JP5395352B2 - Alcohol having a fluorene skeleton - Google Patents

Description

  The present invention relates to a novel alcohol having a fluorene skeleton (specifically, a 9,9-bisphenylfluorene skeleton).

  A compound having a fluorene skeleton such as a 9,9-bisphenylfluorene skeleton has an excellent function in terms of refractive index, heat resistance and the like, and is known to be used as a resin raw material or an additive. As a method for expressing such an excellent function of the fluorene skeleton in the resin and making it moldable, a fluorene compound having a reactive group (such as a hydroxyl group) such as bisphenol fluorene (BPF), biscresol fluorene ( BCF), bisphenoxyethanol fluorene (BPEF) or the like is used as a constituent component of the resin, and a method of introducing a fluorene skeleton into a part of the skeleton structure of the resin is known.

  For example, as an example in which a compound having a fluorene skeleton is used as an epoxy resin raw material, Japanese Patent No. 3659533 (Patent Document 1) discloses an epoxy resin represented by the following formula (1).

(In the formula, each R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and G represents a glycidyl group.)
In this document, regarding the group R, a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group and the like are mentioned as preferable groups, and it is described that a hydrogen atom or a methyl group is particularly preferable. In the examples of this document, 9,9-bis [4- (2-glycidyloxyethoxy) phenyl] fluorene, 9,9-bis [4- (2-glycidyloxyethoxy) -3-methylphenyl] fluorene It is described that obtained.

  JP-A-2005-162785 (Patent Document 2) discloses a resin composition composed of a compound having a fluorene skeleton and a thermoplastic resin. , 9-bis (4-glycidyloxyphenyl) fluorene, 9,9-bis (4-glycidyloxy-3-methylphenyl) fluorene, 9,9-bis (4-glycidyloxy-3,5-dimethylphenyl) fluorene 9,9-bis (4-glycidyloxyethoxyphenyl) fluorene, 9,9-bis (4-glycidyloxyethoxy-3-methylphenyl) fluorene, 9,9-bis (4-glycidyloxyethoxy-3,5) It is stated that glycidyl ethers such as -dimethylphenyl) fluorene can be used.

  Since the epoxy resins described in these documents have a 9,9-bisphenylfluorene skeleton, heat resistance can be improved as compared with conventional epoxy resins such as bisphenol A type epoxy resins. However, such an epoxy resin often has a high melt viscosity and is often not sufficient in terms of handleability.

  Also, as optical material applications such as optical overcoat agent, hard coat agent, antireflection film, spectacle lens, optical fiber, optical waveguide, hologram, etc., bisphenols (bisphenol A etc.) or diacrylates of ethylene oxide adducts thereof, etc. Multifunctional acrylates are used. Such polyfunctional acrylates are required to have improved properties such as moisture resistance, heat resistance, and high refractive index. Like the epoxy resin, a compound having a fluorene skeleton is used as a polyfunctional acrylate raw material. It is also known to use.

  For example, Japanese Patent Laid-Open No. 4-325508 (Patent Document 3) discloses a copolymer of a composition capable of radical polymerization, the main component of which is a compound represented by the following formula (1), having a refractive index of 1. More than 60 plastic lens materials are disclosed.

(Wherein R ₁ and R ₂ are hydrogen or a methyl group, m and n are integers of 0 to 5)
In this document, as a compound represented by the formula (1), a compound obtained by reacting 9,9-bis (4-hydroxyphenyl) fluorene with (meth) acrylic acid chloride, or 9,9-bis (4- It describes compounds in which (meth) acrylic acid is reacted after addition of ethylene oxide or propylene oxide to (hydroxyphenyl) fluorene.

  Patent Document 2 discloses a resin composition composed of a compound having a fluorene skeleton and a thermoplastic resin. As the compound having a fluorene skeleton, 9,9-bis (4- ( (Meth) acryloyloxyphenyl) fluorene, 9,9-bis (3-methyl-4- (meth) acryloyloxyphenyl) fluorene, 9,9-bis (3-methyl-4- (2- (meth) acryloyloxyethoxy) It is stated that bifunctional (meth) acrylates such as) phenyl) fluorene can be used.

  Furthermore, JP 2007-91870 A (Patent Document 4) discloses a specific polyfunctional (meth) acrylate having a fluorene skeleton, a hydrolytic condensable organosilicon compound having a polymerizable group, and a photoacid generator, In addition to 9,9-bis (mono to trihydroxyphenyl) fluorenes (meth) acrylates, 9,9- is also disclosed as the polyfunctional (meth) acrylate. It is described that (meth) acrylates of alkylene oxide adducts of 9,9-bis (mono to trihydroxyphenyl) fluorenes such as bis (4- (meth) acryloyloxyethoxy-3-phenylphenyl) fluorene can also be used. Yes.

  Since the (meth) acrylates described in these documents have a 9,9-bisphenylfluorene skeleton, compared to conventional (meth) acrylates such as di (meth) acrylates of bisphenols or ethylene oxide adducts thereof. Various properties can be improved, such as a higher refractive index. However, some of the (meth) acrylates described in these documents are not sufficient in terms of handling properties, such as being easily solidified after synthesis, and the development of (meth) acrylates with even more practicality is expected. Has been.

As described above, there is a demand for a compound having a fluorene skeleton that can further improve characteristics such as handling properties and heat resistance when used as a resin raw material.
Japanese Patent No. 3659533 (Claim 1, paragraph number [0013], Example) Japanese Patent Laying-Open No. 2005-162785 (Claim 1, paragraph numbers [0043] and [0044]) JP-A-4-325508 (Claim 1, paragraph number [0011]) JP 2007-91870 A (Claim 1, paragraph number [0041])

  Accordingly, an object of the present invention is to provide a novel fluorene skeleton-containing alcohol that can impart excellent handling properties even if it has a fluorene skeleton (9,9-bisphenylfluorene skeleton).

  Another object of the present invention is to provide a novel fluorene skeleton-containing alcohol capable of reducing the melt viscosity.

