preferably 370 to 450°C, and more preferably 400 to 420°C.

Note that the refractive index after curing, the glass transition temperature Tg, and the 5% mass reduction temperature can be measured by the method described in the Examples described later.

The present invention will be explained in more detail below based on Examples, but the present invention is not limited by these Examples. The evaluation method and raw materials are shown below.

[Evaluation method]
(HPLC)
The HPLC purity [area %] of the sample was calculated by high performance (or high performance) liquid chromatography (HPLC) based on the following measuring device and conditions.

Equipment: “L-2000” manufactured by Hitachi High-Technologies Co., Ltd.
Column: "Cadenza CL-C18 (3 μm) 3.0 x 250 mm" manufactured by Imtakt Co., Ltd.
Guard column: “GCCD0S” manufactured by Imtakt Co., Ltd.
Detector: L-2420 type UV-VIS detector (D ₂ lamps, 254 nm)
Mobile phase: Acetonitrile/distilled water (volume ratio) = 80/20 (Kanto Kagaku Co., Ltd., LC grade) (Examples 1 and 2) or acetonitrile/distilled water (volume ratio) = 90/10 (Kanto Kagaku Co., Ltd., LC grade) (Examples 1 and 2) Co., Ltd., LC grade) (Examples 3 and 4)
Flow rate: 0.5ml/min.

( ^1H -NMR)
¹ H-NMR using a nuclear magnetic resonance apparatus (BRUKER "ULTRA SHIELD (registered trademark) 300"), deuterated chloroform (CDCl ₃ ) as a solvent, and tetramethylsilane (TMS) as a standard substance. The spectrum was measured.

(FD-MS)
Mass spectrometry (MS) was performed based on the following measuring device and conditions.

Equipment used: “JMS-T200GC” manufactured by JEOL Ltd.
Ionization method: FD (field desorption)
Emitter: Carbon Emitter current: 0-50mA (25mA/min)

(heated residue)
Using a measuring device (“HG53 Halogen Moisture Meter” manufactured by METTLER TOLEDO Co., Ltd.), the heating residue (mass %) of the acrylate compound before curing was measured at 200°C, and the reaction solvent, etc. It was confirmed that almost no volatile components remained.

(Refractive index nD)
The refractive index of the sample before and after curing was measured at a temperature of 25° C. and a wavelength of 589 nm using a refractometer (manufactured by Atago Co., Ltd., DR-M2 <circulating constant temperature water bath 60-C3>). Note that the refractive index of the didroxy compound of Example 1 and the diacrylate compound before curing of Example 2 was determined by dissolving the sample in a solvent and preparing a solution with a predetermined concentration (Example 1: 8.4% by mass and 25% by mass). 6% by weight tetrahydrofuran (THF) solution, Example 2: 11.4 and 25.6% by weight toluene solution, Example 3: 12.5% by weight and 26.3% by weight THF solution, Example 4: The concentration was calculated by extrapolating the concentration to 100% by mass in the calibration curve (approximate straight line) created by preparing toluene solutions of 18.2 and 74.0% by mass and measuring the refractive index of the obtained solutions. .

(Glass transition temperature Tg)
The glass transition temperature of the cured product was measured using a differential scanning calorimeter (DSC6220 manufactured by SII Nanotechnology Co., Ltd.) at a measurement temperature of 30 to 220°C and a heating time of 10°C/min.

(5% mass reduction temperature)
Using a thermogravimetric measurement-differential thermal analyzer (TG-DTA) ("TG/DTA6200" manufactured by SII Nanotechnology Co., Ltd.), under a nitrogen atmosphere at a temperature increase rate of 10 ° C / min, The temperature at which the mass of the sample decreased by 5% by mass was measured. In addition, regarding the acrylate compound, a cured product was used as a sample.

