JP5179808B2 - New dibenzofluorene compounds - Google Patents

Description

  The present invention relates to a novel dibenzofluorene compound having excellent heat resistance and high refractive index and useful as a resin raw material, a method for producing the same, and a resin containing the dibenzofluorene compound as a polymerization component.

  In resin and resin raw materials, resin polymerization components can be selected and the resin can be modified to give or improve important properties such as thermal properties (heat resistance, etc.) and optical properties (high refractive index, etc.) A method such as adding a compound is taken. For example, a compound having a fluorene skeleton (such as a 9,9-bisphenylfluorene skeleton) is known to have an excellent function in terms of refractive index, heat resistance, and the like. As a method for expressing such an excellent function of the fluorene skeleton in a resin, a fluorene compound having a reactive group (hydroxyl group, amino group, etc.), for example, bisphenol fluorene (BPF), biscresol fluorene (BCF), bis A general method is to use phenoxyethanol fluorene (BPEF) or the like as a constituent component of a resin and introduce a fluorene skeleton into a part of the skeleton structure of the resin. For example, as an example using such a resin having a fluorene skeleton, JP-A No. 2002-284864 (Patent Document 1) discloses a molding material composed of a polyester resin having a 9,9-bisphenylfluorene skeleton. It is disclosed. JP-A-2004-339499 (Patent Document 2) discloses a resin having a fluorene skeleton such as bisphenolfluorene, bisaminophenylfluorene, or bisphenoxyethanolfluorene as a polymerization component (polyester resin, polycarbonate resin, A urethane resin, an acrylic resin, a polyamide resin, a polyimide resin, an epoxy resin, a vinyl ester resin, a phenol resin, an aniline resin, and the like) and an additive are disclosed.

  Japanese Patent No. 3440110 (Patent Document 3) discloses the following general formula:

(Where X is

Each independently represents an unsubstituted aryl group having 6 to 12 carbon atoms, and R ¹ , R ² , R ³ and R ⁴ each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms or a carbon atom. Represents an unsubstituted aryl group of 6 to 12, a and b each independently represent an integer of 0 to 4, c and d each independently represents an integer of 0 to 6, Z represents a single bond, -O -, - CO -, - S- or -SO ₂ - it represents. The bisphenol derivative represented by this is disclosed.

  In this document, the bisphenol derivative is obtained by reacting a phenol with a carbonyl compound. (I) Examples of the phenol include o-phenylphenol and o- (4-methylphenol). -Phenylphenol is preferred, and (ii) carbonyl compounds include fluorenone, anthrone, pentacenone and the like, and it is usually described that fluorenone is preferably used.

Under such circumstances, the development of materials that are superior in heat resistance, refractive index, and the like is required.
JP 2002-284864 A (Claims) JP 2004-339499 A (claims, paragraph number [0032]) Japanese Patent No. 3440110 (claims, paragraph numbers [0007] to [0011], Examples)

  Accordingly, an object of the present invention is to provide a novel dibenzofluorene compound having characteristics such as excellent heat resistance and high refractive index, a production method thereof, and a resin containing the compound as a polymerization component.

  Another object of the present invention is to provide a novel dibenzofluorene compound having excellent reactivity and handling properties, a method for producing the same, and a resin containing the compound as a polymerization component.

  Still another object of the present invention is to provide a novel dibenzofluorene compound having low thermal expansibility and high dimensional accuracy, a method for producing the same, and a resin containing the compound as a polymerization component.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that aromatic carbonization having a hydroxyl group or the like at the 9-position of dibenzofluorenes (specifically, 2,3: 6,7-dibenzofluorenes). A novel dibenzofluorene compound in which two hydrogen rings (phenol skeleton, naphthol skeleton, etc.) are bonded has been found to have excellent heat resistance, high refractive index, low linear expansion properties, etc. completed.

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

(In the formula, ring Z represents an aromatic hydrocarbon ring, E represents an oxygen atom or sulfur atom, R ¹ and R ² are the same or different, and are a cyano group, a halogen atom, an alkyl group, a hydroxyalkyl group, a carboxyl group. , Alkoxycarbonyl group, R ³ is hydrocarbon group, alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, substituted amino group, hydroxyalkyl R represents a group or a carboxyl group, R ⁴ represents an alkylene group, k is an integer of 0 to 2, l is an integer of 0 to 3, m is an integer of 0 or more, n is an integer of 0 or more, and p is 1 or more. (It is an integer.)
In the compound of the present invention, in the formula (1), ring Z may be a benzene ring, R ³ may be an alkyl group, and m may be 0 to 2. Such a compound can improve handling properties compared to a compound in which R ³ is an aryl group (such as a phenyl group) and m is 1 or more (for example, 1). It is also excellent in reactivity (specifically, reactivity of hydroxyl group or mercapto group). Therefore, it is easy to apply as a resin raw material (for example, a polyol component or a polythiol component of a poly (thio) ester-based resin) and has high practicality.

Further, the compound of the present invention may be a compound in which the ring Z is a naphthalene ring in the formula (1). Such a compound can further improve heat resistance as compared with a compound in which R ³ is an aryl group (such as a phenyl group), and m is 1 or more (for example, 1), and has a thermal expansion property or linearity. Expandability can be reduced. Therefore, it can be used as a resin raw material with high dimensional stability.

  The compound may typically be a compound that satisfies any of the following (i) to (iii).

(I) In the formula (1), the ring Z is a benzene ring, E is an oxygen atom, m is 0, R ⁴ is a C _2-4 alkylene group, and n is 0 to 10 (for example, 0-4), and p is 1-3 (for example, 1-2, especially 1). (Ii) In formula (1), ring Z is a benzene ring, E is an oxygen atom, R ³ is a C _1-4 alkyl group (such as a methyl group), m is 1 to 2, R ⁴ is a C _2-4 alkylene group, and n is 0 to 10 (for example, 0 to 4). , P is 1 to 3 (for example, 1 to 2, particularly 1) (iii) In formula (1), ring Z is a naphthalene ring, E is an oxygen atom, and R ⁴ is C _2-4 alkylene. Group, n is 0 to 10 (for example, 0 to 4), and p is 1 to 3 (for example, 1 to 2, particularly 1).

In particular, the compounds are 9,9-bis (hydroxyphenyl) -2,3: 6,7-dibenzofluorene, 9,9-bis (mono or diC _1-4 alkyl-hydroxyphenyl) -2,3: 6,7 dibenzo fluorene, 9,9-bis (hydroxy _{C 2-4} alkoxyphenyl) -2,3: 6,7-dibenzo fluorene, 9,9-bis (hydroxy _{C 2-4} alkoxy - mono- or di-C _1-4 alkylphenyl) -2,3: 6,7-dibenzofluorene, 9,9-bis (hydroxynaphthyl) -2,3: 6,7-dibenzofluorene, and 9,9-bis (hydroxyC _{2- 4} alkoxy naphthyl) -2,3: 6,7-dibenzofluorene may be used.

In particular, the compound is 9,9-bis (mercaptophenyl) -2,3: 6,7-dibenzofluorene, 9,9-bis (mono or diC _1-4 alkyl-mercaptophenyl) -2, 3: 6,7-dibenzofluorene, 9,9-bis (mercapto C _2-4 alkoxyphenyl) -2,3: 6,7-dibenzofluorene, 9,9-bis (mercapto C _2-4 alkoxy-mono or di _{C 1-4} alkyl phenyl) -2,3: 6,7-dibenzo fluorene, 9,9-bis (mercaptomethyl naphthyl) -2,3: 6,7-dibenzo fluorene, and 9,9-bis (mercapto C _2-4 alkoxynaphthyl) -2,3: 6,7-dibenzofluorene may be used.

  The present invention also includes a method for producing the compound through at least the step (A) of reacting the compound represented by the following formula (2) with the compound represented by the following formula (3) or a derivative thereof. .

(In the formula, Z, E, R ¹ , R ² , R ³ , R ⁴ , k, l, m, n and p are the same as above.)
The present invention includes a resin having the compound as a polymerization component (that is, a polyol component or a polythiol component). In such a resin, when the compound is (i) a compound in which E is an oxygen atom in the formula (1), as a polyol component (for example, a diol component), (ii) E in the formula (1) Can be used as a polythiol component (for example, a dithiol component). That is, the resin is usually a resin comprising a polyol component or a polythiol component composed of the compound (or at least including the compound) or a polythiol component as a polymerization component (or monomer). Such a resin may be, for example, a resin selected from a poly (thio) ester resin, a poly (thio) carbonate resin, and a (thio) epoxy resin.

  Typically, the resin may be the following resin.

  A polyester resin having an ester unit represented by the following formula (A1).

(In the formula, A ¹ represents a residue of the dicarboxylic acid component (b), and Z, R ¹ , R ² , R ³ , R ⁴ , k, l, m, and n are the same as described above.)
A polyether resin having an ether unit represented by the following formula (A2).

(In the formula, A ² is a residue of compound (C) having a plurality of halogen atoms, and Z, R ¹ , R ² , R ³ , R ⁴ , k, l, m and n are the same as described above.)
A polythioether resin having a thioether unit represented by the following formula (A3).

(Wherein A ³ is the residue of compound (D) having a plurality of halogen atoms, and Z, R ¹ , R ² , R ³ , R ⁴ , k, l, m and n are the same as above)

  The novel dibenzofluorene compound of the present invention has properties such as excellent heat resistance and high refractive index. In particular, a dibenzofluorene compound excellent in reactivity and handling can be obtained by using a benzene ring or a cresol ring as the type of the aromatic hydrocarbon ring bonded to the 9-position of dibenzofluorenes. In addition, when the aromatic hydrocarbon ring is a condensed aromatic hydrocarbon ring such as a naphthalene ring, a dibenzofluorene compound having low thermal expansibility and high dimensional accuracy can be obtained. Such a dibenzofluorene compound of the present invention can be suitably used as a resin component or the like.

  The compound of the present invention (sometimes referred to as a dibenzofluorene compound) is located at the 9th position of dibenzofluorenes (specifically, sometimes referred to as 2,3: 6,7-dibenzofluorenes, simply dibenzofluorene, fluorene, etc.). , A compound substituted by an aromatic hydrocarbon ring having a hydroxyl group or a mercapto group, and may be a compound represented by the following formula (1).

(In the formula, ring Z represents an aromatic hydrocarbon ring, E represents an oxygen atom or sulfur atom, R ¹ , R ² and R ³ are the same or different and represent a substituent, and R ⁴ represents an alkylene group.) Is an integer of 0 to 2, l is an integer of 0 to 3, m is an integer of 0 or more, n is an integer of 0 or more, and p is an integer of 1 or more.)
In the above formula (1), examples of the aromatic hydrocarbon ring represented by ring Z include a benzene ring and a condensed polycyclic aromatic hydrocarbon ring (specifically, a condensed polycyclic hydrocarbon ring containing at least a benzene ring). ) And the like. Examples of the condensed polycyclic aromatic hydrocarbon corresponding to the condensed polycyclic aromatic hydrocarbon ring include condensed bicyclic hydrocarbons (for example, C _8-20 condensed bicyclic hydrocarbons such as indene and naphthalene, preferably C _10-16 condensed bicyclic hydrocarbons) and condensed tricyclic hydrocarbons (for example, anthracene, phenanthrene, etc.) and the like, and the like. Preferable condensed polycyclic hydrocarbons include condensed polycyclic aromatic hydrocarbons (naphthalene, anthracene, etc.), and naphthalene is particularly preferable. The two rings Z substituted at the 9-position of dibenzofluorenes may be the same or different rings, and may usually be the same ring.

  Preferred ring Z includes a benzene ring and a naphthalene ring (particularly a benzene ring). In addition, when the ring Z is a condensed polycyclic aromatic hydrocarbon ring, the substitution position of the ring Z substituted at the 9-position of dibenzofluorenes is not particularly limited. For example, the naphthyl group substituted at the 9-position is , 1-naphthyl group, 2-naphthyl group and the like.

Further, the substituent represented by the group R ¹ and the group R ² is not particularly limited, and for example, a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), hydroxyalkyl group (for example , Hydroxy C _1-4 alkyl groups such as methylol groups), carboxyl groups, alkoxycarbonyl groups (such as C _1-4 alkoxycarbonyl groups such as methoxycarbonyl groups), hydrocarbon groups [for example, alkyl groups, aryl groups (phenyl groups) C _6-10 aryl group such as, etc.], etc.], etc., in particular often an alkyl group. Examples of the alkyl group include C _1-6 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group (for example, a C _1-4 alkyl group, particularly a methyl group). . In addition, when k or l is plural (two or more), the group R ¹ or the group R ² may be different from each other or the same. Further, the group R ¹ or the group R ² substituted on two benzene rings constituting the dibenzofluorene (or dibenzofluorene skeleton) may be the same or different. Further, the bonding position (substitution position) of the group R ¹ or the group R ² with respect to the benzene ring constituting the dibenzofluorene is not particularly limited. Preferred substitution numbers k and l are each 0 or 1, in particular 0. In the two benzene rings constituting dibenzofluorene, the substitution number k or l may be the same or different from each other.

Examples of the substituent R ³ substituted on the ring Z include, for example, an inert group or a non-reactive group {for example, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an s-butyl group, _{C 1-20} alkyl groups such as t- butyl group, preferably a _{C 1-8} alkyl group, more preferably a _{C 1-6} alkyl group), a cycloalkyl group (cyclopentyl group, cyclohexylene, such as cyclohexyl group _{C 5- 10} cycloalkyl group, preferably C _5-8 cycloalkyl group, more preferably C _5-6 cycloalkyl group, etc., aryl group [for example, phenyl group, alkylphenyl group (methylphenyl group (or tolyl group, 2- methylphenyl group, 3-methylphenyl group), a dimethylphenyl group (xylyl)), _{C 6-10} aryl group such as a naphthyl group, The Mashiku _{C 6-8} aryl group, especially a phenyl group, a hydrocarbon group such as an aralkyl group (a benzyl group and _{C 6-10} aryl _{-C 1-4} alkyl group such as a phenethyl group); an alkoxy group (methoxy Ether groups such as C _1-4 alkoxy groups such as ethoxy groups, propoxy groups, n-butoxy groups, isobutoxy groups, t-butoxy groups); acyl groups (C _1-6 acyl groups such as acetyl groups) Alkoxycarbonyl group (C _1-4 alkoxycarbonyl group such as methoxycarbonyl group); halogen atom (fluorine atom, chlorine atom etc.); nitro group; cyano group; substituted amino group (dialkylamino group etc.)}, hydroxy alkyl group (e.g., hydroxy C _1-4 alkyl group such as a methylol group), and a carboxyl group

Preferred substituents R ³ are hydrocarbon groups such as alkyl groups (for example, C _1-6 alkyl groups), alkoxy groups (C _1-4 alkoxy groups, etc.), and in particular, C _1-4 alkyl groups (particularly, A methyl group) is preferred. The substituent R ³ may be substituted alone or in combination of two or more in the same ring Z (that is, when m is plural, R ³ may be the same or different). Further, the substituents R ³ substituted on different rings Z may be the same or different from each other, and may usually be the same.

The substitution number m of the substituent R ³ can be appropriately selected according to the type of the ring Z and the like, and is not particularly limited. For example, 0 to 8, preferably 0 to 6 (for example, 1 to 5), and more preferably 0. It may be about ~ 4. In particular, when the ring Z is a benzene ring, the substitution number m is, for example, 0 to 3, preferably 0 to 2, and more preferably 0 or 1. Further, when the ring Z is a condensed aromatic hydrocarbon ring such as a naphthalene ring, the preferred substitution number m may be 0 to 8, preferably 0 to 4, more preferably 0 or 1, particularly 0. . The number of substitutions m may be the same or different in the two rings Z, and is usually the same in many cases. Incidentally, the substitution position of the substituent ^{R 3} is not particularly limited, groups for Ring Z ^- can be appropriately selected depending on the substitution position of _{[(OR 4) n -E-} H]. For example, when the ring Z is a benzene ring, it can be substituted at an appropriate position on the 2-6 position of the phenyl group (eg, 3-position, 3,5-position, etc.).

In the group-[(OR ⁴ ) _n -EH] substituted on the ring Z, the alkylene group represented by the group R ⁴ is not particularly limited, but for example, a C _2-10 alkylene group (for example, an ethylene group) , Trimethylene group, propylene group, butane-1,2-diyl group, C _2-6 alkylene group such as hexylene group) and the like, in particular, C _2-4 alkylene group (particularly ethylene group, propylene group, etc.). C _2-3 alkylene group) is preferred. R ⁴ may be the same or different alkylene group in the same ring Z (that is, when n is plural, R ⁴ may be the same or different). That is, when n is 2 or more, the polyalkoxy (polyoxyalkylene) group may be composed of the same oxyalkylene group, and a plurality of oxyalkylene groups (for example, an oxyethylene group and an oxypropylene group). It may be configured. In general, R ³ may be the same alkylene group in the same ring Z. R ⁴ may be the same or different in different rings Z, and may usually be the same.