  Still another object of the present invention is to provide a novel fluorene skeleton-containing alcohol capable of reducing the flexural modulus at high temperatures.

  Another object of the present invention is to provide a novel fluorene skeleton-containing alcohol capable of achieving both improved heat resistance and reduced melt viscosity.

  Still another object of the present invention is to provide a novel fluorene skeleton-containing alcohol capable of imparting excellent handling properties and a high refractive index.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have a novel fluorene skeleton containing a combination of a 9,9-bis (monoarylphenyl) fluorene skeleton and a branched oxyalkylene group (such as an oxypropylene group). When alcohol is used as a resin raw material (epoxy resin raw material, acrylate raw material, polyester raw material, etc.) or the like, a conventional fluorene skeleton-containing compound [for example, 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene, 9, Compared to a compound having the same fluorene skeleton such as 9-bis (4-hydroxyethoxy-3-phenylphenyl) fluorene or its ethylene oxide adduct], it has a 9,9-bisphenylfluorene skeleton. And found that it can give excellent handling properties, Invention has been completed.

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

(In the formula, R ¹ represents a cyano group, a halogen atom or an alkyl group, R ² represents a branched alkylene group, R ³ represents a hydrocarbon ring group, k is an integer of 0 to 4, and m is 1 or more. (It is an integer.)
In the formula (1), R ² may be, for example, a branched C _3-4 alkylene group (eg, propylene group), and m may be about 1 to 4. In the formula (1), R ³ may be an aryl group such as a C _6-10 aryl group (for example, a phenyl group). In particular, in the formula (1), R ² may be a propylene group, m may be 1 to 2, and R ³ may be a phenyl group.

  Typical compounds represented by the formula (1) include compounds represented by the following formula (1A).

(Wherein R ¹ , R ² , R ³ , k, and m are the same as described above.)
In particular, the compound represented by the formula (1) is 9,9-bis [4- (2-hydroxypropoxy) -3-C _{6-10phenylphenyl} ] fluorene {for example, 9,9-bis [4- (2-hydroxypropoxy) -3-phenylphenyl] fluorene, etc.}.

  The present invention also includes a resin containing the compound as a polymerization component. Such a resin may be, for example, a polyester (polyester resin) having a diol component composed of at least the compound (compound represented by the formula (1)) and a dicarboxylic acid component as polymerization components. .

  In the present specification, the “class” such as a compound name includes a case of “having no substituent” and a case of “having a substituent”, and “may have a substituent”. May mean.

  The novel fluorene skeleton-containing alcohol of the present invention can be used as a resin raw material (for example, an epoxy resin raw material, an acrylate raw material, etc.) and the like without causing high viscosity, single curing immediately after synthesis, etc. Even if it has a 9-bisphenylfluorene skeleton, excellent handling properties can be imparted.

  Moreover, when the fluorene skeleton containing alcohol of this invention is used as a resin raw material (epoxy resin raw material etc.), melt viscosity can be reduced. For example, the epoxy resin using the fluorene skeleton-containing alcohol of the present invention as a raw material is an epoxy resin [9,9-bis (4-glycidyloxy-3-phenylphenyl) fluorene, 9, Compared with compounds having the same fluorene skeleton such as 9-bis (4-glycidyloxyethoxy-3-phenylphenyl) fluorene or glycidyl ethers of ethylene oxide adducts thereof, etc., the melt viscosity can be greatly reduced and the handling property is excellent. ing. Furthermore, when the alcohol of the present invention is used, for example, as an epoxy resin raw material, the bending elastic modulus at a high temperature can be reduced.

  Furthermore, the alcohol of the present invention has a 9,9-bis (monoarylphenyl) fluorene skeleton and the like and a branched oxyalkylene group (oxypropylene group, etc.). When used as a compound having a conventional 9,9-bisphenylfluorene skeleton (9,9-bis (phenyl) fluorene skeleton, 9,9-bis (methylphenyl) fluorene skeleton, etc.) (9,9-bis ( 4-hydroxyethoxyphenyl) fluorene, 9,9-bis (4-hydroxyethoxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxyethoxy-3,5-dimethylphenyl) fluorene, etc.) Compared to the heat resistance, the heat resistance is higher and the melt viscosity is unexpectedly lower. Compatible the door.

  Moreover, when the alcohol of the present invention is used as a resin raw material such as a (meth) acrylate raw material or a polyester raw material, it can provide excellent handling properties and a high refractive index as compared with an ethylene oxide adduct.

  Therefore, the alcohol of the present invention can impart excellent properties such as high heat resistance and a high refractive index to a resin and the like, and has high practical value.

  The compound of the present invention is a compound represented by the following formula (1).

(In the formula, R ¹ represents a substituent, R ² represents a branched alkylene group, R ³ represents a hydrocarbon ring group, k is an integer of 0 to 4, and m is an integer of 1 or more.)
In the above formula (1), examples of the substituent represented by the group R ¹ include a cyano group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a hydrocarbon group [for example, an alkyl group, an aryl group ( Non-reactive substituents such as a C _6-10 aryl group such as a phenyl group], and the like, and particularly a halogen atom, a cyano group or an alkyl group (particularly 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 is plural (two or more), the groups R ¹ may be different from each other or the same. Further, the groups R ¹ substituted on the two benzene rings constituting the fluorene (or fluorene skeleton) may be the same or different. Further, the bonding position (substitution position) of the group R ¹ with respect to the benzene ring constituting the fluorene is not particularly limited. The preferred substitution number k is 0 to 1, in particular 0. In the two benzene rings constituting fluorene, the number of substitutions k may be the same or different from each other.

In the formula (1), examples of the branched alkylene group represented by the group R ² include branched C _3-6 alkylene groups such as a propylene group (or 1,2-propanediyl group) and 1,2-butanediyl group. A branched C _3-4 alkylene group is preferable, and a propylene group is more preferable. In addition, when m is 2 or more, the branched alkylene group may be composed of different branched alkylene groups, and may be generally composed of the same branched alkylene group. In the two benzene rings, the groups R ² may be the same or different, and may usually be the same.