(Scratch resistance)
Using a surface property measuring device (“HEIDON-14DR” manufactured by Shinto Kagaku Co., Ltd.), steel wool #0000 was attached to the tip of the surface property measuring device, and a load of 250 g was applied to the cured product (50 mm x 15 mm x 2 mm). The cured product was moved under a vertical load at a speed of 1 mm/s, and the presence or absence of scratches and recovery of the scratches were visually confirmed. This operation was performed on five cured products.

[material]
BCF: 9,9-bis(4-hydroxy-3-methylphenyl) fluorene, manufactured by Osaka Gas Chemical Co., Ltd. BNF: 9,9-bis(6-hydroxy-2-naphthyl) fluorene, manufactured by Osaka Gas Chemical Co., Ltd. Made

[Example 1]
In a four-necked 2L flask, under a nitrogen stream, add 167 g (0.44 mol) of BCF, 198 g (1.06 mol) of m-bromobenzyl alcohol, 334 g of N,N'-dimethyl-2-imidazolidinone (DMI), and potassium carbonate. 91.5 g (0.66 mol), 3.5 g (35.4 mmol) of copper(I) chloride, and 5.1 g (35.1 mmol) of 8-quinolinol were charged and reacted at 140° C. for 72 hours. After cooling the reaction solution to room temperature, it was extracted and separated using 600 g of toluene and 300 g of ion-exchanged water. The organic layer was washed twice with 150 g of 1N hydrochloric acid to decompose insoluble matter (decomposed at pH 2 to 3), and washed twice with 100 g of ion-exchanged water. Thereafter, neutralization treatment was performed twice with 150 g of a 2% by mass aqueous sodium hydroxide solution, and washing was performed 10 times with 200 g of ion-exchanged water to bring the pH of the aqueous layer to 7. The organic layer was concentrated under reduced pressure to obtain 329 g of a brown viscous liquid. The brown viscous liquid was dissolved in 450 g of toluene at 50° C., seed crystals were introduced (added), and after recrystallization in a freezer overnight, the precipitate was washed three times with 50 g of toluene and collected. The same recrystallization operation was performed five times to collect the precipitate, which was then dried under reduced pressure at 60 to 80°C to obtain the desired product represented by the following formula (2-1), 9,9-bis[4- 81.0 g of (3-(hydroxymethyl)phenyloxy)-3-methylphenyl]fluorene was obtained in the form of light brown crystals (yield 31.1%, HPLC purity 96.4 area %). ¹ H-NMR measurement results are shown below.

¹ H-NMR (CDCl ₃ , 300 MHz): δ (ppm) 1.6 (t, 2H), 2.1 (s, 6H), 4.6 (d, 4H), 6.7-7.8 ( m, 22H).

[Example 2]
49.0 g (0.08 mol) of 9,9-bis[4-(3-(hydroxymethyl)phenyloxy)-3-methylphenyl]fluorene obtained in Example 1 was placed in a 500 mL three-necked flask equipped with a Dean Stark. , 15.5 g (0.22 mol) of acrylic acid, 81 g of toluene, and 0.18 g (1.5 mmol) of 2-methoxyphenol were charged. After purging the system with nitrogen and raising the temperature to 60 ° C. to homogenize the components, 1.97 g (10.4 mmol) of p-toluenesulfonic acid monohydrate was added, and after purging with nitrogen again, The mixture was dehydrated under reflux for 4 hours. The reaction temperature was 110-115°C. The obtained solution (reaction mixture) was washed with 289 g of toluene and 30 g of 20 mass% saline, then neutralized with 30 g of 10 mass% caustic soda water (sodium hydroxide aqueous solution) and 30 g of 20 mass% saline, and the aqueous layer was separated. It was confirmed that the pH was 10 or more. After homogenizing the solution (organic layer) by adding 500 mass ppm of 2-methoxyphenol to the entire organic layer, it was washed twice with 30 g of 20 mass% saline and twice with 30 g of ion-exchanged water. It was confirmed that the aqueous layer had a pH of 7. Thereafter, the organic layer was treated with activated carbon, and after celite filtration and microfiltration, the filtrate was concentrated to obtain the target product (BCF benzyl alcohol) represented by the following formula (1-1), 9,9-bis[4-( 3-(Acryloyloxymethyl)phenyloxy)-3-methylphenyl]fluorene was obtained in the form of a pale yellow viscous liquid. The HPLC purity of the obtained target product was 85.0 area %, and the heating residue was 95.6 mass %. The measurement results of ¹ H-NMR and FD-MS are shown below.