The number (addition mole number) n of oxyalkylene groups (OR ⁴ ) can be selected from a range of about 0 to 15, for example, 0 to 12 (for example, 1 to 12), preferably 0 to 8 (for example, 1 to 1). 8), more preferably 0 to 6 (for example, 1 to 6), particularly 0 to 4 (for example, 1 to 4). The number of substitutions n may be the same or different in different rings Z. In the two rings Z, the total of the oxyalkylene groups (n × 2) can be selected from the range of about 0 to 30, for example, 0 to 24 (for example, 2 to 20), preferably 0 to 16 (for example, 2 to 14), more preferably 0 to 12 (for example, 2 to 10), particularly 0 to 8 (for example, 2 to 8).

In addition, the substitution number p of the group-[(OR ⁴ ) _n -EH] substituted on the ring Z may be an integer of 1 or more, for example, 1 to 8, preferably 1 to 5, and more preferably. It may be 1-4, especially 1-3. In particular, when ring Z is a benzene ring, p may be 1 to 4, preferably 1 to 3, more preferably 1 to 2 (particularly 1). Note that p may be the same or different in different rings Z, and may usually be the same.

In addition, although group E is an oxygen atom or a sulfur atom, when p is plural (2 or more), in the group-[(OR ⁴ ) _n -EH] substituted on the same ring Z, E is the same. Or different. In the group-[(OR ⁴ ) _n -EH] substituted with two different rings Z, E may be the same or different. Usually, in any case, E is often the same (for example, all E are oxygen atoms).

The substitution position of the group-[(OR ⁴ ) _n -EH] substituted on the ring Z is not particularly limited, and can be appropriately selected depending on the number of p and the like. For example, when the ring Z is a benzene ring, the substitution position of the group-[(OR ⁴ ) _n -EH] substituted on the ring Z is the 2-6 position of the phenyl group substituted on the 9-position of dibenzofluorenes. Any of these may be used. In particular, at least the 4-position of the phenyl group may be substituted with a group-[(OR ⁴ ) _n -EH]. Further, when the ring Z is a naphthalene ring, the group-[(OR ⁴ ) _n -EH] depends on the substitution position of the naphthyl group (1 or 2-naphthyl group) substituted with dibenzofluorenes, etc. Any of the 5th to 8th positions (for example, the 5th and 6th positions) may be substituted at least with the ring Z. In particular, when a 2-naphthyl group (β-naphthyl group) is substituted at the 9-position of dibenzofluorenes, the group — [(OR ⁴ ) _n -EH] is substituted at the 6-position of the naphthyl group. In many cases, when the 1-naphthyl group (α-naphthyl group) is substituted at the 9-position of the dibenzofluorenes, a group — [( OR ⁴ ) _n -E-H] is often substituted.

Typically, the substitution position of the group-[(OR ⁴ ) _n -EH] substituted on ring Z is (1) when ring Z is a benzene ring and p is 1, the 9-position of dibenzofluorenes 2 to 6 positions (particularly the 4 position) of the phenyl group to be substituted with (2) When ring Z is a naphthalene ring and p is 1, the naphthyl group to be substituted at the 9 position of dibenzofluorenes Depending on the substitution position of (1- or 2-naphthyl group, etc.), it may be substituted at any of 5-8 positions (for example, 5-position, 6-position, etc.), and (3) Ring Z is benzene. When p is 2 and p is 2, two substitution positions (for example, the 3-position and 4-position; 2-position and 4-position; (4) Ring Z is a benzene ring, and p is both 3 In some cases, 3 substitution positions (for example, 2nd, 3rd and 4th positions; 2nd, 4th and 5th positions; 3rd, 4th and 5th positions; 2nd, 4th and 6th positions).

  As a specific dibenzofluorene compound having a hydroxyl group (dibenzofluorene compound in which E is an oxygen atom in the formula (1)), a dibenzofluorene compound having two hydroxyl groups [for example, 9,9-bis (hydroxyphenyl) ) -2,3: 6,7-dibenzofluorenes, 9,9-bis (hydroxy (poly) alkoxyphenyl) -2,3: 6,7-dibenzofluorenes, 9,9-bis (hydroxynaphthyl)- 2,3: 6,7-dibenzofluorene, 9,9-bis (hydroxy (poly) alkoxynaphthyl) -2,3: 6,7-dibenzofluorene, etc.] benzofluorene having three or more hydroxyl groups Compounds {eg, 9,9-bis (polyhydroxyphenyl) -2,3: 6,7-dibenzofluore 9,9-bis [poly (hydroxy (poly) alkoxy) phenyl] -2,3: 6,7-dibenzofluorenes, 9,9-bis (polyhydroxynaphthyl) -2,3: 6,7- Dibenzofluorenes, 9,9-bis [poly (hydroxy (poly) alkoxy) naphthyl] -2,3: 6,7-dibenzofluorenes, etc.}.

  Hereinafter, in the dibenzofluorene compound, “2,3: 6,7-dibenzofluorene” may be simply referred to as “dibenzofluorene”.

Examples of 9,9-bis (hydroxyphenyl) dibenzofluorenes (compounds in which ring Z is a benzene ring, n is 0, E is an oxygen atom, and p is 1 in the formula (1)) include, for example, 9,9 -Bis (hydroxyphenyl) dibenzofluorene [9,9-bis (4-hydroxyphenyl) dibenzofluorene and the like], 9,9-bis (alkyl-hydroxyphenyl) dibenzofluorene [9,9-bis (4-hydroxy-3) -Methylphenyl) dibenzofluorene, 9,9-bis (4-hydroxy-3-ethylphenyl) dibenzofluorene, 9,9-bis (3-hydroxy-2-methylphenyl) dibenzofluorene, 9,9-bis (4 -Hydroxy-3,5-dimethylphenyl) dibenzofluorene, 9,9-bis (4-hydroxy-2,6-dimethyl) Butylphenyl) 9,9-bis such dibenzofluorene (mono- or _{di-C 1-4} alkyl - hydroxyphenyl) dibenzo fluorene, 9,9-bis (aryl - hydroxyphenyl) dibenzo fluorene [e.g., 9,9-bis (4-hydroxy-3-phenylphenyl) dibenzofluorene, etc.].

9,9-bis (hydroxy (poly) alkoxyphenyl) dibenzofluorenes (in the formula (1), ring Z is a benzene ring, n is 1 or more, E is an oxygen atom, and p is 1), For example, 9,9-bis (hydroxyalkoxyphenyl) dibenzofluorene {eg, 9,9-bis [4- (2-hydroxyethoxy) phenyl] dibenzofluorene, 9,9-bis [4- (3-hydroxypropoxy) 9,9-bis (hydroxyC) such as phenyl] dibenzofluorene, 9-bis [4- (2-hydroxypropoxy) phenyl] dibenzofluorene, 9,9-bis [4- (4-hydroxybutoxy) phenyl] dibenzofluorene _2-4 alkoxyphenyl) dibenzofluorene and the like}, 9,9-bis (hydroxyalkoxy-a Ruylphenyl) dibenzofluorene {eg, 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] dibenzofluorene, 9,9-bis [2- (2-hydroxyethoxy) -5-methylphenyl Dibenzofluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-ethylphenyl] dibenzofluorene, 9,9-bis [4- (3-hydroxypropoxy) -3-methylphenyl] dibenzofluorene, 9 such as 9,9-bis [4- (4-hydroxybutoxy) -3-methylphenyl] dibenzofluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] dibenzofluorene , 9-bis (hydroxy _{C 2-4} alkoxy - mono- or _{di-C 1-6} alkyl phenyl) dibenzofluorenyl 9,9-bis (hydroxyalkoxy-arylphenyl) dibenzofluorene {e.g., 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] dibenzofluorene}. -Bis (hydroxyalkoxyphenyl) dibenzofluorenes (in the formula (1), ring Z is a benzene ring, n is 1, E is an oxygen atom, p is 1), and these compounds, 9,9-bis (hydroxypolyalkoxyphenyl) dibenzofluorenes {for example, 9,9-bis {4- [2- (2-hydroxyethoxy) ethoxy] phenyl} dibenzo, wherein n is 2 or more in formula (1) 9,9-bis fluorene [(hydroxy _{C 2-4 alkoxy) C 2-4} alkoxyphenyl] Jibenzofu (Compound of n = 2) Oren etc.} and the like.

Examples of 9,9-bis (hydroxynaphthyl) dibenzofluorenes (compounds in which the ring Z is a naphthalene ring, n is 0, E is an oxygen atom, and p is 1 in the formula (1)) include, for example, 9,9 -Bis (hydroxynaphthyl) dibenzofluorenes {for example, 9,9-bis [6- (2-hydroxynaphthyl)] dibenzofluorene, 9,9-bis [1- (6-hydroxynaphthyl)] dibenzofluorene, 9, 9,9-bis (hydroxynaphthyl) dibenzofluorene} which may have a substituent such as 9-bis [1- (5-hydroxynaphthyl)] dibenzofluorene}. Also, 9,9-bis (hydroxy (poly) alkoxynaphthyl) dibenzofluorenes (in the formula (1), ring Z is a naphthalene ring, n is 1 or more, E is an oxygen atom, and p is 1). Is, for example, 9,9-bis (hydroxyalkoxynaphthyl) dibenzofluorene {eg, 9,9-bis [6- (2- (2-hydroxyethoxy) naphthyl)] dibenzofluorene, 9,9-bis [1- Optionally having substituents such as (6- (2-hydroxyethoxy) naphthyl)] dibenzofluorene, 9,9-bis [1- (5- (2-hydroxyethoxy) naphthyl)] dibenzofluorene 9, 9-bis (hydroxyC _2-4 alkoxynaphthyl) dibenzofluorene etc.} and the like.

  Examples of 9,9-bis (polyhydroxyphenyl) dibenzofluorenes include 9,9-bis (di or trihydroxyphenyl) dibenzofluorenes. 9,9-bis (di- or trihydroxyphenyl) dibenzofluorenes (in the formula (1), ring Z is a benzene ring, n is 0, E is an oxygen atom, and p is 2 or 3) Compounds corresponding to the 9,9-bis (hydroxyphenyl) dibenzofluorenes, wherein p is 2 or 3 in the formula (1), such as 9,9-bis (dihydroxyphenyl) dibenzofluorene [9,9-bis (3,4-dihydroxyphenyl) dibenzofluorene, 9,9-bis (3,5-dihydroxyphenyl) dibenzofluorene and the like], 9,9-bis (trihydroxyphenyl) dibenzofluorene [for example, 9,9-bis ( 2,4,6- or 2,4,5- or 3,4,5-trihydroxyphenyl) dibenzofluorene etc.].

The 9,9-bis [poly (hydroxy (poly) alkoxy) phenyl] dibenzofluorenes include 9,9-bis [di or tri (hydroxy (poly) alkoxy) phenyl] dibenzofluorenes. 9,9-bis [di or tri (hydroxy (poly) alkoxy) phenyl] dibenzofluorenes (in formula (1), ring Z is a benzene ring, n is 1 or more, E is an oxygen atom, p is 2 or 3 A compound corresponding to 9,9-bis (di or trihydroxyphenyl) dibenzofluorenes, and a compound in which n is 1 or more in the formula (1), for example, 9,9-bis [di (hydroxy Alkoxy) phenyl] dibenzofluorene {eg, 9,9-bis [3,4- or 3,5-di (2-hydroxyethoxy) phenyl] dibenzofluorene, 9,9-bis [3,4-di (2- or 3-hydroxypropoxy) phenyl] 9,9-bis such dibenzofluorene [di (hydroxy _{C 2-4} alkoxy) phenyl] dibenzo fluorene}, 9,9-bi Su [tri (hydroxyalkoxy) phenyl] dibenzofluorene {eg, 9,9-bis [2,3,4- or 2,4,6- or 3,4,5-tri (2-hydroxyethoxy) phenyl] dibenzo 9,9-bis fluorene [tri (hydroxy _{C 2-4} alkoxy) phenyl] dibenzo fluorene}, corresponding to these compounds, the n in formula (1) is 2 or more 9,9-bis [di Or tri (hydroxypolyalkoxy) phenyl] dibenzofluorenes.

9,9-bis (polyhydroxynaphthyl) dibenzofluorenes (in the formula (1), ring Z is a naphthalene ring, n is 0, E is an oxygen atom, p is 2 or more), Compounds corresponding to 9-bis (hydroxynaphthyl) dibenzofluorenes, such as 9,9-bis (di or trihydroxynaphthyl) dibenzofluorene, are included. Moreover, as 9,9-bis [poly (hydroxy (poly) alkoxy) naphthyl] dibenzofluorenes, compounds corresponding to the 9,9-bis (hydroxy (poly) alkoxynaphthyl) dibenzofluorenes, for example, 9, such as 9-bis [di- or tri (hydroxy _{C 2-4} alkoxy) naphthyl] dibenzo fluorene such as 9,9-bis [di or tri (hydroxy (poly) alkoxy) naphthyl] dibenzo fluorenes include.

Among dibenzofluorene compounds having a hydroxyl group, preferred compounds having two hydroxyl groups include 9,9-bis (hydroxyphenyl) dibenzofluorene, 9,9-bis (alkyl-hydroxyphenyl) dibenzofluorene [for example, 9 , 9-bis (mono or diC _1-4 alkyl-hydroxyphenyl) dibenzofluorene], 9,9-bis (hydroxy (poly) C _2-4 alkoxyphenyl) dibenzofluorene [eg, 9,9-bis (hydroxy C _2-4 alkoxyphenyl) dibenzofluorene and the like], 9,9-bis (hydroxyC _2-4 alkoxy-alkylphenyl) dibenzofluorene {eg, 9,9-bis (hydroxy (poly) C _2-4 alkoxy-alkyl Phenyl) dibenzofluorene [ Example, 9,9-bis (hydroxy _{C 2-4} alkoxy - mono- or _{di-C 1-4} alkyl phenyl) dibenzo fluorene], etc.}, 9,9-bis (hydroxy naphthyl) dibenzo fluorene, 9,9-bis ( Hydroxy (poly) C _2-4 alkoxynaphthyl) dibenzofluorene [eg, 9,9-bis (hydroxyC _2-4 alkoxynaphthyl) dibenzofluorene] and the like.

  Among these compounds having two hydroxyl groups, dibenzofluorene compounds such as 9,9-bis (alkyl-hydroxyphenyl) dibenzofluorene are compared with dibenzofluorene compounds in which ring Z is substituted with an unsubstituted phenyl group. This is advantageous in terms of handling. In addition, the reactivity is also excellent because the steric hindrance of the molecule is small. Furthermore, it is easier to produce than a dibenzofluorene compound in which a ring Z is substituted with a phenyl group, which is industrially advantageous.

  In addition, dibenzofluorene compounds in which a ring Z such as 9,9-bis (hydroxynaphthyl) dibenzofluorene is a condensed aromatic hydrocarbon ring such as a naphthalene ring are excellent in heat resistance and at a higher level. This is preferable because the expandability can be reduced. Moreover, such a compound can also impart a high refractive index.

Typical dibenzofluorene compounds having 3 or more hydroxyl groups include 9,9-bis (dihydroxyphenyl) dibenzofluorene, 9,9-bis (trihydroxyphenyl) dibenzofluorene, and 9,9-bis [di. (Hydroxy C _2-4 alkoxy) phenyl] dibenzofluorene, 9,9-bis [tri (hydroxy C _2-4 alkoxy) phenyl] dibenzofluorene and the like are included.

Further, the dibenzofluorene compound having a specific mercapto group (dibenzofluorene compound in which E is a sulfur atom in the formula (1)) corresponds to the dibenzofluorene compound in which E is an oxygen atom, The compound which replaced the oxygen atom with the sulfur atom is mentioned. Such compounds include, for example, 9,9-bis (mercaptophenyl) dibenzofluorenes [for example, 9,9-bis (mercaptophenyl) dibenzofluorene such as 9,9-bis (4-mercaptophenyl) dibenzofluorene. 9,9-bis (mono or diC _1-4 alkyl-mercaptophenyl) dibenzofluorene, etc.] such as 9,9-bis (4-mercapto-3-methylphenyl) dibenzofluorene], 9,9-bis (mercapto) (poly) alkoxyphenyl) dibenzo fluorenes [e.g., 9,9-bis (mercapto _{C 2-4} alkoxyphenyl) dibenzo fluorene, 9,9-bis (mercapto _{C 2-4} alkoxy - mono- or _{di-C 1-6} alkyl Phenyl) dibenzofluorene], 9,9-bis (mercaptonaphthyl) ) Dibenzofluorene compounds having two mercapto groups such as dibenzofluorenes, 9,9-bis (mercapto (poly) alkoxynaphthyl) dibenzofluorenes; 9,9-bis (polymercaptophenyl) dibenzofluorenes, 9,9 -Bis [poly (mercapto (poly) alkoxy) phenyl] dibenzofluorenes, 9,9-bis (polymercaptonaphthyl) dibenzofluorenes, 9,9-bis [poly (mercapto (poly) alkoxy) naphthyl] dibenzofluorenes And dibenzofluorene compounds having three or more mercapto groups.