The number (number of added moles) m of the oxyalkylene group (OR ² ) can be selected from the range of about 1 to 15 (eg, 1 to 12), for example, 1 to 8, preferably 1 to 6, and more preferably 1 -4 (e.g. 1-3), especially 1-2. The number of substitutions m may be the same or different in different benzene rings. Moreover, in two benzene rings, the total (mx2) of oxyalkylene groups can be selected from the range of about 2 to 30 (for example, 2 to 24), for example, 2 to 16 (for example, 2 to 14), Preferably it may be 2 to 12 (eg 2 to 10), more preferably 2 to 8 (eg 2 to 6), especially 2 to 4 (eg 2 to 3).

In the formula (1), examples of the hydrocarbon ring group represented by the group R ³ include a cycloalkyl group and an aryl group. Examples of the cycloalkyl group include C _4-10 cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, and a cycloheptyl group, preferably a C _5-8 cycloalkyl group. As the aryl group, for example, phenyl group, tolyl group (2-tolyl group, 3-tolyl group, 4-tolyl group), xylyl group (2,6-xylyl group, 2,4-xylyl group, 3,4- A C _6-10 aryl group such as a xylyl group), preferably a C _6-8 aryl group, and more preferably a phenyl group. Preferred R ³ is an aryl group. The groups R ⁴ substituted on different benzene rings may be the same or different from each other, and may usually be the same.

  Typical compounds represented by the formula (1) include 9,9-bis (hydroxy-branched alkoxy-monoarylphenyl) fluorenes (compounds in which m is 1 in the formula (1)), 9,9 -Bis (hydroxypolybranched alkoxy-monoarylphenyl) fluorenes (compounds in which m is 2 or more in the formula (1)) are included.

The 9,9-bis (hydroxy-branched alkoxy-monoarylphenyl) fluorenes include, for example, 9,9-bis (hydroxy-branched C _3-4 alkoxy-monoarylphenyl) fluorenes {eg, 9,9-bis [ 9,9-bis (hydroxy-branched C ₃₋ such as 4- (2-hydroxypropoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -3-tolylphenyl] fluorene ₄ alkoxy-mono C _6-10 arylphenyl) fluorene, preferably 9,9-bis (2-hydroxypropoxy-mono C _6-8 arylphenyl) fluorene} and the like.

9,9-bis (hydroxypolybranched alkoxy-monoarylphenyl) fluorenes corresponds to the 9,9-bis (hydroxy-branched alkoxy-monoarylphenyl) fluorenes, and m is 2 or more, for example, 9,9-bis (hydroxydibranched C _3-4 alkoxy-monoarylphenyl) fluorenes {eg, 9,9-bis {4- [2- (2-hydroxypropoxy) propoxy] -3-phenylphenyl} 9,9-bis (hydroxydibranched C _3-4 alkoxy-mono C _6-10 arylphenyl) fluorene such as fluorene, preferably 9,9-bis [2- (2-hydroxypropoxy) propoxy-mono C _{6- 8} arylphenyl] fluorene} and the like.

Among these, preferable compounds represented by the formula (1) include compounds in which the substitution position of R ³ is the 3-position in the formula (1), that is, compounds represented by the following formula (1A). .

(Wherein R ¹ , R ² , R ³ , k, and m are the same as described above.)
Particularly preferable compounds represented by the formula (1) include compounds in which R ² is a propylene group among the compounds represented by the formula (1A), such as 9,9-bis [4- (2- Hydroxypropoxy) -3-arylphenyl] fluorenes {eg, 9,9-bis [4- (2-hydroxypropoxy) -3-C _6-10 arylphenyl] fluorene}, 9,9-bis {4- [2- (2-Hydroxypropoxy) propoxy] -3-arylphenyl} fluorenes {eg, 9,9-bis {4- [2- (2-hydroxypropoxy) propoxy] -3-C _6-10 arylphenyl] } Fluorene} and the like.

(Method for producing compound represented by formula (1))
Alkylene wherein the compound represented by formula (1) is not particularly limited, for example, corresponding to (1) a compound represented by the following formula (2A), an alkylene oxide or a radical R ² corresponds to the radical R ² It can be obtained by a method of reacting with carbonate, (2) a method of reacting a compound represented by the following formula (2B) with a compound represented by the following formula (2C), or the like.

(Wherein R ¹ , R ² , R ³ , k, m are the same as above)
(Method (1))
In the method (1), examples of the compound represented by the formula (2A) include compounds corresponding to the compound represented by the formula (1), such as 9,9-bis (hydroxy-monoarylphenyl) fluorenes. [For example, 9,9-bis (hydroxy-mono C _6-10 arylphenyl) fluorene such as 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene] and the like.

  The compound represented by the formula (2A) may be a commercially available product. For example, an acid (for example, an inorganic acid such as hydrochloric acid or sulfuric acid, a solid acid) or a thiol (mercaptocarboxylic acid) may be used. Manufactured by a method of reacting the compound represented by the formula (2B) (fluorenones) with a corresponding phenol (for example, hydroxybiphenyl such as 2-hydroxybiphenyl) in the presence of an acid, etc. May be used.

  The purity of the compound represented by the formula (2A) used as a raw material is not particularly limited, but is usually 95% by weight or more, and preferably 99% by weight or more.

In method (1), the alkylene oxide corresponding to the group R ² may be a branched C _3-6 alkylene oxide such as propylene oxide or butylene oxide (1,2-epoxybutane), preferably a branched C _3-4 alkylene. And oxides. Examples of the alkylene carbonate corresponding to the group R ² include branched C _3-6 alkylene carbonates such as propylene carbonate and butylene carbonate, preferably branched C _3-4 alkylene carbonates. 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 (2A). When alkylene carbonate is used, oxyalkylene units (branched alkoxy units) are introduced by the decarboxylation reaction after addition of alkylene carbonate.