¹ H-NMR (CDCl ₃ , 300 MHz): δ (ppm) 2.1 (s, 6H), 5.1 (s, 4H), 5.8 (dd, 2H), 6.1 (dd, 2H) , 6.4 (dd, 2H), 6.7-7.8 (m, 22H)

FD-MS: m/z 698 (M+)

The target product obtained in Example 2 was collected in a brown bottle, and 3 parts by mass of Irgacure 184 (manufactured by BASF Japan Co., Ltd.) was added as a photopolymerization initiator to 100 parts by mass of the target product obtained in Example 2. A curable composition was obtained by heating and dissolving at 120°C. A mold was placed on glass sprayed with a mold release agent, the obtained curable composition was poured into the mold, the other side was sandwiched between two pieces of glass treated with the same treatment, and UV irradiation (500 mJ/cm ² ) was applied. This was repeated four times to produce a cured product.

[Example 3]
In a four-necked 2L flask, under a nitrogen stream, add 150 g (0.33 mol) of BNF, 150 g (0.80 mol) of m-bromobenzyl alcohol, 500 g of N,N'-dimethyl-2-imidazolidinone (DMI), and potassium carbonate. 69.0 g (0.50 mol), 3.3 g (33.3 mmol) of copper(I) chloride, and 4.8 g (33.1 mmol) of 8-quinolinol were charged and reacted at 140° C. for 72 hours. After cooling the reaction solution to room temperature, it was extracted and separated using 960 g of methyl isobutyl ketone (MIBK) and 300 g of ion-exchanged water. The organic layer was washed twice with 150 g of 1N hydrochloric acid to decompose insoluble matter (decomposed at pH 2 to 3), and washed twice with 100 g of ion-exchanged water. Thereafter, neutralization treatment was performed twice with 150 g of a 2% by mass aqueous sodium hydroxide solution, and washing was performed 10 times with 200 g of ion-exchanged water to bring the pH of the aqueous layer to 7. The organic layer was concentrated under reduced pressure to obtain 246 g of brown crystals. The brown crystals were dissolved in 780 g of isopropanol (IPA) at 80°C, allowed to cool to room temperature, cooled to 5°C in an ice bath, and stirred for 1 hour. Thereafter, the precipitate was collected by decantation and dried to obtain 131 g of pale brown crystals. The crystals were roughly purified by column chromatography (silica gel carrier 1.5 kg, developing solvent: toluene/THF=10/1) to obtain 94.5 g of yellow crystals. The obtained crystals were developed in 180 g of n-hexane, stirred at room temperature for 1 hour, filtered, and washed three times with 20 g of n-hexane. By drying the filtrate overnight under reduced pressure at 120°C, the target product (BNF benzyl alcohol) represented by the following formula (2-2), 9,9-bis[6-(3-(hydroxymethyl)phenyloxy) )-2-naphthyl]fluorene in the form of yellow crystals (yield 37.9%, heating residue 98.4%, HPLC purity 91.4 area %). ¹ H-NMR measurement results are shown below.