Among dibenzofluorene compounds having a mercapto group, preferred compounds having two mercapto groups include 9,9-bis (mercaptophenyl) dibenzofluorene, 9,9-bis (alkyl-mercaptophenyl) dibenzofluorene [for example, 9 , 9-bis (mono- or _{di-C 1-4} alkyl - mercapto phenyl) dibenzo fluorene, 9,9-bis (mercapto _{C 2-4} alkoxyphenyl) dibenzo fluorene, 9,9-bis (mercapto _{C 2-4} alkoxy - alkylphenyl) dibenzo fluorene [e.g., 9,9-bis (mercapto _{C 2-4} alkoxy - mono- or _{di-C 1-4} alkyl phenyl) dibenzo fluorene, 9,9-bis (mercaptomethyl naphthyl) dibenzo fluorene, 9 , 9-bis (mercapto _{C 2 4} alkoxy naphthyl) such as dibenzo fluorene and the like.

  Particularly, among compounds having two mercapto groups, 9,9-bis (mercaptophenyl) dibenzofluorene, 9,9-bis (alkyl-mercaptophenyl) dibenzofluorene, 9,9-bis (mercaptonaphthyl) dibenzofluorene, etc. The specific dibenzofluorene compound is suitable for the same reason as described above.

Typical compounds having three or more mercapto groups include 9,9-bis (dimercaptophenyl) dibenzofluorene, 9,9-bis (trimercaptophenyl) dibenzofluorene, 9,9-bis [di ( mercapto _{C 2-4} alkoxy) phenyl] dibenzo fluorene, and the like 9,9-bis [tri (mercapto _{C 2-4} alkoxy) phenyl] dibenzo fluorene.

[Method for producing dibenzofluorene compound]
Although the manufacturing method of the dibenzofluorene compound of this invention is not specifically limited, Usually, it can manufacture through the process with which the compound corresponding to dibenzofluorene and the compound corresponding to the ring Z are made to react. Typically, the compound of the present invention undergoes at least a step of reacting a compound represented by the following formula (2) with a compound represented by the following formula (3) or a derivative thereof (step (A)). Can be manufactured.

(In the formula, Z, E, R ¹ , R ² , R ³ , R ⁴ , k, l, m, n and p are the same as above.)
The compound represented by the above formula (2) is a compound (dibenzofluorenone) corresponding to dibenzofluorenes in the compound represented by the above formula (1). A typical dibenzofluorenone is 9-dibenzofluorenone (specifically 2,3: 6,7-dibenzo-9-fluorenone). The purity of the dibenzofluorenones to be used is not particularly limited, but is usually 95% by weight or more, preferably 99% by weight or more.

  As dibenzofluoronones, commercially available products may be used, or synthesized ones may be used.

  As a method for producing dibenzofluorenones, for example, (1) a method in which phenyl 2-formylbenzylsulfonate and benz [f] indenone are reacted in the presence of t-butoxide (Synthesis 2006, No. 15, 2556). -2562), (2) α, α, α ′, α′-tetrabromo-o-xylene and 2-cyclopenten-1-one are reacted in the presence of sodium iodide to produce a benz [f Indan-1-one was obtained, and the obtained benz [f] indan-1-one was reacted in the presence of NBS (N-bromosuccinimide) and benzoyl peroxide to obtain benz [f] inden-1-one. Obtained and obtained benz [f] inden-1-one and α, α, α ′, α′-tetrabromo-o-xylene were sodium iodide (The method described in Journal of Organic Chemistry, Vol. 59, No. 21, 1994 6484-6486 (1994)) and the like.

  As described above, the compound represented by the formula (1) is obtained by reacting the compound represented by the formula (2) with the compound represented by the formula (3) or a derivative thereof. The case where E is a compound in which E is an oxygen atom in formula (1) and the case where a compound in which E is a sulfur atom in formula (1) are obtained will be described in detail.

(Method for producing a compound in which E is an oxygen atom in formula (1))
The compound in which E is an oxygen atom in the formula (1) includes the compound represented by the formula (2) (dibenzofluorenones) and the compound in which E is an oxygen atom in the formula (3) (that is, the following formula It can be obtained through a step of reacting (compound represented by (3A)) (step (A1)).

(In the formula, Z, R ³ , R ⁴ , m, n and p are the same as above.)
The compound represented by the above formula (3A) (aromatic hydrocarbon having a hydroxyl group, aromatic hydrocarbon compound having a hydroxyl group) corresponds to the aromatic hydrocarbon ring having a hydroxyl group in the formula (1). doing. That is, in the formula (3A), the ring Z corresponds to the ring Z in the formula (1), and examples thereof include the aromatic hydrocarbon rings exemplified above (benzene ring and naphthalene ring). In the formula (3A), the substituents R ³ , R ⁴ , m, n and p are the same as those described above, and the preferred embodiments are also the same.

  The compound represented by the formula (3A) can be roughly classified into (i) a compound in which n is 0 and (ii) a compound in which n is 1 or more.

(I) Compound in which n is 0 As a typical compound in which n is 0 in the formula (3A), a compound in which the ring Z is a benzene ring and a compound in which the ring Z is a naphthalene ring are exemplified.

Examples of the compound in which ring Z is a benzene ring include phenols {for example, phenol, phenol having a substituent [for example, alkylphenol (for example, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2 , 5-dimethylphenol, mono- or di-C _1-4 alkyl-phenols such as 2,6-dimethylphenol), cycloalkylphenols (eg C _5-8 cycloalkyl-phenols such as 2-cyclohexylphenol), arylphenols (For example, C _6-10 aryl-phenol such as o-phenylphenol), alkoxyphenol (such as C _1-4 alkoxy-phenol such as o-methoxyphenol), etc.], polyhydroxybenzenes {for example, dihydroxybenzene (carbon Dihydroxybenzenes such as techol, resorcinol, hydroquinone), alkyl-dihydroxybenzene [mono- or di-C _1-4 alkyl-dihydroxybenzene, etc. such as dihydroxytoluene, dihydroxyxylene]; Etc.) and the like.

In addition, examples of the compound in which the ring Z is a naphthalene ring include naphthols {that is, a compound in which the ring Z is a naphthalene ring and p is 1 in the formula (3A), such as naphthol (1-naphthol, 2-naphthol), substituted Naphthol having a group [for example, alkyl naphthol such as methyl naphthol, ethyl naphthol and dimethyl naphthol (for example, C _1-4 alkyl naphthol)], alkoxy naphthol (for example, C _1-4 alkoxy naphthol such as ethoxy naphthol), etc. }, Polyhydroxynaphthalenes corresponding to these naphthols (or monohydroxynaphthalenes) (that is, compounds in which ring Z is a naphthalene ring and p is 2 or more in formula (3A), such as 1,3-dihydroxynaphthalene) 1,4-dihydroxynaphth 2,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,2,4- And di- or trihydroxynaphthalenes such as trihydroxynaphthalene and 1,3,8-trihydroxynaphthalene).

(I) Compound in which n is 1 or more As a typical compound in which n is 1 or more in the formula (3A), alkylene glycol monophenyl ethers [for example, alkylene glycol monophenyl ether (for example, 2-phenoxyethanol (for example) Ethylene glycol monophenyl ether), propylene glycol monophenyl ether, _C2-4 alkylene glycol monophenyl ether such as tetramethylene glycol monophenyl ether), alkylene glycol monoalkylphenyl ether (for example, 2- (2-methylphenoxy) ethanol) , C _2-4 alkylene glycol mono (mono or di C _1-4 alkylphenyl) ether) such as 2- (2,6-dimethylphenoxy) ethanol, alkylene glycol mono (ali Ether phenyl) ether (for example, C _2-4 alkylene glycol mono (mono or di C _6-10 arylphenyl) ether such as ethylene glycol monobiphenylyl ether (such as ethylene glycol mono (2-biphenylyl) ether)), alkylene glycol mono C _2-4 alkylene glycol mono (mono or di C _1-4 alkyl-mono or di C _6-10 aryl such as (alkyl-arylphenyl) ether (eg ethylene glycol mono (3-methyl-2-biphenylyl) ether) In the above formula (3A), such as -phenyl) ether), etc.] n and p are both 1; dialkylene glycol monophenyl ethers [eg dialkylene glycol monophenyl ether (eg Glycol monophenyl ether, alcohols p such dipropylene glycol di C _2-4 alkylene glycol monophenyl ether, such as monophenyl ether), etc.] is 1, n is 2 or more; response to these, n is 3 Corresponding to these, alcohols corresponding to these, wherein ring Z is a naphthalene ring (such as alkylene glycol mononaphthyl ethers); corresponding to these, compounds having p of 2 or more, and the like.

  These compounds represented by the formula (3A) may be used alone or in combination of two or more.

  The purity of the compound represented by the formula (3A) used as a raw material (for example, phenols, naphthols, alkylene glycol monophenyl ethers, etc.) is not particularly limited, but is usually 95% by weight or more, preferably 99% by weight or more.

  In the reaction, the ratio (use ratio) of the compound represented by the formula (3A) (aromatic hydrocarbon having a hydroxyl group) is 1 mol of the compound represented by the formula (2) (dibenzofluorenones). For example, 2 to 100 mol (for example, 2.3 to 80 mol), preferably 2.5 to 70 mol (for example, 2.7 to 60 mol), and more preferably about 3 to 50 mol. Good. In particular, when an inorganic acid or organic acid described later is used as the acid catalyst, the ratio of the compound represented by the formula (3A) is, for example, 2 to 1 mol of the compound represented by the formula (2). It may be about 20 mol, preferably 2.2 to 10 mol, more preferably about 2.5 to 5 mol.

The reaction (condensation reaction) between the compound represented by the formula (2) and the compound represented by the formula (3A) is not particularly limited, but can usually be performed in the presence of an acid catalyst. Examples of the acid catalyst include inorganic acids [sulfuric acid, hydrogen chloride, hydrochloric acid (5 to 36% by weight, preferably about 20 to 36% by weight aqueous hydrogen chloride solution), phosphoric acid and the like], organic acids [sulfonic acid (methanesulfone). And alkane sulfonic acids such as acids). The sulfuric acid includes dilute sulfuric acid (for example, sulfuric acid having a concentration of about 30 to 90% by weight), concentrated sulfuric acid (for example, sulfuric acid having a concentration of 90% by weight or more), fuming sulfuric acid, and the like, and can be converted into sulfuric acid in the reaction system. If present, sulfur trioxide may be used as the sulfuric acid precursor. Usually, as sulfuric acid, 80 to 99% by weight (for example, 85 to 98% by weight), preferably about 90 to 97.5% by weight sulfuric acid (concentrated sulfuric acid) may be used in terms of H ₂ SO ₄ .

Moreover, a solid acid can also be used as an acid catalyst. Examples of the solid acid include inorganic solid acids [metal compounds (SiO ₂ , Al ₂ O ₃ , TiO ₂ , Fe ₂ O ₃ , ZrO ₂ , SnO ₂ , V ₂ O ₅ and other oxides, SiO ₂ —Al ₂ O _3]. , SiO ₂ —TiO ₂ , TiO ₂ —ZrO ₂ , SiO ₂ —ZrO ₂ and other complex oxides, sulfides such as ZnS, CaSO ₄ , Fe ₂ (SO ₄ ) ₃ , CuSO ₄ , NiSO ₄ , Al ₂ ( SO ₄ ) ₃ , MnSO ₄ , BaSO ₄ , CoSO ₄ , ZnSO ₄ and other sulfates, P, Mo, V, W, Si and other polyacids (AlPO ₄ , Ti phosphates, etc.) salts, _etc.)); clay minerals (acid clay, montmorillonite and the like);; _{(NH 4)} 2 SO ₄ nonmetal sulfates such as zeolite (Y-type having an acidic OH group, X type, a type, ZSM , _Mordenite, VIPI _5, AlPO 4 _-5, including AlPO ₄ -11); kaolin, etc.], can be exemplified an organic solid acid (such as ion-exchange resins). The solid acid may be porous or non-porous depending on the type of solid acid.

The ion exchange resin mainly includes strong acid cation exchange resin [for example, ion exchange resin having sulfonic acid group [sulfonated product of crosslinked polystyrene such as styrene-divinylbenzene copolymer, sulfonic acid group (or —CF ₂ CF _2]. A fluorine-containing resin having a SO ₃ H group (for example, a block copolymer of [2- (2-sulfotetrafluoroethoxy) hexafluoropropoxy] trifluoroethylene and tetrafluoroethylene (Nafion manufactured by DuPont), etc. Fluorine-containing ion exchange resins, etc.], weak acid cation exchange resins [for example, ion exchange resins having a carboxylic acid group (methacrylic acid-divinylbenzene copolymer, etc.), etc.] ), Etc. In addition, heat resistance with bromine introduced into the molecule Can also be used in the ion exchange resin. Among these solid acid cation exchange resin is preferred.

The ion exchange resin may be a gel type ion exchange resin, but usually, from the viewpoint of catalytic activity, a porous ion exchange resin [in addition to micropores, macropores (for example, pores having a pore diameter of about 50 to 1000 mm) are used. Having an ion exchange resin]. Among porous ion exchange resins, for example, an ion exchange resin based on a styrene-divinylbenzene copolymer having a high divinylbenzene ratio (crosslinking degree) is called a high porous resin. The porosity of the porous ion exchange resin is usually about 0.03 to 0.6 cm ³ / g, for example, 0.05 to 0.55 cm ³ / g, preferably 0.1 to 0.5 cm ³ / g. g, more preferably about 0.15 to 0.45 cm ³ / g (particularly 0.2 to 0.4 cm ³ / g). The nitrogen adsorption specific surface area of the ion exchange resin is usually about 10 to 90 m ² / g, for example, 15 to 80 m ² / g, preferably 20 to 70 m ² / g, more preferably 25 to 60 m ² / g ( In particular, it may be about 30 to 50 m ² / g). Commercially available ion exchanges such as “Levacit K2649” manufactured by Bayer; “Amberlist 31”, “Amberlist 131”, “Amberlist 121” manufactured by Organo; “Nafion” manufactured by DuPont, etc. A resin may be used.

  There is no restriction | limiting in particular in the form of a solid acid, Although a film form may be sufficient, Usually, it is granular and fine particle may be sufficient.

  The acid catalysts may be used alone or in combination of two or more.

  Preferred acid catalysts include sulfuric acid from the viewpoint of catalytic activity. In particular, when sulfuric acid and thiols described below are combined, a high-purity dibenzofluorene compound with a low residual sulfur content can be obtained in a high yield simply and efficiently.

The amount of the acid catalyst used can be selected according to the type of the acid catalyst. For example, when the inorganic acid or the organic acid is used, the amount of the dibenzofluorenone (the compound represented by the formula (2)) is 100 parts by weight. 0.001 to 1000 parts by weight, preferably 0.005 to 300 parts by weight, and more preferably about 0.01 to 100 parts by weight. In particular, when sulfuric acid is used as a catalyst, the amount of sulfuric acid (in terms of H ₂ SO ₄ ) is usually 0.1 to 30 parts by weight (eg 0.5 to 25 parts per 1 part by weight of dibenzofluorenones). For example, about 1 to 20 parts by weight, preferably about 3 to 15 parts by weight, and more preferably about 5 to 12 parts by weight (for example, 7 to 10 parts by weight). In addition, when a compound (for example, alkylene glycol monophenyl ethers) in which n is 1 or more is used as the compound represented by the formula (3A), a relatively large amount of an acid catalyst such as dibenzofluorenone ( 1 to 1000 parts by weight, preferably 3 to 500 parts by weight, more preferably about 5 to 200 parts by weight, and usually about 10 to 300 parts by weight with respect to 100 parts by weight of the compound represented by the formula (2). An acid catalyst may be used.

In general, the condensation reaction may be performed in combination with a thiol as a co-catalyst in addition to the acid catalyst. By combining with thiols, the condensation reaction can proceed effectively. Examples of thiols include conventional thiols that function as promoters, such as mercaptocarboxylic acid (thioacetic acid, β-mercaptopropionic acid, α-mercaptopropionic acid, thioglycolic acid, thiooxalic acid, mercaptosuccinic acid, mercaptobenzoic acid. Etc.), alkyl mercaptans (such as C _1-16 alkyl mercaptans (especially C _1-4 alkyl mercaptans) such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, dodecyl mercaptan), aralkyl mercaptans (benzyl mercaptan) Etc.) or a salt thereof. Examples of the salt include alkali metal salts (for example, sodium salts such as methyl mercaptan sodium and ethyl mercaptan sodium). Among these thiols, mercapto C _2-6 carboxylic acid (for example, β-mercaptopropionic acid) is preferable. Thiols can be used alone or in combination of two or more.