In the method (1), the amount of alkylene carbonate corresponding to the alkylene oxide or a radical R ² corresponds to the group R ² may be adjusted according to the number of alkylene oxide units to be added is represented by the formula (2A) For example, 2 to 50 mol (eg 2 to 40 mol), preferably 2 to 30 mol (eg 2 to 25 mol), more preferably 2 to 20 mol (eg 2 to 15 mol) per mol of the compound. Mol) degree.

  The reaction may be carried out in the absence of a catalyst, but can usually be carried out in the presence of a catalyst. Examples of the catalyst include a base catalyst and an acid catalyst, and usually a base catalyst can be used. Base catalysts include metal hydroxides (alkali metals such as sodium hydroxide or alkaline earth metal hydroxides), metal carbonates (alkali metals such as sodium carbonate or alkaline earth metal carbonates, sodium hydrogen carbonate, etc.) Inorganic bases such as alkali metals or alkaline earth metal hydrogen carbonates; amines [for example, tertiary amines (trialkylamines such as triethylamine, aromatic tertiary amines such as N, N-dimethylaniline) , Heterocyclic tertiary amines such as 1-methylimidazole, etc.], 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). The catalyst (base catalyst) may be used alone or in combination of two or more.

  The usage-amount of a catalyst can be adjusted according to the kind of catalyst, for example, 0.001-1 weight part (for example, 0.003-0.3.0) with respect to 1 weight part of compounds represented by the said Formula (2A). 5 parts by weight), preferably 0.005 to 0.3 parts by weight, more preferably about 0.01 to 0.1 parts by weight.

The reaction may be performed in a solvent. The solvent is not particularly limited and can be selected according to the raw material to be used. For example, when using an alkylene oxide, an ether solvent (dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane, Anisole, etc.), halogen solvents (halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride), hydrocarbon solvents (aromatic hydrocarbons such as benzene, toluene, xylene, etc.). When alkylene carbonate is used, in addition to the solvents exemplified above, alcohols (C _1-4 alcohols such as methanol and ethanol, (poly) C ₂ such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol) are used. _-3 alkylene glycol, etc.) may be used. The solvents may be used alone or in combination of two or more. The amount of the solvent to be used is, for example, 1 to 30 parts by weight, preferably 1.5 to 20 parts by weight, more preferably about 2 to 10 parts by weight with respect to 1 part by weight of the compound represented by the formula (2A). It may be.

  The reaction is often performed at, for example, about 0 to 170 ° C., preferably 10 to 150 ° C., more preferably about 20 to 130 ° C., depending on the type of compound to be added (alkylene oxide, alkylene carbonate) and the like. In particular, when alkylene carbonate is used, in order to efficiently perform the decarboxylation reaction, for example, the reaction is often performed at 70 to 150 ° C, preferably about 80 to 120 ° C. The reaction time is, for example, 30 minutes to 48 hours, usually 1 to 24 hours, preferably about 2 to 10 hours.

  The reaction may be performed with stirring, may be performed in air or in an inert atmosphere (such as nitrogen or a rare gas), or may be performed under normal pressure or under pressure. Moreover, you may react, removing the gas (carbon dioxide etc.) which generate | occur | produces as needed.

  The target product (compound represented by formula (1)) may be purified from the reaction mixture after completion of the reaction using a conventional purification method (extraction, crystallization, etc.).

(Method (2))
In the method (2), examples of the compound represented by the formula (2B) include fluorenones such as 9-fluorenone. The purity of the compound represented by formula (2B) used in the reaction (fluorenones) is not particularly limited, but may be usually 95% by weight or more, preferably 99% by weight or more.

In the method (2), examples of the compound represented by the formula (2C) include branched alkylene glycol mono (monoarylphenyl) ethers {for example, branched C _3-4 alkylene glycol monobiphenylyl ether [2 Alcohols in which m is 1 in the above formula (2C), such as branched C _3-4 alkylene glycol mono (mono C _6-10 arylphenyl) ether, etc.] such as — (2-biphenylyloxy) propanol; branched alkylene glycol mono (monoaryl phenyl) ethers {e.g., di-branched C _3-4 di- branched C _3-4 alkylene glycol mono (mono C _6, such as alkylene glycol mono biphenylyl ether [dipropylene glycol monomethyl biphenylyl, etc.] _-10 aryl) ether } And alcohols m is 2 or more in the formula (2C), such as.

  The purity of the compound (alcohol) represented by the formula (2C) is not particularly limited, but is usually 95% by weight or more, preferably 97% by weight or more, more preferably 99% by weight or more. Good.

  The reaction may be performed in the presence of a catalyst. Usually, an acid catalyst can be used as the 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, about 30 to 90% by weight sulfuric acid), 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. For example, sulfur trioxide may be used as the sulfuric acid precursor. A solid acid (such as a cation exchange resin) may be used. The acid catalysts may be used alone or in combination of two or more.

In addition to the acid catalyst, thiols as a co-catalyst may be used in combination. Examples of thiols include conventional thiols that function as promoters, such as mercaptocarboxylic acids (mercaptoacetic acid, β-mercaptopropionic acid, α-mercaptopropionic acid, thioglycolic acid, mercaptosuccinic acid, mercaptobenzoic acid, etc.) Thiocarboxylic acid (thioacetic acid, thiooxalic acid, etc.), alkyl mercaptan (methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, dodecyl mercaptan, etc., C _1-16 alkyl mercaptan (especially C _1-4 alkyl mercaptan) Etc.), aralkyl mercaptan (such as benzyl mercaptan) or a salt thereof. Examples of the salt include alkali metal salts (sodium salt and the like). 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 reaction (liquid phase reaction) is carried out using a reaction solvent such as an aromatic solvent (aromatic hydrocarbons such as benzene, toluene and xylene, anisole, etc.), an ether solvent (dialkyl ethers such as diethyl ether, tetrahydrofuran, etc. , Cyclic ethers such as dioxane, etc.), halogen solvents (halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, etc.) and the like.