¹ H-NMR (CDCl ₃ , 300 MHz): δ (ppm) 1.7 (s, 2H), 4.7 (s, 4H), 6.9-7.8 (m, 28H)

[Example 4]
In a 500 mL three-necked flask equipped with a Dean-Stark, 41.0 g (0.06 mol) of 9,9-bis[6-(3-(hydroxymethyl)phenyloxy)-2-naphthyl]fluorene obtained in Example 3, 11.6 g (0.16 mol) of acrylic acid, 60 g of toluene, and 0.13 g (1.1 mmol) of 2-methoxyphenol were charged. After purging the system with nitrogen and raising the temperature to 60 ° C. to homogenize the components, 1.47 g (7.7 mmol) of p-toluenesulfonic acid monohydrate was added, and after purging with nitrogen again, The mixture was dehydrated under reflux for 4 hours. The reaction temperature was 110-115°C. The obtained solution (reaction mixture) was washed with 215 g of toluene and 22 g of 20 mass% saline, and then neutralized with 22 g of 10 mass% caustic soda water (sodium hydroxide aqueous solution) and 22 g of 20 mass% saline, and the aqueous layer was separated. It was confirmed that the pH was 10 or more. After homogenizing the solution (organic layer) by adding 500 mass ppm of 2-methoxyphenol to the entire organic layer, it was washed twice with 22 g of 20 mass% saline and twice with 22 g of ion-exchanged water. It was confirmed that the aqueous layer had a pH of 7. Thereafter, the organic layer was treated with activated carbon, filtered through celite and microfiltered, and the filtrate was concentrated and dried to obtain the target product represented by the following formula (1-2), 9,9-bis[6-(3-( Acryloyloxymethyl)phenyloxy)-2-naphthyl]fluorene was obtained in the form of yellow crystals. The HPLC purity of the obtained target product was 68.0 area %, and the heating residue was 97.3 mass %. The measurement results of ¹ H-NMR and FD-MS are shown below.

¹ H-NMR (CDCl ₃ , 300 MHz): δ (ppm) 5.2 (s, 4H), 5.8 (dd, 2H), 6.1 (dd, 2H), 6.4 (dd, 2H) , 7.0-7.8 (m, 28H)

FD-MS: m/z 770 (M+)

The target product obtained in Example 4 was collected in a brown bottle, and 3 parts by mass of Irgacure 184 (manufactured by BASF Japan Co., Ltd.) was added as a photopolymerization initiator to 100 parts by mass of the target product obtained in Example 4. A curable composition was obtained by heating and dissolving at 120°C. A mold was placed on glass sprayed with a mold release agent, the obtained curable composition was poured into the mold, the other side was sandwiched between two pieces of glass treated with the same treatment, and UV irradiation (500 mJ/cm ² ) was applied. This was repeated four times to produce a cured product.

[Comparative example 1]
According to Comparative Example 1 of Japanese Patent No. 6017222, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene (hereinafter referred to as BPEFA) was prepared. A curable composition and a cured product were prepared in the same manner except that BPEFA was used in place of the compound obtained in Example 2, and the composition was heated to 100° C. to dissolve it.

The evaluation results are shown in Table 1 below.

As is clear from Table 1, the diol compounds obtained in Examples 1 and 3, the acrylate compounds obtained in Examples 2 and 4, and their cured products exhibited high refractive index and high heat resistance. Note that the scratch resistance of the cured products of Comparative Example 1 and Example 2 was almost the same.

In addition, the refractive index nD of Example 2 before curing was surprisingly higher than the refractive index nD (1.606 and 1.591) of Comparative Examples 4 and 6 described in Patent Document 1, which also have a BCF skeleton. . Note that in the field of optical materials, it is recognized that even an increase in refractive index of 0.001 is a significant difference, so the degree of increase in Example 2 was found to be extremely significant.

In Patent Document 1, in which a benzyl group is introduced into the arene ring substituted at the 9,9-position of the fluorene skeleton, it is suggested that the refractive index decreases. It was a very surprising result that in Example 2 of the present application, in which the acryloyl group was introduced between the acryloyl group and the acryloyl group, the refractive index could be significantly improved.