  The amount of thiols used can be selected from the range of about 0 to 1 part by weight with respect to 1 part by weight of dibenzofluorenones (compound represented by the formula (2)), for example, 0.001 to 0.8 Parts by weight, preferably 0.005 to 0.7 parts by weight (e.g., 0.01 to 0.6 parts by weight), more preferably about 0.02 to 0.5 parts by weight. It may be about 001 to 0.5 parts by weight.

Moreover, the usage-amount of thiols can be selected from the range of about 0-50 weight part with respect to 1 weight part of acid catalysts (inorganic acid or organic acid), for example, 0.1-40 weight part, Preferably it is 0. It may be about 5 to 30 parts by weight, more preferably about 1 to 20 parts by weight. In particular, when sulfuric acid is used, 0.001 to 1 part by weight (for example, 0.03 to 0.7 part by weight) of thiols with respect to 1 part by weight of sulfuric acid (in terms of H ₂ SO ₄ ), preferably 0.05 to 0.5 parts by weight (for example, 0.05 to 0.3 parts by weight), more preferably 0.06 to 0.1 parts by weight (for example, 0.065 to 0.09 parts by weight) It may be about 0.001 to 0.1 parts by weight.

  The condensation reaction may be performed in the absence of a solvent or in a solvent. The solvent (reaction solvent) is not particularly limited as long as it is non-reactive with the acid catalyst and can dissolve the dibenzofluorenones and the compound represented by the formula (3A), and can be used in a wide range. Typical solvents (organic solvents) include ether solvents (dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane), halogenated solvents (halogenated such as methylene chloride, chloroform, carbon tetrachloride). Hydrocarbons), aromatic solvents (aromatic hydrocarbons such as benzene, toluene and xylene, anisole and the like). An excess of the compound represented by the formula (3A) may be used as a solvent. The solvents may be used alone or in combination of two or more.

  The usage-amount of a solvent can be selected from the range of about 0-50 weight part (for example, 0.5-30 weight part) with respect to 1 weight part of dibenzofluorenones, for example, 1-20 weight part, Preferably it is 2 It may be about -15 parts by weight, more preferably about 3-10 parts by weight.

  The condensation reaction varies depending on the types of raw materials and catalysts used, but is usually 10 to 150 ° C., preferably 20 to 120 ° C., more preferably about 30 to 80 ° C. (for example, 40 to 70 ° C.). There are many cases. Moreover, reaction time can be adjusted according to the kind of raw material, reaction temperature, the density | concentration in a solvent, etc., for example, 30 minutes-48 hours, Usually, 1 to 20 hours, Preferably it is about 1 to 10 hours. The reaction may be performed with stirring, may be performed in air or in an inert atmosphere (nitrogen, rare gas, etc.), or may be performed at normal pressure or under pressure.

  The reaction mixture after completion of the reaction usually contains unreacted dibenzofluorenones, unreacted alcohols, catalysts (acid catalysts, thiols), side reactions, in addition to the generated compound represented by the formula (1). Products etc. are included. Therefore, separation and purification can be performed by a conventional method, for example, separation means such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, reprecipitation, or a combination of these. For example, after removing the acid catalyst (and thiols) by a conventional method (e.g., neutralizing by adding an aqueous alkali solution), adding a crystallization solvent, cooling to crystallize, and then separating by filtration You may refine by doing.

Examples of the crystallization solvent include hydrocarbons [aliphatic hydrocarbons (hexane, heptane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated hydrocarbons (dichloromethane, etc. ), Etc.], water, alcohols [lower aliphatic alcohols such as methanol, ethanol, n-propanol, isopropanol ( _C1-3 alkanols, etc.)], ketones [acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, ethylpropyl ketone, di -n- propyl ketone, (such as C _3-7 dialkyl ketones) lower aliphatic ketones such as diisopropyl ketone, cyclohexanone, etc.], ethers (diethyl ether, and dialkyl ethers such as diisopropyl ether), nitriles, Cerro Lube, amides (dimethylformamide, etc.), and the like sulfoxides. The crystallization solvents may be used alone or in combination of two or more. Moreover, the usage-amount of a crystallization solvent is not specifically limited, It is 0.5-50 weight part with respect to 1 weight part of reaction mixtures (solid content conversion), Preferably it is 1-10 weight part, More preferably, it is 1-1 weight part. It may be about 5 parts by weight.

  Such a crystallization operation may be performed once or may be repeated a plurality of times. In particular, when the acid catalyst (especially sulfuric acid) and thiols are combined in the condensation reaction, the residual sulfur concentration is simple and efficient, and even in a single crystallization operation (or recrystallization). [For example, the sulfur concentration relative to the entire reaction product (or crystallized product, purified product) is 30 ppm or less (for example, 0 to 25 ppm), preferably 20 ppm or less (for example, 1 to 15 ppm) in terms of the weight of sulfur S, More preferably, the compound represented by the formula (1) can be obtained at 10 ppm or less (for example, 2 to 9 ppm).

By the above process (process (A1)), a compound in which E is an oxygen atom in the formula (1) can be obtained. In the formula (1), a compound in which E is an oxygen atom and n is 1 or more is a compound in which n is 0 as the compound represented by the formula (3A) in the step (A1). And after producing a compound in which n is 0 in the formula (1), the produced compound (a compound in which E is an oxygen atom and n is 0 in the formula (1)) and an alkylene group R ⁴ (or It can also be obtained through a step of reacting a compound corresponding to the oxyalkylene group OR ⁴ ) (step (B)).

Examples of the compound corresponding to the alkylene group R ⁴ include alkylene oxide (C _2-4 alkylene oxide such as ethylene oxide, propylene oxide and butylene oxide, particularly C _2-3 alkylene oxide) and alkylene carbonate (ethylene carbonate, propylene carbonate and butylene). _{C 2-4} alkylene carbonates such as carbonates, such as especially _{C 2-3} alkylene carbonate), halo alkanol (e.g., 3-reaction with a halo _{C 2-6} alkanol, etc.), such as chloropropanol (or addition) products such as Is mentioned. These compounds may be used alone or in combination of two or more. When alkylene oxide or alkylene carbonate is reacted, a (poly) oxyalkylene unit can be introduced through the hydroxyl group of the compound represented by the formula (1) (a compound in which n is 0). When using an alkylene carbonate, an oxyalkylene unit (alkoxy unit) is introduced by decarboxylation after the addition of the alkylene carbonate.

(Method for producing a compound in which E is a sulfur atom in formula (1))
The compound in which E is a sulfur atom in the formula (1) is a step of reacting the compound represented by the formula (2) (dibenzofluorenones) with the compound represented by the formula (3) or a derivative thereof. (Step (A)) can be obtained at least.

  Among such production methods, the compound in which E is a sulfur atom and n is 0 in the formula (1) is typically represented by (i) the compound represented by the formula (2) and the above A step (A1) of reacting a compound represented by formula (3A) with a compound in which n is 0, and a product obtained by this step (A1) (that is, in the formula (1), E Compound in which n is an oxygen atom and n is 0) and a step (A2) of reacting N-substituted thiocarbamic acids, (ii) the compound represented by the above formula (2) and the following formula (3B) Or (iii) reacting the compound represented by the formula (2) with the compound represented by the formula (3C) (A4). And azotize the amino group of the product obtained by this step (A4) It is reacted with a sulfate anion can be produced through the step of hydrolyzing (A5).

(In the formula, Pro represents a protecting group, and Z, R ³ , m and p are the same as above.)

(In the formula, Z, R ³ , m and p are the same as above.)
(Method (i))
In the method (i), the step (A1) is the same as the method described in the method for producing a compound in which E is an oxygen atom in the formula (1), and preferable reaction conditions are also the same.

In the method (i), N-substituted thiocarbamic acids include N-substituted thiocarbamic acids [for example, N-alkyl-substituted thiocarbamic acids (for example, N-methylcarbamic acid, N-ethylcarbamic acid, N, N- N-mono or diC _1-6 alkyl-carbamic acid such as dimethylcarbamic acid and N, N-diethylcarbamic acid, preferably N-diC _1-4 alkylcarbamic acid)], N-substituted carbamic acid derivatives [ For example, N-alkyl substituted thiocarbamoyl halides (eg N-mono or diC _1-6 alkyl-thiocarbamoyl halides such as N, N-dimethylthiocarbamoyl chloride, preferably N-diC _1-4 alkyl-thiocarbamoyl Halides corresponding to the N-substituted thiocarbamic acid such as halide)] And so on. These N-substituted thiocarbamic acids may be used alone or in combination of two or more.

  In the step (A2), the reaction may be performed in the presence of a solvent or may be performed in the absence of a solvent. In step (A2), the reaction may be performed in the presence of a suitable catalyst (eg, a base catalyst such as an amine (eg, a tertiary amine such as triethylamine)).

  By such a step (A2), a compound in which the hydrogen atom of the hydroxyl group is usually substituted with an N-substituted thiocarbonyl group in the formula (1) is obtained. And after obtaining such a compound, by heating at high temperature (for example, about 200-350 degreeC) and hydrolyzing, the target product (In said Formula (1), E is a sulfur atom, n Can be obtained. When heated at a high temperature, thermal rearrangement of the N-substituted thiocarbonyloxy group occurs and an N-substituted carbonylthio group is generated. The hydrolysis treatment may be performed, for example, in the presence of a base (or an alkali, for example, an alkali metal such as sodium hydroxide or potassium hydroxide or an alkaline earth metal hydroxide). The hydrolysis treatment time may be about 2 to 120 minutes.

(Method (ii))
In the method (ii), the compound represented by the formula (3B) corresponds to the aromatic hydrocarbon ring (thiol) having a mercapto group in the formula (1). Examples of the thiol corresponding to formula (3B) (compound in which Pro is a hydrogen atom in formula (3B)) include monothiophenols (for example, C _1-4 such as thiophenol and alkyl-thiophenol (p-methylthiophenol). Alkyl-mercaptobenzene), thionaphthols (1-thionaphthol, 2-thionaphthol, etc.), polythiophenols (eg, 1,2-dimercaptobenzene, etc.), hydroxy-mercaptobenzene (p-mercaptophenol, etc.) ) Etc. are included.

In the formula (3B), the protecting group Pro may be any group that can be removed, such as an alkyl group [eg, methyl group, ethyl group, isopropyl group, t-butyl group, chloromethyl group, A C _1-6 alkyl group (preferably a C _1-4 alkyl group) which may have a substituent such as 2-hydroxyethyl group, benzyl group, 4-methoxybenzyl group, diphenylmethyl group, etc.], acyl group (For example, C _1-6 alkylcarbonyl groups such as acetyl and propionyl) and the like.

  In the method (ii), the ratio (use ratio) of the compound represented by the formula (3B) is, for example, 2 to 10 mol, preferably 2 with respect to 1 mol of the compound represented by the formula (2). .About 1-7 mol, more preferably about 2.5-5 mol.

  The reaction between the compound represented by the formula (2) and the compound represented by the formula (3B) may be performed at room temperature or under heating. The reaction temperature may be, for example, about 30 to 80 ° C., and the reaction time may be about 1 to 8 hours.

  After the reaction, by removing (deprotecting) the protecting group Pro from the obtained product, the desired product (a compound in which E is a sulfur atom and n is 0 in the formula (1)) can be obtained. . The elimination can be performed in the presence of an acid (for example, an inorganic acid such as hydrochloric acid or sulfuric acid; an organic acid such as trifluoroacetic acid) depending on the type of the protecting group.

(Method (iii))
In the method (iii), examples of the compound represented by the formula (3C) include anilines (for example, aniline, alkyl-aniline (C _1-4 alkyl-aniline such as toluidine), etc.), naphthylamines (1-naphthylamine). , 2-naphthylamine, etc.), polyaminobenzenes (eg, benzenediamine, toluenediamine, etc.), polyaminonaphthalenes (eg, naphthalenediamine, etc.) and the like.

  In the method (iii), the ratio (use ratio) of the compound represented by the formula (3C) is, for example, 2 to 100 mol (for example, 2) with respect to 1 mol of the compound represented by the formula (2). .3 to 80 mol), preferably 2.5 to 70 mol (for example, 2.7 to 60 mol), more preferably about 3 to 50 mol.

  In the step (A4), the reaction may be performed in the presence of a solvent or may be performed in the absence of a solvent. In step (A4), the reaction may be performed in the presence of a suitable catalyst. In addition, you may perform reaction of the compound represented by the said Formula (2), and the compound represented by the said Formula (3C) under normal temperature or a heating. You may select reaction temperature and reaction time suitably. In the step (A5), azotization can be performed, for example, by reacting a metal nitrite (such as sodium nitrite). In the step (A5), examples of the sulfate anion include xanthate. Hydrolysis can be performed using a base (metal hydroxide such as sodium hydroxide) or the like.

Further, in the formula (1), the compound in which E is a sulfur atom and n is 1 or more is obtained by converting a hydroxyl group of the compound in which E is an oxygen atom and n is 1 or more into a mercapto group. Can be obtained by substitution (or conversion). As a method for substitution with a mercapto group, for example, a compound in which E is a sulfur atom and n is 1 or more in the formula (1) is reacted with a halogenating agent (for example, a chlorinating agent such as thionyl chloride). Obtained by halogenating the hydroxyl group of the compound and further reacting the obtained halide with a sulfurizing agent (for example, sodium sulfide Na ₂ S) [further treatment with an acid (sulfuric acid, etc.)] Can do. In addition, the compound in which E is an oxygen atom and n is 1 or more in the formula (1) can be obtained by the method described above.

  The reaction product (target product) may be separated and purified by the same method as described above (crystallization, etc.).

  In addition, the manufacturing method of the compound whose E is a sulfur atom in Formula (1) can also refer to the method as described in Unexamined-Japanese-Patent No. 2002-338540.

[Uses of dibenzofluorene compounds]
The dibenzofluorene compound of the present invention has a dibenzofluorene skeleton and an aromatic hydrocarbon skeleton (benzene skeleton, naphthalene skeleton, etc.), and has various properties (optical characteristics, heat resistance, water resistance, It has excellent moisture resistance, chemical resistance, electrical properties, mechanical properties, dimensional stability, etc.) and is useful for improving or improving these properties in various applications. Moreover, it has a high refractive index due to the skeleton. Furthermore, as described above, by selecting the type of the aromatic hydrocarbon skeleton, the handling property and the reactivity can be further improved, and the dimensional stability can be improved by reducing the linear expansion property. For this reason, such a dibenzofluorene compound can be used suitably as an additive, a resin raw material (monomer etc.), etc., and can be used as a compound for providing the above outstanding characteristics efficiently.

(Additive use and resin composition)
Examples of the additive include a resin additive (or resin additive), a curing agent (such as a resin curing agent), and the like. When used as an additive, a resin composition (thermoplastic resin composition, thermal or photocurable resin composition) containing a resin and the dibenzofluorene compound (for example, a dibenzofluorene compound having a hydroxyl group) can be constituted. In such a resin composition, the resin is not particularly limited, and a wide range of resins (thermoplastic resin, heat or photocurable resin, etc.) can be used.

Examples of the thermoplastic resin include olefin resins, halogen-containing vinyl resins (polyvinyl chloride, fluororesins, etc.), acrylic resins, styrene resins, polycarbonate resins, polyester resins [for example, polyalkylene terephthalate ( Poly _C2-4 alkylene terephthalate such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, etc., polyalkylene arylate resin such as polyethylene naphthalate, polyarylate resin (for example, aromatic dicarboxylic acid ( Terephthalic acid) and aromatic diols (biphenol, bisphenol A, xylylene glycol, alkylene oxide adducts thereof) as polymerization components Arylate resins, etc.)], polyacetal resins, polyamide resins, polyphenylene ether resins, polysulfone resins, polyphenylene sulfide resins, polyimide resins, polyether ketone resins, thermoplastic elastomers, and the like. The thermoplastic resins may be used alone or in combination of two or more.

  Among these thermoplastic resins, a thermoplastic resin containing an aromatic ring (such as a benzene ring), for example, an aromatic polycarbonate resin (such as bisphenol A polycarbonate), an aromatic polyester resin (such as the polyalkylene arylate resin) ), Polysulfone resins, polyphenylene ether resins, polyphenylene sulfide resins and the like are preferable. The dibenzofluorene compound is highly compatible with these aromatic ring-containing resins, and therefore has high dispersibility in the resin.