  Although reaction temperature is not specifically limited, For example, 20-200 degreeC, Preferably it is 40-180 degreeC, More preferably, about 50-150 degreeC may be sufficient. 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 24 hours, Preferably it may be about 1 to 10 hours. Good.

  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 may be performed while dehydrating.

  The target product (compound represented by formula (1)) may be purified from the reaction mixture after completion of the reaction using a conventional purification method (extraction, crystallization, etc.).

  As described above, the compound represented by the formula (1) is obtained. The compound represented by the formula (1) obtained by the reaction may be a single compound or a mixture containing a plurality of compounds represented by the formula (1). For example, the compound represented by the formula (1) is a mixture of a compound in which m is 1 in the formula (1) and a compound in which m is 2 or more (for example, 2) in the formula (1). There may be. In such a mixture, the proportion of the single compound is, for example, 70% by weight or more (for example, 75 to 99.9% by weight), preferably 80% by weight or more (for example, 85 to 99.7% by weight), Preferably, it may be about 90% by weight or more (for example, 95 to 99.5% by weight).

[Use of compound represented by formula (1)]
Since the compound of the present invention has a specific fluorene skeleton, it is excellent in various properties (optical properties, heat resistance, water resistance, moisture resistance, chemical resistance, electrical properties, mechanical properties, dimensional stability, etc.). And are useful in improving or improving these properties in various applications. Moreover, it has a high refractive index due to the skeleton. In particular, when the compound of the present invention is used as a resin raw material, the handling property of the resin can be improved or improved.

  Therefore, such a compound of the present invention is a functional material [for example, an additive (resist additive, etc.), a raw material or intermediate of a reagent (pharmaceutical, agricultural chemical, etc.)] (or a raw material or intermediate thereof). It can be suitably used as a resin raw material (monomer or the like), and can be used as a compound for efficiently imparting the above-described excellent characteristics.

(Additive use and resin composition)
Examples of the additive include resin additives (or resin additives), curing agents (such as resin curing agents), and the like. When used as an additive, a resin composition (thermoplastic resin composition, heat or photocurable resin composition) containing a resin and the compound 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, these alkylene oxide adducts, etc.) 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 fluorene 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 the said compound, the said compound may act as a hardening | curing agent (or hardening accelerator). Among the resins, a typical resin that can use the compound as a curing agent is an epoxy resin. 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, bisphenol A and epichlorohydrin. 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 ratio of the compound is, for example, 1 to 700 parts by weight, preferably 50 to 600 parts by weight, and more preferably 100 parts by weight with respect to 100 parts by weight of the resin (in particular, a thermoplastic resin such as a thermoplastic resin having an aromatic ring). About 500 parts by weight (for example, 200 to 300 parts by weight) may be used. Moreover, when using the said compound as a hardening | curing agent, the functional group (for example, phenolic hydroxyl group) of the said compound with respect to 1 functional group (or curable functional group, for example, epoxy group) of resin (epoxy resin etc.) Such as hydroxyl group, amino group, etc.) are 0.1 to 4.0 equivalents, preferably 0.3 to 2.0 equivalents, more preferably 0.5 to 1.5 equivalents. You may adjust the ratio of a component.

  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 compound of the present invention can be used as a resin raw material. For example, since the compound of the present invention has two hydroxyl groups, it can be used as a monomer component of a thermoplastic resin or a thermosetting resin (or a precursor thereof). That is, such a resin is a resin containing the compound as a polymerization component.

  Specifically, the resin is a resin in which a polyol component is a monomer component (or a polymerization component), and a part or all of the polyol component is a resin composed of the compound (or a derivative thereof). Also good.

  As a resin having a polyol component (for example, diol component) as a monomer component (or polymerization component), a thermoplastic resin [polyester resin, polycarbonate resin, polyurethane resin, polyether resin (polyether ether ketone, etc.) ), Etc.], thermosetting resins [for example, unsaturated polyester resins, thermosetting polyurethane resins, epoxy resins (such as polyglycidyl ethers of the above compounds), vinyl ester resins, phenol resins, polyol poly (meth) acrylates. (Di (meth) acrylate of the compound, or a reaction product of the compound with (meth) acrylic acid or a derivative thereof ((meth) acrylic acid halide, etc.), urethane (meth) acrylate], etc.] .

  In a resin having such a polyol component as a monomer component (or polymerization component), the polyol component can be composed of a compound represented by the formula (1). In such a resin, the compounds represented by the formula (1) may be used alone or in combination of two or more.

  Hereinafter, epoxy resins (epoxy compounds), di (meth) acrylates, and polyesters will be described in detail as typical resins.

(Epoxy resin)
As an epoxy resin (epoxy compound), the compound represented by following formula (3) is mentioned, for example.

(In the formula, R ⁴ represents a hydrogen atom or a methyl group, and R ¹ , R ² , R ³ , k, and m are the same as described above.)
Representative epoxy resins (or compounds represented by the above formula (3)) include 9,9-bis (glycidyloxy-branched alkoxy-monoarylphenyl) fluorenes (m is 1 in the above formula (3)). And a 9,9-bis (glycidyloxy-polybranched alkoxy-monoarylphenyl) fluorene (a compound in which m is 2 or more in the formula (3)).

The 9,9-bis (glycidyloxy-branched alkoxy-monoarylphenyl) fluorenes include, for example, 9,9-bis (glycidyloxy-branched C _3-4 alkoxy-monoarylphenyl) fluorenes {eg, 9, 9,9-bis such as 9-bis [4- (2-glycidyloxypropoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-glycidyloxypropoxy) -3-tolylphenyl] fluorene (Glycidyloxy-branched C _3-4 alkoxy-mono C _6-10 arylphenyl) fluorene, preferably 9,9-bis (2-glycidyloxypropoxy-mono C _6-8 arylphenyl) fluorene} and the like.