Furthermore, the refractive index nD of Examples 3 and 4 is both high, and unlike Examples 1 and 2, the acrylate compound of Example 4 has a higher refractive index nD than the diol compound of Example 3. It was also surprising.

The fluorene derivative represented by the formula (1) of the present invention, the curable composition containing the derivative, and the cured product thereof can be used for various purposes, such as graphitization precursors; CO ₂ gas separation membranes, etc. Gas separation membranes; membranes for fuel cells; luminescent materials such as organic EL luminescent materials; organic semiconductors; adhesives or adhesives such as optical adhesives and optical adhesives; coating agents (coating agents), specifically , optical overcoating agents such as coating agents for LED (light emitting diode) elements, hard coating agents, ink materials, etc.; lenses, specifically pickup lenses such as pickup lenses for DVD (digital versatile discs); Microlenses such as microlenses for liquid crystal projectors, spectacle lenses, etc.; Films or sheets, especially optical films or optical sheets, specifically, reflective films such as polarizing films such as polarizing films for liquid crystal displays, antireflection films for display devices, etc. Prevention film (or anti-reflection film), touch panel film, flexible substrate film, display film, in detail, PDP (plasma display), LCD (liquid crystal display), VFD (vacuum fluorescent display), SED (surface conduction type) Displays such as electron-emitting device displays), FEDs (field emission displays), NEDs (nano-emissive displays), cathode ray tubes, electronic paper, etc., especially filters, protective films, prism sheets, etc. for thin displays; optical fibers; optical waveguides; holograms, etc. It can be suitably used for.

In addition, since the compound of the present invention has a high refractive index, it can be effectively used in optical applications, such as coating agents and optical films (or optical sheets) such as prism sheets, and is particularly suitable as optical members for displays. It is.

Note that the first dihydroxy compound represented by the formula (2), which is an intermediate of the derivative, may be a resin additive such as a refractive index improver or a heat resistance improver, a polyester resin, a polycarbonate resin, a polyurethane resin, It can be effectively used as a raw material for resins such as epoxy resins or monomers.

Claims (7)

The following formula (1)

(In the formula,
R ¹ represents a substituent, k represents an integer of 0 to 8,
Z ^1a and Z ^1b are the same or different from each other and represent an arene ring,
R ^2a and R ^2b are the same or different from each other and represent a substituent, m1 and m2 are the same or different from each other and represent an integer of 0 or more,
A ^1a and A ^1b are the same or different from each other and represent a linear or branched alkylene group, n1 and n2 are the same or different from each other and represent an integer of 0 or more,
Z ^2a and Z ^2b are the same or different from each other and represent an arene ring,
R ^3a and R ^3b are the same or different from each other and represent a substituent, p1 and p2 are the same or different from each other and represent an integer of 0 or more,
A ^2a and A ^2b are the same or different from each other and represent a linear or branched alkylene group,
A ^3a and A ^3b are the same or different from each other and represent a linear or branched alkylene group, q1 and q2 are the same or different from each other and represent an integer of 0 or more,
R ^4a and R ^4b are the same or different and represent a hydrogen atom or a methyl group)
A compound represented by In formula (1),
Z ^1a and Z ^1b are the same or different from each other and represent a C _6-10 arene ring,
R ^2a and R ^2b are the same or different from each other and represent a hydrocarbon group, m1 and m2 are the same or different from each other and represent an integer from 0 to 4;
A ^1a and A ^1b are the same or different from each other and represent a linear or branched C _2-6 alkylene group, n1 and n2 are the same or different from each other and represent an integer from 0 to 10,
Z ^2a and Z ^2b are the same or different from each other and represent a C _6-10 arene ring,
R ^3a and R ^3b are the same or different from each other and represent a hydrocarbon group, p1 and p2 are the same or different from each other and represent an integer from 0 to 4,
A ^2a and A ^2b are the same or different from each other and represent a linear or branched C _1-4 alkylene group,
A claim where A ^3a and A ^3b are the same or different from each other and represent a linear or branched C _2-6 alkylene group, and q1 and q2 are the same or different from each other and represent an integer from 0 to 10. Item 1. Compound according to item 1. In formula (1),
Z ^1a and Z ^1b are the same or different from each other and represent a benzene ring or a naphthalene ring,
R ^2a and R ^2b are the same or different from each other and represent an alkyl group or an aryl group, m1 and m2 are the same or different from each other and represent an integer from 0 to 2,
A ^1a and A ^1b are the same or different from each other and represent a linear or branched C _2-4 alkylene group, n1 and n2 are the same or different from each other and represent 0 or 1,
Z ^2a and Z ^2b are the same or different from each other and represent a benzene ring,
R ^3a and R ^3b are the same or different from each other and represent an alkyl group or an aryl group, p1 and p2 are the same or different from each other and represent an integer from 0 to 2,
A ^2a and A ^2b are the same or different from each other and represent a C _1-2 alkylene group,
Claim 1 wherein A ^3a and A ^3b are the same or different from each other and represent a linear or branched C _2-4 alkylene group, and q1 and q2 are the same or different from each other and represent 0 or 1. or the compound described in 2. A curable composition comprising the compound according to any one of claims 1 to 3. A cured product obtained by curing the curable composition according to claim 4. The following formula (2)