  Thermosetting resins (or photocurable resins) include phenolic resins, furan resins, amino resins (urea resins, melamine resins, etc.), unsaturated polyester resins, diallyl phthalate resins, epoxy resins, vinyl ester resins, polyurethanes. Resin, thermosetting polyimide resin, silicon resin (silicone resin, polysilane, etc.), photopolymerizable monomer or oligomer (for example, (meth) such as epoxy (meth) acrylate, polyurethane (meth) acrylate, polyester (meth) acrylate) Examples thereof include acrylate compounds). The thermosetting resin may be an initial condensate. Thermosetting resins may be used alone or in combination of two or more.

  In addition, when combining a thermosetting resin and a dibenzofluorene compound, a dibenzofluorene compound may act as a hardening | curing agent (or hardening accelerator). Among the resins, dibenzofluorene compounds [for example, dibenzofluorene compounds having a hydroxyl group, particularly dibenzofluorene compounds having a phenolic hydroxyl group (dibenzofluorene compound in which E is an oxygen atom and n is 0 in formula (1)) As a typical resin that can be used as a curing agent, an epoxy resin can be given. Epoxy resins include bisphenol-type epoxy resins (for example, reaction products (condensates) of bisphenols such as 4,4-biphenol, 2,2-biphenol, bisphenol F, bisphenol AD, and bisphenol A with epichlorohydroline. Bisphenol A type epoxy resin, etc.), novolak type epoxy resin [phenol novolak type epoxy resin (phenol novolak type glycidyl ether, etc.), cresol novolac type epoxy resin (cresol novolac type glycidyl ether, etc.)], amine type epoxy resin, etc. Is included. Epoxy resins may be used alone or in combination of two or more.

  The proportion of the dibenzofluorene compound is, for example, 1 to 700 parts by weight, preferably 50 to 600 parts by weight, more preferably 100 parts by weight of resin (particularly thermoplastic resin such as a thermoplastic resin having an aromatic ring). About 100-500 weight part (for example, 200-300 weight part) may be sufficient. Moreover, when using a dibenzofluorene compound as a hardening | curing agent, the functional group (for example, phenol) of 1 functional group (or curable functional group, for example, epoxy group) of resin (epoxy resin) with respect to 1 equivalent. Of hydroxyl groups such as a functional hydroxyl group) is 0.1 to 4.0 equivalents, preferably 0.3 to 2.0 equivalents, more preferably 0.5 to 1.5 equivalents. The proportion may be adjusted.

  The resin composition has various additives depending on applications, for example, fillers, flame retardants, reinforcing agents, plasticizers, polymerization initiators, catalysts, stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers, etc. ), Mold release agent, antistatic agent, colorant (dye / pigment), antifoaming agent, leveling agent, dispersant, flow regulator, carbon material (carbon black, graphite, carbon fiber, activated carbon, fullerene, carbon nanotube, etc.) Etc. may be included. These additives may be used alone or in combination of two or more. The resin composition may be a composition containing a solvent (such as a coating composition) depending on the type of resin.

(Resin raw materials and resins)
The dibenzofluorene compound of the present invention can be used as a resin raw material. For example, since the dibenzofluorene compound of the present invention has a plurality of hydroxyl groups and / or mercapto groups as functional groups, it can be used as a polyol component or a polythiol component of a thermoplastic resin or a thermosetting resin. That is, the resin of the present invention is a resin having the dibenzofluorene compound (or a derivative thereof) as a polymerization component (polyol component or polythiol component). Specifically, the resin of the present invention is a resin having a polyol component or a polythiol component as a polymerization component, wherein a part or all of the polyol component or polythiol component is the dibenzofluorene compound (a dibenzofluorene compound having a plurality of hydroxyl groups, It is a resin composed of a dibenzofluorene compound having a plurality of mercapto groups) (or a derivative thereof).

  Such a resin can be selected according to the type of the functional group (hydroxyl group or mercapto group) of the dibenzofluorene compound, and includes various thermoplastic resins and thermosetting resins (or photocurable resins). Resins having a polyol component (for example, diol component) as a polymerization component include thermoplastic resins [polyester resins, polycarbonate resins, polyurethane resins, polyether resins (such as polyether ether ketone)], thermosetting resins, and the like. Resins [for example, unsaturated polyester resins, thermosetting polyurethane resins, epoxy resins (polyglycidyl ethers of the above-mentioned dibenzofluorene compounds having a hydroxyl group), vinyl ester resins, phenol resins, polyol poly (meth) acrylates ( Poly (meth) acrylate of the dibenzofluorene compound having a hydroxyl group, or a reaction product of the dibenzofluorene compound and (meth) acrylic acid or a derivative thereof ((meth) acrylic acid halide), urethane (meth) a Relate]], and others.

  Examples of the resin having a polythiol component (for example, a dithiol component) as a polymerization component include thermoplastic resins [polythioester resins, polythiocarbonate resins, polythiourethane resins, polysulfone resins, polythioether resins, for example. Etc.], thermosetting resins (for example, thermosetting polythiourethane resins, thioepoxy resins, polythiol poly (meth) acrylates, etc.).

  In these resins, the dibenzofluorene compound as a component constituting the polyol component or the polythiol component may be used alone or in combination of two or more.

  In these resins (especially thermoplastic resins), the dibenzofluorene compound may be used for at least part of the polyol component or polyol component, and part or all of the polyol component or polythiol component may be replaced with the dibenzofluorene compound. It may be configured.

  Typical resins include poly (thio) ester resins (polyester resins, polythioester resins), poly (thio) ether resins, poly (thio) carbonate resins, (thio) epoxy resins, and the like. Hereinafter, typical resins will be described in detail.

(Polyester resin)
The polyester resin is, for example, a polyester resin having a diol component (a) composed of at least a dibenzofluorene compound having a hydroxyl group and a dicarboxylic acid component (b) as polymerization components. In such a polyester-based resin, the dibenzofluorene compound having a hydroxyl group is usually represented by the following formula (a1): a compound in which E is an oxygen atom and p is 1 in the formula (1). It may be a dibenzofluorene compound (or diol component (a1)).

(In the formula, Z, R ¹ , R ² , R ³ , R ⁴ , k, l, m and n are the same as above.)
Examples of the compound represented by the formula (a1) include dibenzofluorene compounds having two hydroxyl groups exemplified above [for example, 9,9-bis (hydroxyphenyl) dibenzofluorene, 9,9-bis (C _1-4). Alkyl-hydroxyphenyl) dibenzofluorene, 9,9-bis (hydroxynaphthyl) dibenzofluorene, etc.].

In the polyester resin, the diol component (a) may contain another diol component (a diol component other than the dibenzofluorene compound (a1)) as long as it is composed of the dibenzofluorene compound (a1). Examples of such other diol components (diol component (a2)) include alkanediols (ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2- C _2-10 alkanediols such as butanediol, 1,3-butanediol, 1,4-pentanediol, 1,5-pentanediol, 1,3-pentanediol, neopentylglycol, preferably _C2-6 alkane Diols, more preferably C _2-4 alkane diols), polyalkane diols (eg di- or tri-C _2-4 alkane diols such as diethylene glycol, dipropylene glycol, triethylene glycol etc.), cycloalkane diols (eg cyclohexane diol) _{C 5-8} Sik, such as Alkanediol), di (hydroxyalkyl) cycloalkanes (e.g., cyclopentane dimethanol, cyclohexane dimethanol (hydroxy _{C 1-4} alkyl, such as _{dimethanol) C 5-8} cycloalkane, etc.), dihydroxy arene (hydroquinone, resorcinol, etc.) Araliphatic diol [di (hydroxy C _1-4 alkyl) C _6-10 arene etc. such as 1,4-benzenedimethanol, 1,3-benzenedimethanol], biphenol, bisphenol [eg bisphenol A etc. Bis (hydroxyphenyl) C _1-10 alkane and the like], diols having a fluorene skeleton [eg, 9,9-bis (hydroxyphenyl) fluorene such as 9,9-bis (4-hydroxyphenyl) fluorene; -Screw (4 Hydroxy-3-methylphenyl) 9,9-bis fluorene (mono- or _{di-C 1-4} alkyl - hydroxyphenyl) fluorene; 9 such as 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene 9,9-bis (hydroxyC _2-4 alkoxy-phenyl) fluorene; 9,9-bis (hydroxyC _2-4 such as 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene 9,9-bis (hydroxyC _2-4 alkoxynaphthyl) such as alkoxy-mono or di-C _1-6 alkylphenyl) fluorene; 9,9-bis [6- (2- (2-hydroxyethoxy) naphthyl)] fluorene ) Fluorene etc.]. Other diol components may be used alone or in combination of two or more.

  In the diol component (a), the proportion of the dibenzofluorene compound (a1) is, for example, 30 mol% or more (for example, about 40 to 100 mol%), preferably 50 mol% or more, based on the entire diol component (a). (For example, about 60 to 99 mol%), more preferably 70 mol% or more (for example, about 80 to 95 mol%), and usually 90 mol% or more (for example, 95 mol% or more), Also good.

  If necessary, in addition to the diol component, a polyol component having three or more hydroxyl groups [for example, alkane polyol such as glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, polyol having a fluorene skeleton (biscatechol) A small amount of a dibenzofluorene compound having 3 or more hydroxyl groups (for example, the above-mentioned exemplified compound such as 9,9-bis (di or trihydroxyphenyl) -dibenzofluorene) and the like] may be used.

In the polyester resin, examples of the dicarboxylic acid component include alkanedicarboxylic acids (C _2-20 alkane-dicarboxylic acids such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, preferably C _2-14. Aliphatic dicarboxylic acids such as alkane-dicarboxylic acids; cycloalkane dicarboxylic acids (C _5-10 cycloalkane-dicarboxylic acids such as cyclohexanedicarboxylic acid), di- or tricycloalkane dicarboxylic acids (decalin dicarboxylic acid, norbornane dicarboxylic acid), Alicyclic dicarboxylic acids such as adamantane dicarboxylic acid; arene dicarboxylic acids (terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, anthracene dicarboxylic acid, _{C 6-14} arene such as cement dicarboxylic acids - such as dicarboxylic acid), and biphenyl dicarboxylic acid (2,2'-biphenyl dicarboxylic acid), diphenyl alkane dicarboxylic acid (4,4'-diphenylmethane dicarboxylic acid, 2,2 Diphenyl C _1-10 alkane dicarboxylic acid such as di (4-carboxyphenyl) hexafluoropropane), diphenyl ketone dicarboxylic acid (such as 4,4′-diphenyl ketone dicarboxylic acid), diphenyl ether dicarboxylic acid (eg, 4,4′- such as diphenyl ether dicarboxylic acid), aromatic dicarboxylic acids such as dicarboxylic acids having a fluorene skeleton, derivatives (dicarboxylic acid halide, dicarboxylic acid anhydrides, lower alkyl esters (methyl ester, C _1-4 alkyl such as ethyl ester Ester, preferably such as _{C 1-2} alkyl esters), etc.) and the like. These dicarboxylic acid components may be used alone or in combination of two or more.

  Among these dicarboxylic acid components, an aromatic dicarboxylic acid component (aromatic dicarboxylic acid or a derivative thereof) is preferable for the purpose of imparting higher properties such as heat resistance to the polyester resin. In particular, when the aromatic dicarboxylic acid component is composed of a dicarboxylic acid component having a fluorene skeleton, characteristics such as heat resistance and refractive index can be further improved in the polyester resin. The dicarboxylic acid component (b1) having a fluorene skeleton is not particularly limited as long as it has a fluorene skeleton, but is usually a dicarboxylic acid represented by the following formula (b1A), a dicarboxylic acid represented by the following formula (b1A), or these Or a derivative thereof.

(In the formula, R ⁵ represents a substituent, and R ⁶ represents a divalent hydrocarbon group which may have a substituent. Q is an integer of 0 to 4.)

(Wherein, ^{R 7} and ^{R 8,} .r showing the same or different substituents is an integer of 0 to 3, s is an integer of 0-1.)
In the above formula (b1A), examples of the substituent represented by the group R ⁵ include groups similar to the substituents exemplified for the substituent R ¹ in the formula (1) (for example, an alkyl group). The groups R ⁵ substituted on different benzene rings may be different from each other or the same. When q is 2 or more, the groups R ⁵ may be different or the same in the same benzene ring. The preferred substitution number p is 0 or 1, especially 0. Incidentally, the substitution number p of radicals R ⁵ to be substituted with different benzene rings may be different, but usually the same.

In the formula (b1A), the divalent hydrocarbon group represented by the group R ⁶ includes an aliphatic hydrocarbon group {for example, an alkylene group (for example, a methylene group, an ethylene group, an ethylidene group, a trimethylene group, C _1-8 alkylene groups such as propylene group, propylidene group, tetramethylene group, ethylethylene group, butane-2-ylidene group, 1,2-dimethylethylene group, pentamethylene group, pentane-2,3-diyl group, Preferably a C _1-4 alkylene group), a cycloalkylene group (eg, a C _5-10 cycloalkylene group such as a cyclohexylene group, a methylcyclohexylene group, an alkylene-cycloalkylene group [eg, a methylene-cyclohexylene group, Ethylene-cyclohexylene, ethylene-methylcyclohexylene, ethylidene-cyclo C _1-6 alkylene such as xylene group-C _5-10 cycloalkylene group}, aromatic hydrocarbon group {eg, arylene group (C _6-10 arylene group such as phenylene group, naphthalenediyl group), alkylene (or Alkylidene) -arylene group [for example, C _1-4 alkylene-C _6-10 arylene group such as methylene-phenylene group, ethylene-phenylene group, ethylene-methylphenylene group, ethylidenephenylene group, preferably C _1-2 alkylene- The divalent hydrocarbon group represented by the group R ⁶ may have a substituent, for example, a substituent in the above formula (1). same groups as the substituents exemplified for group R ² (e.g., an alkyl group, a cycloalkyl group, a hydrocarbon group such as an aryl group) And the like.

In the formula (b1B), examples of the substituent represented by the group R ⁷ include the same groups as the substituents exemplified for the substituent R ¹ in the formula (1). The groups R ⁷ substituted on different benzene rings may be different from each other or the same. When r is 2 or more, the groups R ⁷ may be different or the same in the same benzene ring. A preferred substitution number r is 0 or 1, in particular 0. The number of substitutions r of the groups R ⁷ substituted on different benzene rings may be different but is usually the same. As the substituent represented by groups R ^8, the same groups as the substituents exemplified in the substituents R ³ in Formula (1) (e.g., a hydrocarbon group such as an alkyl group). Preferred substituents R ⁸ include alkyl groups (for example, C _1-20 alkyl groups such as methyl group and ethyl group, preferably C _1-12 alkyl groups). Two s may be the same or different. When both s is 1, the two groups R ⁸ may be the same or different.

As the dicarboxylic acid component (b1) having a typical fluorene skeleton, for example, 9,9-bis (carboxyalkyl) fluorenes [for example, 9,9-bis (carboxymethyl) fluorene, 9,9-bis (2 -Carboxyethyl) fluorene, 9,9-bis (1-carboxyethyl) fluorene, 9,9-bis (2-carboxy-1-cyclohexylethyl) fluorene, 9,9-bis (2-carboxy-1-phenylethyl) ) Fluorene, 9,9-bis (1-carboxypropyl) fluorene, 9,9-bis (2-carboxypropyl) fluorene, 9,9-bis (2-carboxy-1-methylethyl) fluorene, 9,9- Bis (2-carboxy-1-methylpropyl) fluorene, 9,9-bis (2-carboxybutyl) fluorene 9,9-bis (2-carboxy-1-methylbutyl) fluorene, 9,9-bis (5-carboxypentyl) substituent alkyl groups such as fluorene _{(C 1-4} alkyl _{groups, C 5-8} cycloalkyl group 9,9-bis (carboxy-C _1-6 alkyl) fluorene and the like which may have a C _6-10 aryl group, etc.], 9,9-bis (carboxycycloalkyl) fluorenes [for example, 9 9,9-bis (carboxy-C _5-8 cycloalkyl) optionally having a substituent such as 9,9-bis (4-carboxycyclohexyl) fluorene, 9,9-bis (1-carboxycyclohexyl) fluorene Fluorene etc.], 9,9-bis (carboxyaryl) fluorenes [for example, 9,9-bis (4-carboxyphenyl) fluorene 9,9-bis (carboxy-C _6-10 aryl) fluorene etc. which may have any substituent], 9,9-bis (carboxyaryl-alkyl) fluorenes [for example, 9,9-bis ( 9,9-bis (carboxy C _6-10 aryl-C _1-4 alkyl) fluorene etc. which may have a substituent such as 4-carboxybenzyl) fluorene], dicarboxyfluorenes [for example, dicarboxyfluorene (For example, 2,7-dicarboxyfluorene (or fluorene-2,7-dicarboxylic acid)), 9,9-dialkyl-dicarboxyfluorene (for example, 2,7-dicarboxy-9,9-dimethylfluorene ( Or 9,9-dimethylfluorene-2,7-dicarboxylic acid), 2,7-dicarboxy-9,9-dihexylfluoro Emissions, 2,7-dicarboxy-9,9-dioctyl fluorene such as _{9,9-di-C 1-20} alkyl - dicarboxylate fluorene, preferably _{9,9-C 1-16} alkyl - dicarboxylate fluorene, further Preferably, dicarboxyfluorene having a substituent at the 9-position of fluorene such as 9,9-diC _1-12 alkyl-dicarboxyfluorene, etc.], further substituted (alkoxy group, acyl group, etc.) on these compounds And the like can be exemplified.