9,9-bis (glycidyloxy-polybranched alkoxy-monoarylphenyl) fluorenes correspond to the 9,9-bis (glycidyloxy-branched alkoxy-monoarylphenyl) fluorenes, and m is 2 or more. Certain compounds, such as 9,9-bis (glycidyloxy-dibranched C _3-4 alkoxy-monoarylphenyl) fluorenes {eg, 9,9-bis {4- [2- (2-glycidyloxypropoxy) propoxy ] 9,9-bis (glycidyloxy-dibranched C _3-4 alkoxy-mono C _6-10 arylphenyl) fluorene, such as 9,3-phenylphenyl} fluorene, preferably 9,9-bis [2- (2- Glycidyloxypropoxy) propoxy-mono C _6-8 arylphenyl] fluorene} and the like .

  The epoxy resin includes, for example, the compound represented by the formula (1), epihalohydrin [or halomethyloxirane, such as epichlorohydrin (chloromethyloxirane), epibromohydrin (bromomethyloxirane), and the like. ] Or 1-halomethyl-2-methyloxirane (such as 1-chloromethyl-2-methyloxirane) can be produced.

  The epoxy resin (the compound represented by the formula (3) or the compound obtained by the method) has a fluorene skeleton (specifically, 9,9-bis (monoarylaryl) fluorene skeleton), It has characteristics specific to a fluorene skeleton such as heat resistance and high refractive index. Moreover, despite having such a fluorene skeleton, the melt viscosity is small. Therefore, the said epoxy compound is excellent in handling property. For example, the melt viscosity (rotation speed 900 rpm) of the compound of the present invention at 150 ° C. is 1 to 600 mPa · s (eg 3 to 550 mPa · s), preferably 5 to 500 mPa · s (eg 10 to 450 mPa · s). More preferably, it may be about 15 to 420 mPa · s (for example, 20 to 400 mPa · s).

In particular, among the compounds of the present invention, in the formula (1), a compound having R ⁴ as an alkyl group has a melt viscosity (rotation speed: 900 rpm) at 150 ° C. of, for example, 1 to 200 mPa · s (for example, 3 to 150 mPa). S), preferably 5 to 100 mPa · s (for example, 10 to 80 mPa · s), more preferably about 15 to 70 mPa · s (for example, 20 to 50 mPa · s).

  The melt viscosity is a value measured by a cone-and-plate (cone and plate) type melt viscometer (such as cone 3).

  The epoxy equivalent of the epoxy resin may be, for example, 300 to 1500 g / eq, preferably 330 to 1200 g / eq, and more preferably about 350 to 1000 g / eq.

  In addition, the said epoxy resin may comprise the epoxy resin composition containing a diluent, a hardening | curing agent, a hardening accelerator, etc.

(Di (meth) acrylate)
Examples of di (meth) acrylate (poly (meth) acrylate) include a compound represented by the following formula (4).

(In the formula, R ¹ , R ² , R ³ , R ⁴ , k, and m are the same as above.)
Representative di (meth) acrylates (or compounds represented by the above formula (4)) include 9,9-bis ((meth) acryloyloxy-branched alkoxy-monoarylphenyl) fluorenes (the above formula (4)). )), 9,9-bis ((meth) acryloyloxy-polybranched alkoxy-monoarylphenyl) fluorenes (compounds wherein m is 2 or more in the formula (4)). .

9,9-bis ((meth) acryloyloxy-branched alkoxy-monoarylphenyl) fluorenes include, for example, 9,9-bis ((meth) acryloyloxy-branched C _3-4 alkoxy-monoarylphenyl) fluorene {E.g., 9,9-bis [4- (2- (meth) acryloyloxypropoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxypropoxy) -3 9,9-bis ((meth) acryloyloxy-branched C _3-4 alkoxy-mono C _6-10 arylphenyl) fluorene such as -tolylphenyl] fluorene, preferably 9,9-bis (2- (meth) acryloyl) Oxypropoxy-mono C _6-8 arylphenyl) fluorene} and the like.

9,9-bis ((meth) acryloyloxy-poly branched alkoxy-monoarylphenyl) fluorenes correspond to the 9,9-bis ((meth) acryloyloxy-branched alkoxy-monoarylphenyl) fluorenes. , M is 2 or more, for example, 9,9-bis ((meth) acryloyloxy-dibranched C _3-4 alkoxy-monoarylphenyl) fluorenes {eg, 9,9-bis {4- [2 9,9-bis ((meth) acryloyloxy-dibranched C _3-4 alkoxy-mono C _{6-10 arylphenyl} ) such as-(2- (meth) acryloyloxypropoxy) propoxy] -3-phenylphenyl} fluorene Fluorene, preferably 9,9-bis [2- (2- (meth) acryloyloxypropoxy) propoxy - and the like mono _{C 6-8} aryl phenyl] fluorene}.

The di (meth) acrylate includes, for example, the compound represented by the formula (1) and (meth) acrylic acid or a derivative thereof [for example, (meth) acrylic acid lower alkyl ester (for example, (meth) acrylic). Methyl methacrylate, ethyl (meth) acrylate, C _1-4 alkyl (meth) acrylate such as butyl (meth) acrylate), (meth) acrylic acid halide (for example, (meth) acrylic acid chloride, etc.), (meta ) Acrylic anhydride etc.].

  The di (meth) acrylate may constitute a resin composition containing a polymerization initiator, a diluent (such as a solvent or a polymerizable diluent), and the like.

(polyester)
As polyester, a diol component (diol component (a)) composed of at least the compound (compound represented by the formula (1)) and a dicarboxylic acid component (dicarboxylic acid component (b)) are used as polymerization components. Polyester (polyester resin) to be used.

The diol component (a) may contain another diol component (a diol component other than the compound (a1)) as long as it is composed of the compound (a1) represented by the formula (1). 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]. Other diol components may be used alone or in combination of two or more.