(In the formula,
R ¹ represents a substituent, k represents an integer of 0 to 8,
Z ^1a and Z ^1b are the same or different from each other and represent an arene ring,
R ^2a and R ^2b are the same or different from each other and represent a substituent, m1 and m2 are the same or different from each other and represent an integer of 0 or more,
A ^1a and A ^1b are the same or different from each other and represent a linear or branched alkylene group, n1 and n2 are the same or different from each other and represent an integer of 0 or more,
Z ^2a and Z ^2b are the same or different from each other and represent an arene ring,
R ^3a and R ^3b are the same or different and each represents a hydrocarbon group, a group [-OR ^a ] (in the formula, R ^a represents the hydrocarbon group), a group [-SR ^a ] (in the formula, R ^a represents the hydrocarbon group), an acyl group, a nitro group, a cyano group, or a mono- or di-substituted amino group, p1 and p2 are the same or different and represent an integer of 0 or more,
A ^2a and A ^2b are the same or different from each other and represent a linear or branched alkylene group,
A ^3a and A ^3b are the same or different from each other and represent a linear or branched alkylene group, and q1 and q2 are the same or different from each other and represent an integer of 0 or more)
A compound represented by The following formula (2)

(In the formula,
R ¹ represents a substituent, k represents an integer of 0 to 8,
Z ^1a and Z ^1b are the same or different from each other and represent an arene ring,
R ^2a and R ^2b are the same or different from each other and represent a substituent, m1 and m2 are the same or different from each other and represent an integer of 0 or more,
A ^1a and A ^1b are the same or different from each other and represent a linear or branched alkylene group, n1 and n2 are the same or different from each other and represent an integer of 0 or more,
Z ^2a and Z ^2b are the same or different from each other and represent an arene ring,
R ^3a and R ^3b are the same or different from each other and represent a substituent, p1 and p2 are the same or different from each other and represent an integer of 0 or more,
A ^2a and A ^2b are the same or different from each other and represent a linear or branched alkylene group,
A ^3a and A ^3b are the same or different from each other and represent a linear or branched alkylene group, and q1 and q2 are the same or different from each other and represent an integer of 0 or more)
A compound represented by the following formulas (3a) and (3b)

(wherein R ^4a and R ^4b are the same as in formula (1) according to claim 1, and R ^5a and R ^5b are the same or different and represent a hydroxyl group, an alkoxy group, or a halogen atom) A method for producing the compound according to any one of claims 1 to 3 by reacting with the represented compound.