  Examples of the dicarboxylic acid derivative having a fluorene skeleton include the same derivatives as described above (dicarboxylic acid halide, dicarboxylic acid anhydride, lower alkyl ester, etc.).

  These dicarboxylic acid components (b1) having a fluorene skeleton may be used alone or in combination of two or more.

  When the dicarboxylic acid component (b) is composed of a dicarboxylic acid component (b1) having a fluorene skeleton, the proportion of the dicarboxylic acid component (b1) is, for example, 30 mol% or more (relative to the entire dicarboxylic acid component (b) ( For example, about 40 to 100 mol%), preferably 50 mol% or more (for example, about 60 to 99 mol%), more preferably 70 mol% or more (for example, about 80 to 95 mol%), Usually, it may be 90 mol% or more (for example, 95 mol% or more).

  If necessary, in addition to the dicarboxylic acid component, a polycarboxylic acid having three or more carboxyl groups (for example, trimellitic acid, pyromellitic acid, polycarboxylic acid having a fluorene skeleton (for example, JP-A-2006-151833). A small amount of a polycarboxylic acid corresponding to the fluorene polycarboxylic acid ester described in the publication No.) may be used.

  As described above, the polyester resin is a polyester resin having a diol component (a) composed of at least the dibenzofluorene compound having a hydroxyl group and a dicarboxylic acid component (b) as polymerization components. It is a polyester resin having an ester unit represented by the formula (A1).

(In the formula, A ¹ represents a residue of the dicarboxylic acid component (b), and Z, R ¹ , R ² , R ³ , R ⁴ , k, l, m, and n are the same as described above.)
The weight average molecular weight of the polyester resin can be selected from the range of, for example, about 3000 to 1000000, for example, about 5000 to 800000, preferably about 8000 to 600000, and more preferably about 10000 to 500000 (for example, 30000 to 500000). Also good. The weight average molecular weight may be a value evaluated by gel permeation chromatography based on polystyrene.

  Moreover, the said polyester resin is excellent in heat resistance. For example, the glass transition temperature Tg of the polyester resin may be 180 ° C. or higher (for example, about 180 to 450 ° C.), preferably 200 to 400 ° C., more preferably about 210 to 380 ° C.

  In addition, the said polyester resin can be obtained by making the said diol component (a) and the said dicarboxylic acid component (b) react (condensation reaction). The condensation reaction (polycondensation reaction) can be produced by using a general polyester resin synthesis method, for example, a transesterification method, a melt polymerization method such as a direct polymerization method, a solution polymerization method or an interfacial polymerization method. .

  In the reaction, the proportion of the diol component (a) and the dicarboxylic acid component (b) can be appropriately selected based on the equivalent ratio of these components. For example, the ratio of the diol component (a) is 0.7 to 1.5 mol, preferably 0.9 to 1.1 mol, more preferably 0.95 to 1 mol of the dicarboxylic acid component (b). It may be about 1.05 mol, and is usually about 1 mol.

  The reaction (condensation reaction or polymerization reaction) may be performed in the absence of a solvent or in the presence of a solvent. The solvent may be any component that is liquid at the reaction temperature. For example, it may be a solid at room temperature or a liquid component at the reaction temperature. Typical solvents (organic solvents) include ether solvents (chain ethers such as diphenyl ether, cyclic ethers such as tetrahydrofuran), halogenated solvents (halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride). , Halogenated aromatic hydrocarbons such as trichlorobiphenyl), aromatic hydrocarbons (benzene, toluene, xylene, etc.), heterocyclic compounds (N-methyl-2-pyrrolidone, etc.), sulfone solvents (sulfolane, dimethyl) Aliphatic sulfone such as sulfone, aromatic sulfone such as diphenyl sulfone) and the like. Among these solvents, high-boiling solvents such as diphenyl ether and trichlorobiphenyl [for example, solvents having a boiling point of 180 ° C. or higher (eg, 200 to 500 ° C., preferably 210 to 450 ° C., more preferably about 220 to 400 ° C.), etc. ] Is preferable. You may use the said solvent individually or in combination of 2 or more types.

  The reaction (condensation reaction, polymerization reaction) may be performed in the presence of a catalyst. The catalyst is not particularly limited, and examples thereof include metal hydroxides (such as alkali metal oxides such as sodium hydroxide), metal carbonates (such as alkali metals such as sodium carbonate or alkaline earth metal carbonates), and amines. (For example, imidazoles, benzotriazoles, etc.), phosphines (triphenisphosphine, etc.), quaternary ammonium salts (tetraalkylammonium halides such as tetraethylammonium chloride and tetraethylammonium bromide; benzyltrimethylammonium chloride, chloride) Benzyltriethylammonium chloride such as benzyltriethylammonium), quaternary phosphonium salts (such as benzyltriphenylphosphonium chloride), aluminum compounds (such as trialkylaluminum), germanium compounds , Tin compounds (tin chloride, tin carboxylates, etc.), titanium compounds (such as titanium alkoxide) can be exemplified. In particular, when a quaternary ammonium salt or the like is used as a catalyst, both the diol component and the dicarboxylic acid can be activated efficiently. You may use a catalyst individually or in combination of 2 or more types.

  The usage-amount of a catalyst can be adjusted according to the kind of catalyst, can be selected from the range of 0-1 mol with respect to 1 mol of total amounts of a diol component (a) and a dicarboxylic acid component (b), for example, 0.0001 ˜0.5 mol, usually 0.001 to 0.3 mol, preferably 0.003 to 0.2 mol, and more preferably about 0.005 to 0.1 mol.

  The polymerization reaction may be usually carried out under heating, for example, 120-350 ° C., preferably 140-330 ° C., more preferably 160-300 ° C. (for example, 170-250 ° C.). For the heating, a temperature raising and / or temperature lowering operation or the like may be used as appropriate, or may be performed in a single step at a substantially constant temperature, or a plurality of steps may be performed at different temperatures. The reaction time may be, for example, about 20 minutes to 24 hours, preferably 30 minutes to 18 hours, and more preferably about 1 to 12 hours (for example, 1 to 6 hours).

  The reaction may be performed in air, but may be performed in an atmosphere or flow of an inert gas (such as helium, nitrogen, argon). Further, the reaction may be performed under normal pressure, increased pressure, or reduced pressure. For example, the reaction may be performed under reduced pressure since the reaction is performed while removing components (water, hydrogen chloride, etc.) generated by the condensation reaction from the reaction system. The progress of the reaction can be confirmed (or traced) by high performance liquid chromatography (HPLC), gas chromatography (GC) or the like.

  After completion of the reaction, the product polyester resin is separated by a conventional separation method such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, or a combination of these. It can be purified.

(Polyether resin)
The polyether resin is, for example, a polyether resin having the diol component (a) (that is, a diol component (a) composed at least of a dibenzofluorene compound having a hydroxyl group) as a polymerization component. In such a polyether resin, the dibenzofluorene compound having a hydroxyl group is usually a compound in which E is an oxygen atom and p is 1 in the formula (1) (that is, represented by the formula (a1)). It may be a dibenzofluorene compound (or diol component (a1)), and such a polyether resin usually contains the diol component (a) and a compound (C) having a plurality of halogen atoms. Resin used as a polymerization component.

  That is, the polyether resin is usually a polyether resin having an ether unit represented by the following formula (A2).

(In the formula, A ² is a residue of compound (C) having a plurality of halogen atoms, and Z, R ¹ , R ² , R ³ , R ⁴ , k, l, m and n are the same as described above.)
In the compound (C) having a plurality of halogen atoms, examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms. Of these atoms, a fluorine atom and a chlorine atom are preferable, and a fluorine atom is particularly preferable. The number of halogen atoms can be selected as appropriate, and may be, for example, 2 to 8, preferably 2 to 6, and more preferably about 2 to 4. Usually, a compound having two halogen atoms is often used.

  Further, the compound having a plurality of halogen atoms may be a compound having an aliphatic skeleton, but is particularly preferably a compound having an aromatic skeleton (or aromatic ring). Furthermore, the compound having a plurality of halogen atoms may have a ketone skeleton or a sulfone skeleton. When a compound having a ketone skeleton is used, a polyether ketone resin is obtained, and when a compound having a sulfone skeleton is used, a polyether sulfone resin is obtained.

Typical compounds having a plurality of halogen atoms include aromatic ketone compounds having a plurality of halogen atoms, aromatic ether compounds having a plurality of halogen atoms, and aromatic sulfone compounds having a plurality of halogen atoms [for example, , Di (haloaryl) sulfone such as 4,4′-difluorodiphenylsulfone (preferably di (haloC _6-10 aryl) sulfone) and the like].

Examples of the aromatic ketone compounds include bis (haloarylcarbonyl) arene compounds [for example, 1,4-di (2-, 3- or 4-fluorobenzoyl) benzene, 5-t-butyl-1,3. -Di (2-, 3- or 4-fluorobenzoyl) benzene, 1,5-di (4-fluorobenzoyl) naphthalene, 1,5-di (4-fluorobenzoyl) -2,6-dimethylnaphthalene, 2, Bis (fluoroarylcarbonyl) arene compounds such as 6-di (2-, 3-, or 4-fluorobenzoyl) naphthalene (preferably bis (fluoroC _6-10 arylcarbonyl) C _6-14 arene compounds); Bis (chloroarylcarbonyl) arene compounds corresponding to bis (fluoroarylcarbonyl) arene compounds, bis Bromoarylcarbonyl) arene compounds and bis (iodoarylcarbonyl) arene compounds], bis (haloarylcarbonylaryl) ether compounds [for example, bis (fluoroarylcarbonyl such as 4,4′-bis (4-fluorobenzoyl) diphenyl ether Aryl) ether compounds (preferably bis (fluoroC _6-10 arylcarbonyl-C _6-10 aryl) ether, more preferably bis (fluoroC _6-10 arylcarbonylphenyl) ether); these bis (fluoroarylcarbonylaryl) ) Bis (chloroarylcarbonylaryl) ether compounds, bis (bromoarylcarbonylaryl) ether compounds and bis (iodoarylcarbonyl) corresponding to ether compounds Reel) ether compounds such as, tri- or Tetoraketon compounds corresponding to these diketone compounds, and the like.

Examples of the aromatic ether compounds include di (haloaryl) ether compounds (for example, di (halo C _6-10 aryl) ether compounds such as 4,4′-dibromodiphenyl ether), aromatic heterocyclic compounds [for example, 2, 5- to 6-membered aromatic heterocyclic compound substituted with two haloaryl groups such as 5-bis (4-fluorophenyl) -1,3,4-oxadiazole] and the like.

The compounds having a plurality of halogen atoms may be used alone or in combination of two or more. If necessary, together with the compound having a plurality of halogen atoms, monohalo compounds, for example, monohaloalkanes such as fluoromethane, fluoroethane, chloroethane (monohalo C _1-20 alkane etc.), monohaloarenes such as fluorobenzene, chlorobenzene, etc. (Such as monohalo C _6-14 arene) may be used in combination. In addition, the halogen atom which these monohalo compounds have is not limited to a fluorine atom or a chlorine atom, but may be a bromine atom or an iodine atom.

  The compound having a plurality of halogen atoms may be a commercially available product, or a compound synthesized by a conventional method may be used. For synthesis of diketone compounds, for example, Ohno, M .; Takata, T .; Endo, T. Macromolecules, 27 [12], 3447-3448 (1994), Ohno, M .; Takata, T .; Endo, TJ Polym. Sci., Part A: Polym. Chem., 33 [15], 2647-2655 (1995) can be referred to.

  The weight average molecular weight of the polyether resin may be, for example, 10,000 to 500,000, preferably 15,000 to 200,000, and more preferably about 20,000 to 100,000. The weight average molecular weight may be a value evaluated by gel permeation chromatography based on polystyrene.

  The polyether resin is excellent in heat resistance. For example, the glass transition temperature Tg of the polyether resin may be 180 ° C. or higher (for example, about 180 to 450 ° C.), preferably 200 to 350 ° C., more preferably about 230 to 340 ° C.

  The polyether-based resin can be obtained by polymerizing the compound having a plurality of halogen atoms, a dibenzofluorene compound having a hydroxyl group (particularly, the diol component (a)) and, if necessary, another monomer.

  The ratio of the compound having a plurality of halogen atoms and the dibenzofluorene compound having a hydroxyl group (particularly the diol component (a)) is the ratio of the halogen atom of the compound having a halogen atom to the hydroxyl group of the dibenzofluorene compound having a hydroxyl group. It can be suitably selected based on the equivalent ratio.

  The polymerization is usually performed under heating in many cases. For example, the polymerization may be performed at a temperature of about 120 to 350 ° C, preferably about 130 to 330 ° C, and more preferably about 140 to 310 ° C. For the heating, a temperature raising and / or temperature lowering operation or the like may be used as appropriate, or may be performed in a single step at a substantially constant temperature, or a plurality of steps may be performed at different temperatures. The reaction time may be, for example, 30 minutes to 48 hours, preferably 1 to 24 hours, more preferably about 1.5 to 12 hours.

  In order to obtain a uniform and high molecular weight polyether resin having a narrow molecular weight distribution width, it is preferable to carry out the polymerization by two-stage heating. In the two-stage heating, the heating temperature in the first stage may be, for example, 120 to 180 ° C, preferably 125 to 175 ° C, more preferably about 130 to 170 ° C. The heating temperature at the second stage may be, for example, 190 to 350 ° C, preferably 200 to 330 ° C, and more preferably about 210 to 310 ° C. In addition, when superposing | polymerizing by several steps of heating, the transition to subsequent heating temperature may be performed continuously and you may carry out at intervals. In the polymerization reaction by two-stage heating, the heating time of the first stage and the second stage is, for example, about 30 minutes to 24 hours, preferably 1 to 12 hours, and more preferably about 1.5 to 6 hours. It can be suitably selected from the range.

  A base catalyst may be used for the polymerization reaction. Examples of such base catalysts include inorganic bases such as metal hydroxides (alkali metal hydroxides such as sodium hydroxide and potassium hydroxide), metal carbonates (alkaline such as sodium carbonate, potassium carbonate, and calcium carbonate). Metal or alkaline earth metal carbonates; alkali metal hydrogen carbonates such as sodium hydrogen carbonate; rare earth metal carbonates such as cesium carbonate, etc.). These base catalysts can be used alone or in combination of two or more.

  The proportion of the base catalyst may be, for example, about 1 to 1000 parts by weight, preferably about 10 to 700 parts by weight, and more preferably about 50 to 500 parts by weight with respect to 100 parts by weight of the dibenzofluorene compound having a hydroxyl group. .

  The polymerization reaction may be performed in the absence of a solvent, but may be performed in the presence of a solvent (such as an organic solvent). As the solvent, the same solvents as described above can be used. A solvent can be used individually or in combination of 2 or more types.

  The reaction may be performed in air, but may be performed in an atmosphere or flow of an inert gas (such as helium, nitrogen, argon). Moreover, you may perform reaction under a normal pressure or pressurization. The progress of the reaction may be confirmed (or traced) by high performance liquid chromatography (HPLC), gas chromatography (GC) or the like.

  After completion of the reaction, the product polyether resin can be separated by a conventional separation method, for example, separation means such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, or a combination means combining these. Separation and purification are possible.

(Polythioether resin)
The polythioether resin is, for example, a polythioether resin containing a dimercapto component having at least a dibenzofluorene compound having a mercapto group or a derivative thereof as a polymerization component. In such a polythioether resin, a dibenzofluorene compound having a mercapto group is usually a compound in which E is a sulfur atom and p is 1 in the above formula (1), that is, a dibenzo represented by the following formula (a2) It may be a fluorene compound. Such a polythioether resin is usually a resin obtained by using the dimercapto component and a compound (D) having a plurality of halogen atoms as polymerization components.

(In the formula, Z, R ¹ , R ² , R ³ , R ⁴ , k, l, m and n are the same as above.)
Examples of the compound represented by the above formula (a2) include dibenzofluorene compounds having two mercapto groups exemplified above [for example, 9,9-bis (mercaptophenyl) dibenzofluorene, 9,9-bis (C _1-4). Alkyl-mercaptophenyl) dibenzofluorene, 9,9-bis (mercaptonaphthyl) dibenzofluorene, etc.].