  In the diol component (a), the ratio of the compound (a1) is, for example, 30 mol% or more (for example, about 35 to 100 mol%), preferably 40 mol% or more (based on the entire diol component (a)). For example, it may be about 45 to 99 mol%), more preferably 50 mol% or more (for example, about 55 to 95 mol%).

  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 fluorene etc.) 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.

  If necessary, in addition to the dicarboxylic acid component, a small amount of a polycarboxylic acid having 3 or more carboxyl groups (for example, trimellitic acid, pyromellitic acid, etc.) may be used.

  As described above, the polyester resin is a polyester resin having the diol component (a) and the dicarboxylic acid component (b) as polymerization components, and usually has a unit represented by the following formula (4A). Polyester.

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

  The glass transition temperature Tg of the polyester may be, for example, about 50 to 350 ° C., preferably 60 to 300 ° C., more preferably 70 to 250 ° C., particularly about 80 to 200 ° 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. .

  The compound of the present invention can impart excellent handling properties while having excellent characteristics such as high heat resistance and high refractive index. Specifically, the compound of the present invention is used as a resin raw material [for example, a thermoplastic resin (polyester, etc.) raw material, a heat or photocurable resin (epoxy resin, polyol poly (meth) acrylate, etc.) raw material], an additive, etc. Available.

  For example, a cured product of a thermosetting resin (such as an epoxy resin) using the compound of the present invention has a property of low bending elasticity at high temperatures, and is highly useful. For example, even when the compound of the present invention (or a cured product thereof) is used in an application where a gas such as water vapor is generated at a high temperature (such as a semiconductor encapsulant application), the gas can be easily discharged. .

  Specifically, the cured product obtained by using the compound of the present invention is useful as an insulating material between electronic component layers, a solder resist for printed circuit boards, a resist material such as a coverlay, and a semiconductor sealing material. In addition, it is useful as all electrical and electronic materials such as color filters, printing inks, sealants (semiconductor sealants, etc.), paints, coating agents, and adhesives. It can also be used in fields such as molding materials, adhesives, composite materials and paints.

  Thermosetting resins such as novolak resins include, for example, curing agents [for example, curing agents for epoxy resins (such as curing agents for epoxy resins for semiconductor encapsulation)], adhesives, paints (such as undercoat paints), and rubbers. Compounding agents, binders (binders for grindstones, abrasive papers, friction materials, etc.), laminated materials (or laminated products such as copper-clad laminates, laminated tubes, laminated bars, etc.), thermal materials (for thermal papers) Materials), carbon materials, insulating materials, foams, pressure-sensitive materials (pressure-sensitive paper materials, etc.), shell molds, various resin materials (raw materials for novolac epoxy resins, resin binders, etc.), molded bodies (electrical / electronic parts) Moldings, thin films, etc.), substrates or circuit forming materials (resist for semiconductor manufacturing, printed wiring boards, transparent substrates, etc.), image forming materials (printing plate materials, relief images, etc.), resists (resist for semiconductor manufacturing, etc.) Layer film (hard mask) can be applied to various applications such as.

Furthermore, photocurable resins such as epoxy (meth) acrylate resins include ink materials, light emitting materials (for example, light emitting materials for organic EL), organic semiconductors, graphitized precursors, gas separation membranes (for example, CO ₂ gas). Separation membranes, etc.), coating agents (for example, optical overcoat agents such as coating agents for LED (light emitting diode) elements, hard coating agents, etc.), lenses [for pickup lenses (eg, DVD (digital versatile discs)) Pickup lens, etc.), microlens (eg, microlens for liquid crystal projector), spectacle lens, etc.], polarizing film (eg, polarizing film for liquid crystal display), antireflection film (or antireflection film, eg, for display device) Anti-reflection film, etc.), touch panel film, flexible substrate film Film, display films [eg, PDP (plasma display), LCD (liquid crystal display), VFD (vacuum fluorescent display), SED (surface conduction electron-emitting device display), FED (field emission display), NED (nano-emissive) -Films for displays (particularly thin displays) such as displays), cathode ray tubes, electronic paper (filters, protective films, etc.)], membranes for fuel cells, optical fibers, optical waveguides, holograms, 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, various measurements were performed as follows.

(HPLC purity)
Using a reverse phase column (ODS-80TM) manufactured by Tosoh Corporation, water / acetonitrile (weight ratio) = 30/70 for 30 minutes at 254 nm, then water / acetonitrile (weight ratio) = 0/100 The purity was measured at 30 minutes.

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

(Melt viscosity)
Using an ICI viscometer (cone & plate type, viscometer CAP2000 + H manufactured by Brookfield), the temperature was measured at 150 ° C. with cone 3 at 900 rpm.

(Epoxy equivalent)
Using an automatic titrator (GT-100, manufactured by Mitsubishi Chemical Corporation), titration was performed with a perchloric acid solution (acetic acid).

(Refractive index)
Using a multiwavelength Abbe refractometer (manufactured by Atago, DR-M2 <use of circulating water bath 60-C3>), the refractive index at 589 nm was measured while maintaining 25 degrees.

(HAZE)
Using a color difference turbidity measuring device (Nippon Denshoku Industries Co., Ltd., COH-300A), measurement was performed by putting acrylate into a test tube (manufactured by Maruemu, A-24 (24 × 200), straight port) or 10 × 10 mm quartz cell. .

(Hue)
Using a color difference turbidity measuring device (Nippon Denshoku Industries Co., Ltd., COH-300A), measurement was performed by putting acrylate into a test tube (manufactured by Maruemu, A-24 (24 × 200), straight port) or 10 × 10 mm quartz cell. .

(L *, a *, b *)
Using a color difference turbidity measuring device (Nippon Denshoku Industries Co., Ltd., COH-300A), measurement was performed by putting acrylate into a test tube (manufactured by Maruemu, A-24 (24 × 200), straight port) or 10 × 10 mm quartz cell. .