The derivative is not particularly limited as long as it can react with the compound (D) having a plurality of halogen atoms to form a polythioether resin. For example, a hydrogen atom of a mercapto group of a dibenzofluorene compound having a mercapto group is Examples thereof include compounds substituted with an N-substituted carbonyl group (for example, an N, N-dialkylcarbonyl group such as an N, N-dimethylcarbonyl group). In addition, the dimercapto component should just be comprised with the dibenzofluorene compound which has a mercapto group, or its derivative (s), other dimercapto components [Dimercapto components other than the dibenzofluorene compound (a2) or its derivative (s), for example, dibenzofluorene compound (a2) ) Dimercapto component having a fluorene skeleton (9,9-bis (mercaptophenyl) fluorene such as 9,9-bis (4-mercaptophenyl) fluorene; 9,9-bis (4-mercapto-3-methylphenyl) fluorene 9,9-bis (such as mono- or _{di-C 1-4} alkyl - mercapto phenyl) fluorene; 9,9-bis [4- (2-mercaptoethyl) phenyl] fluorene such as 9,9-bis (mercapto _{C 2 -4} alkoxy - phenyl) fluorene; 9 It includes - (mono- or _{di-C 1-6} alkylphenyl mercapto _{C 2-4} alkoxy) fluorene] 9- bis [4- (2-mercapto-ethoxy) -3-methyl-phenyl] 9,9-bis fluorene May be.

  In the dimercapto component, the ratio of the dibenzofluorene compound (a2) or a derivative thereof is, for example, 30 mol% or more (for example, about 40 to 100 mol%), preferably 50 mol% or more (for example, for the dimercapto component). About 60 to 99 mol%), more preferably 70 mol% or more (for example, about 80 to 95 mol%), and usually 90 mol% or more (for example, 95 mol% or more).

  Moreover, as the compound (D) having a plurality of halogen atoms, the same compounds as those exemplified in the section of the polyether resin can be used. The compounds having a plurality of halogen atoms may be used alone or in combination of two or more. Further, as in the case of the polyether resin, a monohalo compound or the like may be used in combination with the compound having a plurality of halogen atoms as necessary.

  As described above, the polythioether-based resin is usually a resin obtained by using the dimercapto component and the compound (D) having a plurality of halogen atoms as polymerization components. That is, the polythioether resin is usually a polythioether resin having a thioether unit represented by the following formula (A3).

(Wherein A ³ is the residue of compound (D) having a plurality of halogen atoms, and Z, R ¹ , R ² , R ³ , R ⁴ , k, l, m and n are the same as above)
The polythioether resin is excellent in heat resistance. For example, the glass transition temperature Tg of the polythioether resin may be 180 ° C. or higher (for example, about 180 to 450 ° C.), preferably 200 to 400 ° C., more preferably about 230 to 350 ° C.

  As described above, the polythioether-based resin is obtained by polymerizing the compound (D) having a plurality of halogen atoms, a dibenzofluorene compound having a mercapto group (particularly a dimercapto component), and, if necessary, another monomer. It is done. The ratio of the compound having a plurality of halogen atoms and the dibenzofluorene compound having a mercapto group can be appropriately selected based on the equivalent ratio of the halogen atom of the compound having a halogen atom and the mercapto group of the dibenzofluorene compound having a mercapto group. .

  The polymerization reaction may be performed in the presence of a catalyst. Examples of the catalyst include a base catalyst and an acid catalyst, and usually a base catalyst is often used. Base catalysts include metal hydroxides (alkali metal oxides such as sodium hydroxide), metal carbonates (alkali metals such as sodium carbonate, cesium carbonate, calcium carbonate, or alkaline earth metal carbonates, sodium hydrogen carbonate, etc. Inorganic bases such as alkali metal or alkaline earth metal hydrogen carbonates of amines; amines [for example, tertiary amines (aromatic tertiary amines such as N, N-dimethylaniline, 1-methylimidazole, etc.] Heterocyclic tertiary amines) and the like, and organic bases such as carboxylic acid metal salts (such as alkali metal acetates or alkaline earth metal salts such as sodium acetate and calcium acetate). Of these catalysts, metal carbonates, particularly alkali metal carbonates such as cesium carbonate, alkaline earth metal carbonates such as calcium carbonate, and the like are preferable. You may use a catalyst individually or in combination of 2 or more types.

  The usage-amount of a catalyst can be adjusted according to the kind of catalyst, can be selected from the range of 0-5 mol with respect to 1 mol of dimercapto components, For example, 0.001-4.5 mol, Usually, 0.01- It may be about 4 mol, preferably 0.01 to 3.5 mol, more preferably about 0.05 to 3 mol.

  The polymerization reaction may be performed in the absence of a solvent, but is usually performed in the presence of a solvent in many cases. The solvent is not particularly limited and can be used in a wide range. Typical solvents (organic solvents) include ether solvents (dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane), halogenated solvents (halogenated such as methylene chloride, chloroform, carbon tetrachloride). Hydrocarbons), aromatic hydrocarbons (benzene, toluene, xylene, etc.), heterocyclic compounds (N-methyl-2-pyrrolidone, etc.), sulfone solvents (aliphatic sulfones such as sulfolane, dimethyl sulfone, diphenyl sulfone, etc.) And aromatic sulfones). Among these solvents, in particular, heterocyclic compounds such as N-methyl-2-pyrrolidone; high-boiling solvents such as sulfolane solvents such as sulfolane and diphenylsulfone (for example, boiling point of 180 ° C. or higher (for example, 200 to 500 ° C.) The solvent is preferably 210 to 450 ° C., more preferably about 220 to 400 ° C.). You may use the said solvent individually or in combination of 2 or more types.

  The amount of the solvent used is, for example, 0.1 to 30 parts by weight (for example, 0.3 to 20 parts by weight) with respect to 1 part by weight of the total amount of the dimercapto component and the compound (D) having a plurality of halogen atoms. The amount may preferably be about 0.4 to 10 parts by weight, more preferably about 0.5 to 5 parts by weight.

  The polymerization reaction varies depending on the type of component catalyst used and the like, but is usually carried out under heating, for example, 120 to 350 ° C., preferably 130 to 330 ° C., more preferably 140 to 300 ° C. (for example, , 180-270 ° C.). For the heating, a temperature raising and / or temperature lowering operation or the like may be used as appropriate, or may be performed in a single step at a substantially constant temperature, or a plurality of steps may be performed at different temperatures. The reaction time may be, for example, about 30 minutes to 48 hours, preferably about 1 to 24 hours, and more preferably about 1.5 to 16 hours (for example, 2 to 10 hours).

  When obtaining a uniform and high molecular weight polythioether resin having a narrow molecular weight distribution width, polymerization may be carried out by heating in a plurality of steps. In a plurality of heating steps, the heating temperature is often increased sequentially. In addition, when superposing | polymerizing by several steps of heating, the transition to subsequent heating temperature may be performed continuously and you may carry out at intervals. In the polymerization reaction by two-stage heating, the heating time of the first stage and the second stage is, for example, about 30 minutes to 24 hours, preferably 1 to 12 hours, and more preferably about 1.5 to 6 hours. It can be suitably selected from the range. The reaction may be performed while stirring.

  The reaction may be performed in air, but may be performed in an atmosphere or flow of an inert gas (such as helium, nitrogen, argon). Moreover, you may perform reaction under a normal pressure or pressurization. The progress of the reaction may be confirmed (or traced) by high performance liquid chromatography (HPLC), gas chromatography (GC) or the like.

  After completion of the reaction, the product polythioether resin can be separated by a conventional separation method such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, or a combination of these. Separation and purification are possible.

  The novel dibenzofluorene compound of the present invention has excellent properties such as high heat resistance and a high refractive index, and can be suitably used as a resin additive, a resin raw material, and the like. Further, the dibenzofluorene compound of the present invention has low linear expansion, and can be molded with high dimensional accuracy even when applied to a resin or the like. Furthermore, the dibenzofluorene compound of the present invention is excellent in additive dispersibility and is also suitable as a molding material containing various additives. For example, the novel dibenzofluorene compound of the present invention (or a resin containing a dibenzofluorene compound as a polymerization component) can efficiently disperse an additive such as carbon. Therefore, when applied to a resin or the like, it is possible to efficiently obtain a molded body (including a film and a film) having the above-described excellent characteristics and high strength or high hardness.

  Therefore, the novel dibenzofluorene compound of the present invention (or a resin containing a dibenzofluorene compound as a polymerization component, such as a polyester resin) is an optical lens, an optical film, an optical sheet, a pickup lens, a hologram, a liquid crystal film, an organic EL ( It can be suitably used for an electroluminescence film. In addition, the dibenzofluorene compound of the present invention (or a resin containing a dibenzofluorene compound as a polymerization component) or a molded product thereof (for example, a resin composition containing a function manifesting agent (pigment etc.) and a molded product thereof) Preventive materials, charging trays, conductive sheets, protective films (protective films for electronic devices, liquid crystal members, etc.), optical disks, inkjet printers, digital paper, organic semiconductor lasers, thermal recording materials, hologram recording materials, dye-sensitized solar cells , EMI shield film, photochromic material, organic EL (electroluminescence) element, organic photoreceptor, color filter, sliding member, automotive parts material, aerospace material, carrier transport agent, ink, adhesive, adhesive, building material, Suitable for interior materials, resin fillers, colored glass, light emitters, sensors, etc.

  In particular, since the dibenzofluorene compound of the present invention (or a resin containing a dibenzofluorene compound as a polymerization component) is excellent in optical properties, it forms (or forms) a molded product (optical molded product) for optical use. Useful for. Examples of such an optical molded body include an optical film. As an optical film, a polarizing film (and a polarizing element and a polarizing plate protective film constituting it), a retardation film, an alignment film (alignment film), a viewing angle expansion (compensation) film, a diffusion plate (film), a prism sheet, Light guide plate, brightness enhancement film, near infrared absorption film, reflection film, antireflection (AR) film, reflection reduction (LR) film, antiglare (AG) film, transparent conductive (ITO) film, anisotropic conductive film (ACF) ), Electromagnetic wave shielding (EMI) film, film for electrode substrate, film for color filter substrate, barrier film, color filter layer, black matrix layer, adhesive layer or release layer between optical films. In particular, the film is useful as an optical film for use in device displays. Specifically, as a display member (or display) provided with such an optical film, an FPD device (for example, LCD, etc.) such as a monitor of a personal computer, a television, a mobile phone, a car navigation, a touch panel, etc. PDP etc.).

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

  In the examples, the properties of the compound or polymer were measured or evaluated by the following methods.

(1) Molecular weight measurement The weight average molecular weight Mw of the polymer was 2 continuous linear polystyrene gel columns (Tosoh TSKgel G5000H _XL ) under conditions of 30 ° C. (flow rate 0.085 mL / min) using chloroform as an eluent. Measured by gel permeation chromatography (GPC) on a polystyrene standard with a JASCO Gulliver equipped with G4000H _XL ).

(2) Glass transition temperature (Tg) measurement Using a differential scanning calorimeter (“DSC-60”, manufactured by Shimadzu Corporation), the glass transition temperature (Tg) was measured under a nitrogen flow of 50 mL / min and a temperature rising condition of 10 ° C./min.

(3) Thermogravimetric analysis (TGA)
Thermogravimetric analysis (TGA) was performed at a heating rate of 10 ° C. in a nitrogen atmosphere (Tdpa) and an air atmosphere (Tdpb) (flow rate 50 ml / min) using a “TGA-50” apparatus manufactured by Shimadzu Corporation. The thermal decomposition temperature was measured in minutes.

(4) FT-IR spectrum The FT-IR spectrum was recorded with the FT-IR-230 spectrophotometer made from JASCO.

(5) ¹ H-NMR spectrum
¹ H-NMR spectra were recorded on a JEOL GTX-400 spectrometer using tetramethylsilane as internal standard and CDCl ₃ as solvent.

(6) MALDI-TOF-MASS
MALDI-TOF-MS spectra were obtained with a Shimadzu AXIMA-CFR mass spectrometer.

(7) Refractive Index Measurement After dissolving the polymer in methyl chloride and removing insoluble matter with a 0.2 μm membrane filter, after forming a thin film on silicon well polished at 1000 to 3000 rpm with a spin coater The refractive indexes at λ = 589 nm and λ = 632.4 nm were measured with an optical thin film measuring apparatus F20 (manufactured by Filmetrics).

(Synthesis example)
(1) Synthesis of benz [f] indan-1-one α, α, α ′, α′-tetrabromo-o-xylene 30.0 g (0.0710 mol) and 2-cyclopenten-1-one 5.83 g (0 0.0710 mol) was dissolved in 270 mL of DMF (dimethylformamide). Further, sodium iodide (69.7 g, 0.465 mol) was added, and the resulting mixture was heated to 80 ° C. and stirred overnight to react. The cooled reaction mixture was poured into ice water (500 mL) and the brown color due to iodine was removed by the slow addition of aqueous sodium bisulfite. Filtration gave a yellow precipitate that was recrystallized from 95% ethanol to give benz [f] indan-1-one in 35% yield. The melting point was 144-146 ° C.

¹ H-NMR (400 MHz, CDCl ₃ ) δ: 2.79-2.82 (t, 2H), 3.31-3.34 (t, 2H), 7.48-8.33 (m, 6H)
The reaction formula is shown below.

(2) Synthesis of 2,3: 6,7-dibenzo-9-fluorenone The resulting benz [f] indan-1-one 8.08 g (0.0444 mol), NBS (N-bromosuccinimide) 8.68 g ( 0.0596 mol), and 40 mg of benzoyl peroxide were refluxed in 120 mL of dry CCl ₄ for 2 hours. The solution after reflux was cooled, NBS was removed by filtration, and the resulting crude product was used directly in the next step. The crude bromide product in CCl _{4 was} cooled in an ice bath and then 7.72 mL (5.64 g, 0.056 mol) triethylamine (Et ₃ N) was added slowly. The resulting mixture was allowed to warm to room temperature and stirred overnight. Thereafter, the resulting precipitate was taken out and dried under reduced pressure. The resulting dried product (benz [f] inden-1-one) was used without further purification.

¹ H-NMR (400 MHz, CDCl ₃ ) δ: 6.11-6.14 (d, 2H), 7.30-7.95 (m, 6H)
The reaction formula is shown below.

  Then, α, α, α ′, α′-tetrabromo-o-xylene 18.72 g (44.4 mmol) and the obtained benz [f] inden-1-one 8.0 g (44.4 mmol) were added to 350 mL of DMF. Dissolved in. 43.6 g (290.8 mmol) of sodium iodide was added, and the resulting mixture was reacted at 80 ° C. with stirring overnight. The reaction was stopped in ice water and decolorized with sodium bisulfite. The resulting yellow precipitate was filtered, recrystallized from glacial acetic acid, then recrystallized from xylene, and sublimated to give pale yellow needle-like 2,3: 6,7-dibenzofluorenone in 48% yield. The melting point was 270-273 ° C.

¹ H-NMR (400 MHz, CDCl ₃ ) δ: 7.45-7.58 (m, 4H), 7.85-7.91 (t, 4H), 8.07 (s, 2H), 8.25 (S, 2H)
IR: 1706.2cm < ^-3 >
MALDI-TOF-MASS: 280 (M ^<+> ).

  The reaction formula is shown below.

Example 1
Synthesis of 9,9-bis (4-hydroxyphenyl) -2,3: 6,7-dibenzo-9-fluorene In a 150 mL round bottom flask equipped with a stirrer and a reflux condenser, 2,3 obtained in the synthesis example : 5.0 g (0.017 mol) of 6,7-dibenzofluorenone was charged together with 7.2 g (0.076 mol) of molten phenol. 30 mL of CH ₂ Cl ₂ was added and dissolved by stirring. Then 0.15 mL of 3-mercaptopropionic acid and 1.5 mL of methanesulfonic acid were added to the flask. The mixture was heated to 50 ° C. and reacted for 8 hours. After cooling to room temperature, the reaction mixture was filtered and washed with CH ₂ Cl ₂ and then warm water. After washing, the obtained solid was recovered, and 9,9-bis (4-hydroxyphenyl) -2,3: 6,7-dibenzo-9-fluorene was obtained in a yield of 65%. The melting point was 299-301 ° C.

¹ H-NMR (400 MHz, CDCl ₃ ) δ: 6.64 (d, J = 8, 4H), 7.07 (d, J = 8, 4H), 7.34-7.42 (m, 4H) 7.73 (d, J = 8, 2H), 7.76 (s, 2H), 7.91 (d, J = 8, 2H), 8.37 (s, 2H).

MALDI-TOF-MASS: 451.7 (M ^<+> ).

  The reaction formula is shown below.

(Example 2)
In Example 1, it reacted and collect | recovered similarly to Example 1 except having replaced with phenol 7.2g (0.076 mol), and having used 2-naphthol 10.9g (0.076 mol). -Bis [6- (2-hydroxynaphthyl)]-2,3: 6,7-dibenzo-9-fluorene was obtained in 59% yield. The melting point was 315 to 319 ° C.

MALDI-TOF-MASS: 553.4 (M ⁺ )
The reaction formula is shown below.

(Example 3)
Polyester synthesis 1
0.5631 g (1.2 mmol) of 9,9-bis (4-hydroxyphenyl) -2,3: 6,7-dibenzo-9-fluorene obtained in Example 1 and 4,4′-oxybis (benzoyl chloride) ) [Or di (4-chlorocarbonylphenyl) ether] 0.3689 g (1.2 mmol) dissolved in 3 mL of diphenyl ether in a 100 ml 2-neck round bottom flask equipped with a magnetic stirrer and drying tube. The mixture was heated and stirred at 200 ° C. for 2 hours under an argon flow. The reaction mixture was then poured into 400 mL of methanol and the white precipitate was collected by filtration and washed several times with methanol and water to remove diphenyl ether. The resulting crude polymer was purified by reprecipitation from chloroform solution into methanol. The resulting precipitate was filtered, washed with methanol, and dried at 80 ° C. under reduced pressure for 24 hours to obtain the desired product (polyester) in a yield of 95%. The weight average molecular weight of the obtained polyester was 4.0 × 10 ⁴ , Tg was 266.5 ° C., Tdpa was 522.9 ° C., and Tdpb was 502.3 ° C.

Example 4
Polyester synthesis 2
In Example 3, 0.383 g (1.2 mmol) of 2,7-di (chlorocarbonyl) -9,9-dimethylfluorene was used instead of 0.3689 g of 4,4′-oxybis (benzoyl chloride). Except for the above, polyester was obtained in the same manner as in Example 3 with a yield of 96%. The weight average molecular weight of the obtained polyester was 13.1 × 10 ⁴ , Tg was 298.1 ° C., Tdpa was 506.1 ° C., and Tdpb was 482.7 ° C.

(Example 5)
Polyester synthesis 3
In Example 3, instead of 0.3689 g of 4,4′-oxybis (benzoyl chloride), 0.515 g (1.2 mmol) of 2,2-di (4-chlorocarbonylphenyl) hexafluoropropane was used. Obtained a polyester in a yield of 93% in the same manner as in Example 3. The weight average molecular weight of the obtained polyester was 4.0 × 10 ⁴ , Tg was 355.9 ° C., Tdpa was 540.7 ° C., and Tdpb was 502.1 ° C.

(Example 6)
Polyester synthesis 4
In Example 3, instead of 0.3689 g of 4,4′-oxybis (benzoyl chloride), 0.618 g (1.2 mmol) of 2,7-di (chlorocarbonyl) -9,9-di n-octylfluorene was used. A polyester was obtained in a yield of 95% in the same manner as in Example 3 except that it was used. The weight average molecular weight of the obtained polyester was 42.9 × 10 ⁴ , Tg was 216.3 ° C., Tdpa was 430.7 ° C., and Tdpb was 368.3 ° C.

(Example 7)
Polyester synthesis 5
In Example 3, instead of using 0.3489 g of 4,4′-oxybis (benzoyl chloride), 0.243 g (1.2 mmol) of 1,3-di (chlorocarbonyl) benzene (isophthalic acid dichloride) was used. Produced a polyester in a yield of 98% in the same manner as in Example 3. The weight average molecular weight of the obtained polyester was 7.7 × 10 ⁴ , Tg was 348.4 ° C., Tdpa was 535.9 ° C., and Tdpb was 507.6 ° C.

(Example 8)
Synthesis of polyether 1
Under an argon atmosphere, 0.6757 g (1.5 mmol) of 9,9-bis (4-hydroxyphenyl) -2,3: 6,7-dibenzo-9-fluorene obtained in Example 1 and 0.4146 g of potassium carbonate (3.0 mmol) and a mixture of 4 mL of DMAc (N, N-dimethylacetamide) were reacted by stirring at 140 ° C. for 2 hours. Thereafter, 0.3873 g (1.5 mmol) of 2,5-bis (4-fluorophenyl) -1,3,4-oxadiazole is added to the cooled reaction mixture until a very viscous solution is obtained. The temperature was gradually increased to 170 ° C. over 4 to 6 hours. The reaction mixture was allowed to cool to room temperature, further diluted with DMAc, and the inorganic salt was removed by filtration. The reaction mixture after removing the inorganic salt was then slowly poured into 300 mL of methanol. The precipitate was washed with water and methanol. After washing, the recovered polymer was dried under reduced pressure at 100 ° C. for 24 hours to obtain the desired product (polyether) in a yield of 93%. The obtained polyether had a weight average molecular weight of 56,500, Tg of 301.6 ° C., Tdpa of 532.1 ° C., Tdpb of 552 ° C., a refractive index at λ = 589 nm of 1.6921 and a refractive index at λ = 632.4 nm. Was 1.6831.

Example 9
Synthesis of polyether 2
In Example 8, instead of 0.3873 g of 2,5-bis (4-fluorophenyl) -1,3,4-oxadiazole, 5-t-butyl-1,3-bis (4-fluorobenzoyl) A polyether was obtained in a yield of 90% in the same manner as in Example 8 except that 0.567 g (1.5 mmol) of benzene was used. The obtained polyether had a weight average molecular weight of 53,500, Tg of 258.6 ° C., Tdpa of 550.6 ° C., Tdpb of 564 ° C., refractive index at λ = 589 nm of 1.6693, refractive index at λ = 632.4 nm Was 1.6611.

(Example 10)
Synthesis of polyether 3
In Example 8, instead of 0.3873 g of 2,5-bis (4-fluorophenyl) -1,3,4-oxadiazole, 0.483 g of 1,4-bis (4-fluorobenzoyl) benzene ( 1.5 mmol) A polyether was obtained in a yield of 95% in the same manner as in Example 8 except that it was used. The weight average molecular weight of the obtained polyether was 76600, Tg was 271.5 ° C., Tdpa was 533.8 ° C., Tdpb was 536 ° C., the refractive index at λ = 589 nm was 1.6881, and the refractive index at λ = 632.4 nm. Was 1.6737.

(Example 11)
Synthesis of polyether 4
In Example 8, instead of 0.3873 g of 2,5-bis (4-fluorophenyl) -1,3,4-oxadiazole, 0.621 g of 4,4′-bis (4-fluorobenzoyl) diphenyl ether was used. (1.5 mmol) A polyether was obtained in a yield of 98% in the same manner as in Example 8 except that it was used. The obtained polyether had a weight average molecular weight of 50,000, Tg of 254.9 ° C., Tdpa of 580.1 ° C., and Tdpb of 580 ° C.

(Example 12)
Synthesis of polyether 5
In Example 8, instead of 0.3873 g of 2,5-bis (4-fluorophenyl) -1,3,4-oxadiazole, 0.381 g (1.5 mmol) of di (4-fluorophenyl) sulfone was used. A polyether was obtained in a yield of 96% in the same manner as in Example 8 except that it was used. The weight average molecular weight of the obtained polyether was 58700, Tdpa was 570.0 ° C., Tdpb was 522 ° C., the refractive index at λ = 589 nm was 1.6617, and the refractive index at λ = 632.4 nm was 1.6917. .

(Example 13)
(1) Synthesis of bis (N, N-dimethyl-O-thiocarbamate) 9,9-bis (4) obtained in Example 1 was added to 50 mL of cooled methanol containing 1.68 g (30.0 mmol) of potassium hydroxide. -Hydroxyphenyl) -2,3: 6,7-dibenzo-9-fluorene (6.53 g, 14.4 mmol) was added, and the mixture was stirred at 0 ° C. for 1 hour. Thereafter, 3.70 g (30.0 mmol) of N, N-dimethylthiocarbamoyl chloride was added, the temperature was raised to 60 ° C., and stirring was continued at this temperature for another 4 hours. And white precipitate was collect | recovered by filtration and this precipitate was wash | cleaned by the cooling methanol aqueous solution (Methanol / water = 1/1 (volume ratio)). Further, the white precipitate was recrystallized with a mixed solvent of methanol and chloroform to obtain white crystals (bis (N, N-dimethyl-O-thiocarbamate), the following compound) in a yield of 90% (8.1 g). It was. The melting point of the crystals was 269 to 271 ° C.

¹ H-NMR (CDCl ₃ ) δ: 3.23 (s, 6H), 3.39 (s, 6H), 6.94 (d, J = 8.8, 4H), 7.35 (d, J = 8.8, 4H), 7.40-7.47 (m, 4H), 7.77 (d, J = 8, 2H), 7.85 (s, 2H), 7.93 (d, J = 8, 2H), 8.37 (s, 2H)
MALDI-TOF-MS: 625.7 (M ⁺ )
The reaction formula is shown below.

(2) Synthesis of bis (N, N-dimethyl-S-carbamate) Next, a mixture of 6.0 g (9.6 mmol) of the obtained white crystals and 5 mL of diphenyl ether was put in a round bottom flask equipped with a nitrogen inlet. And continued heating at 260 ° C. for 2 hours. After cooling to room temperature, 100 mL of ether was added to obtain a precipitate. A white precipitate was collected by filtration and washed with a cooled aqueous methanol solution (methanol / water (volume ratio) = 1: 1). Further, the white precipitate was recrystallized with a mixed solvent of methanol and chloroform to obtain white crystals (bis (N, N-dimethyl-S-carbamate), the following compound) in a yield of 80% (4.7 g). . The melting point of the crystals was 352 to 354 ° C.

¹ H-NMR (CDCl ₃ ) δ: 2.93 (s, br, 12H), 7.27-7.41 (m, 12H), 7.67 (d, J = 6.9, 2H), 7 .73 (s, 2H), 7.86 (d, J = 6.9, 2H), 8.28 (s, 2H)
The reaction formula is shown below.

(3) Synthesis of 9,9-bis (4-mercaptophenyl) -2,3: 6,7-dibenzo-9-fluorene Further, 5.0 g (8.0 mmol) of the obtained white crystals and potassium hydroxide 4 .48 g (80.0 mmol) was placed in a 50 mL three-necked flask equipped with a condenser and an argon gas inlet, and 20 mL of methanol was added. And under argon atmosphere, the mixture was stirred at room temperature until potassium hydroxide was completely dissolved, and then heated to reflux. Further, 10 mL of distilled pyridine was added to the flask and stirred for 8 hours. Then, it cooled to room temperature and filtered the solution. The filtrate was diluted with 300 mL of distilled water and acidified with 5% hydrochloric acid. The resulting white precipitate was collected by filtration, purified by two recrystallizations from ethanol, and white crystals (9,9-bis (4-mercaptophenyl) -2,3: 6,7-dibenzo-9- Fluorene, the following compound) was obtained in a yield of 95% (3.7 g). The melting point of the crystals was 281 to 283 ° C.

¹ H-NMR (400 MHz, CDCl ₃ ) δ: 3.35 (s, 2H), 7.11-7.24 (m, 8H), 7.40-7.48 (m, 4H), 7.74 −7.76 (m, 4H), 7.93 (d, J = 8, 2H), 8.34 (s, 2H)
MALDI-TOF-MASS: 485.3 (M ⁺ )
The reaction formula is shown below.

(Example 14)
Synthesis of polythioether 1
0.847 g (0.300 mmol) of bis (N, N-dimethyl-S-carbamate) obtained in Example 13 and 0.077 g of 2,5-bis (4-fluorophenyl) -1,3,4-oxazole (0.300 mmol), 0.048 g (0.150 mmol) of cesium carbonate, 0.09 g (0.900 mmol) of calcium carbonate, and 0.9 g of diphenylsulfone were charged into a 30 mL two-necked round bottom flask under argon flow. The mixture was warmed to 200 ° C. and held at this temperature for 2 hours. Thereafter, the temperature was further raised to 240 ° C. and kept at this temperature for 2 hours. The obtained mixed liquid was cooled and quenched with 0.5 mL of acetic acid, and then poured into methanol to obtain a white powdery polymer precipitate. The precipitate was collected by filtration and washed with methanol. The resulting crude polymer was purified by reprecipitation from a chloroform solution in methanol. And the polymer collect | recovered by filtration was dried at 90 degreeC overnight, and the target object (polythioether) was obtained with 90% or more of yield. The weight average molecular weight of the obtained polythioether was 33600, Tg was 320.8 ° C., Tdpa was 546.4 ° C., and Tdpb was 549 ° C.

(Example 15)
Synthesis of polythioether 2
In Example 14, instead of 0.077 g (0.300 mmol) of 2,5-bis (4-fluorophenyl) -1,3,4-oxadiazole, 5-t-butyl-1,3-bis ( A polythioether was obtained in a yield of 93% in the same manner as in Example 14 except that 0.114 g (0.300 mmol) of 4-fluorobenzoyl) benzene was used. The obtained polythioether had a weight average molecular weight of 47,000, Tg of 247.5 ° C., Tdpa of 513 ° C., and Tdpb of 526 ° C.

(Example 16)
Synthesis of polythioether 3
In Example 14, instead of 0.077 g (0.300 mmol) of 2,5-bis (4-fluorophenyl) -1,3,4-oxadiazole, 1,4-bis (4-fluorobenzoyl) benzene Was obtained in the same manner as in Example 14 except that 0.097 g (0.300 mmol) was used. The weight average molecular weight of the obtained polythioether was 48300, Tg was 262.2 ° C., Tdpa was 560 ° C., and Tdpb was 572 ° C.

(Example 17)
Synthesis of polythioether 4
In Example 14, instead of 0.077 g (0.300 mmol) of 2,5-bis (4-fluorophenyl) -1,3,4-oxadiazole, 4,4′-bis (4-fluorobenzoyl) A polythioether was obtained in a yield of 93% in the same manner as in Example 14 except that 0.124 g (0.300 mmol) of diphenyl ether was used. The obtained polythioether had a weight average molecular weight of 62,000, Tg of 249.0 ° C., Tdpa of 560.0 ° C., and Tdpb of 567 ° C.

Claims (10)

A compound represented by the following formula (1).

(In the formula, ring Z represents an aromatic hydrocarbon ring, E represents an oxygen atom or sulfur atom, R ¹ and R ² are the same or different, and are a cyano group, a halogen atom, an alkyl group, a hydroxyalkyl group, a carboxyl group. , Alkoxycarbonyl group, R ³ is hydrocarbon group, alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, substituted amino group, hydroxyalkyl R represents a group or a carboxyl group, R ⁴ represents an alkylene group, k is an integer of 0 to 2, l is an integer of 0 to 3, m is an integer of 0 or more, n is an integer of 0 or more, and p is 1 or more. An integer, where ring Z is a naphthalene ring or E is a sulfur atom. ) The compound according to claim 1, wherein in formula (1), ring Z is a benzene ring, R ³ is an alkyl group, and m is 0-2.   The compound according to claim 1, wherein in formula (1), ring Z is a naphthalene ring. 9, 9-bis (hydroxynaphthyl) -2,3: 6,7-dibenzo fluorene, and 9,9-bis (hydroxy _{C 2-4} alkoxy naphthyl) -2,3: is selected from 6,7-dibenzofluorene The compound according to claim 1, which is at least one kind. 9,9-bis (mercaptophenyl) -2,3: 6,7-dibenzofluorene, 9,9-bis (mono or diC _1-4 alkyl-mercaptophenyl) -2,3: 6,7-dibenzofluorene , 9,9-bis (mercapto _{C 2-4} alkoxyphenyl) -2,3: 6,7-dibenzo fluorene, 9,9-bis (mercapto _{C 2-4} alkoxy - mono- or _{di-C 1-4} alkyl phenyl) 2,3: 6,7-dibenzo fluorene, 9,9-bis (mercaptomethyl naphthyl) -2,3: 6,7-dibenzo fluorene, and 9,9-bis (mercapto _{C 2-4} alkoxy naphthyl) -2 The compound according to claim 1, wherein the compound is at least one selected from 3,6,7-dibenzofluorene. The method to manufacture the compound of Claim 1 through at least the process (A) of making the compound represented by following formula (2), the compound represented by following formula (3), or its derivative (s) react.

(In the formula, Z, E, R ¹ , R ² , R ³ , R ⁴ , k, l, m, n and p are the same as above.)   Resin which uses the polyol component or polythiol component comprised with the compound of Claim 1 as a polymerization component. In the formula (1), a ring Z is a naphthalene ring, an E is an oxygen atom, and a diol component (a) composed of at least a compound having p of 1 is polymerized with a dicarboxylic acid component (b). The resin according to claim 7, which is a polyester resin as a component . In the formula (1), ring Z is a naphthalene ring, E is an oxygen atom, and p is 1, and a diol component (a) composed of at least a compound having a plurality of halogen atoms (C The resin according to claim 7, which is a polyether resin having a polymerization component . A polythioether comprising, as a polymerization component, a dimercapto component composed of at least a compound or a derivative thereof wherein E is a sulfur atom and p is 1 in the formula (1) and a compound (D) having a plurality of halogen atoms The resin according to claim 7, which is a resin.