(Tg)
Using a differential scanning calorimeter (DSC 6220, manufactured by Seiko Instruments Inc.), a sample was put in an aluminum pan, and Tg was measured in the range of 30 ° C to 200 ° C.

(Molecular weight)
Using gel permeation chromatography (manufactured by Tosoh Corporation, HLC-8120GPC), the sample was dissolved in chloroform and the molecular weight was measured in the range of 10 to 20 minutes.

Example 1
In a 10 L separable flask, 503 g (1.0 mol) of 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene (BOPPF, manufactured by Osaka Gas Chemical Co., Ltd.), 1029 g (10 mol) of propylene carbonate, and a solvent. After adding 10 g of 1-methylimidazole (manufactured by Wako Pure Chemical Industries, Ltd.) as a catalyst, the mixture was reacted for 5 hours by heating to 100 ° C. After completion of the reaction, 5000 ml of isopropyl alcohol And was cooled to 10 ° C. to obtain 464 g of a white powder, which was analyzed and found to have a purity of 99.2% by HPLC and 2 mol of oxyoxy per 1 mol of BOPPF used as a raw material. The target compound to which a propylene group (propoxy group) is added (the following formula The compound represented, that BOPPF-PO) were obtained.

¹ H-NMR (CDCl ₃ , δ) ppm: 1.1 ppm (d, 6H), 3.6-4.2 ppm (m, 8H), 6.9 ppm (s, 2H), 7.1-7.6 ppm (M, 20H), 7.8 (d, 2H).

(Example 2)
In a 300 ml separable flask equipped with a Dean Stark and a reflux tube, 74.3 g (0.12 mol) of the compound obtained in Example 1 and 87.7 g of chloromethyloxirane (special grade, manufactured by Kishida Chemical Co., Ltd.) 0.9 mol) and 2.0 g of tetramethylammonium chloride (special grade, manufactured by Kanto Chemical Co., Inc.) were added and dissolved by heating at 60 ° C. for 1 hour. Thereafter, 5 g of flaky sodium hydroxide (special grade, manufactured by Futaba Chemical Co., Ltd.) was added in small portions within 100 minutes so as to keep the temperature at 60 ° C. or lower (45 to 55 ° C.).

  During the reaction, produced water was discharged out of the system by azeotropy together with chloromethyloxirane, and chloromethyloxirane was returned to the system. As a result of stirring for 5 hours while maintaining the temperature at 60 ° C. or lower (45 to 55 ° C.) for 5 hours after adding sodium hydroxide, disappearance of BCF-PO as a raw material was confirmed by HPLC. Thereafter, 200 ml of water was added to terminate the reaction. Further, the aqueous layer was discarded together with sodium chloride produced during the reaction, the organic layer was transferred to a 1 L eggplant-shaped flask, and chloromethyloxirane was concentrated and removed with an evaporator at 130 ° C. under heating conditions to obtain a pale yellow viscous product. .

  Subsequently, methyl isobutyl ketone (manufactured by Kanto Chemical Co., Inc.) was added and dissolved by heating to 70 ° C., then transferred to a 1 L separable flask, heated to 85 ° C., and 12 g of 30% aqueous sodium hydroxide solution was added. The mixture was stirred for 1 hour while maintaining at 85 ° C. or lower (80 to 85 ° C.). Thereafter, 200 ml of water was added to terminate the reaction, and washing was performed to remove the generated sodium chloride. Furthermore, 200 g of ion-exchanged water was added and the aqueous layer was discarded. This operation was repeated 5 times until the pH became neutral (pH 7). The obtained product was transferred to an eggplant-shaped flask, and methyl isobutyl ketone was removed at 80 ° C. or lower (60 to 80 ° C.) with an evaporator. Then, it dried for 5 hours at 90 degreeC in dryer, and 39.8g of pale yellow viscous substances were obtained. The yield of this pale yellow viscous product was 45.3%.

  The HPLC purity of the resulting viscous product was 17.6% for the compound in which one chloromethyloxirane was added to BOPPF-PO, and 76.3% in the target product in which two were added (the following formula). And the melt viscosity in 150 degreeC of the obtained viscous material was 396 mPa * s, and the epoxy equivalent was 443 g / eq.

¹ H-NMR (CDCl ₃ , δ): 1.2 ppm (d, 6H), 2.1 ppm (s, 6H), 2.2-2.6 ppm (m, 5H), 3.6-4.2 ppm ( m, 14H), 6.9 ppm (s, 2H), 7.2-7.6 ppm (m, 20H), 7.8 (d, 2H).

(Comparative Example 1)
59. 60.2 g (0.12 mol) of 9-bis (4-hydroxy-3-phenylphenyl) fluorene (manufactured by Osaka Gas Chemical Co., Ltd., BOPPF) and chloromethyloxirane (special grade, manufactured by Kishida Chemical Co., Ltd.) Dissolved in 8 g (0.96 mol), 2.0 g of benzyltriethylammonium chloride (special grade, manufactured by Kanto Chemical Co., Inc.) was further added and stirred at 60 ° C. for 1 hour. Next, under reduced pressure (650 mmHg), 30 g of a 40% aqueous sodium hydroxide solution was added dropwise at 45 ° C. over 1.5 hours. Meanwhile, the water produced was removed from the system by azeotropy with chloromethyloxirane, and the distilled chloromethyloxirane was returned to the system. After completion of the dropwise addition, the reaction was continued for another 3 hours. Then, the salt produced | generated by filtration was removed, and also after washing with water, chloromethyl oxirane was distilled off until solid content became 50%, and 300g of methanol was added. The precipitated crystals were separated by filtration and dried to obtain a white powder.

  The HPLC purity of the obtained white powder was 0.5% for the compound in which one chloromethyloxirane was added to BOPPF, 94.9% for the target product (in the following formula), and dimer (in the following formula in the following formula). The dimer of the compound represented) was 2.8%.

  The melt viscosity at 170 ° C. of the obtained white powder was as high as 1290 mPa · s, and it was found that the handleability was inferior. In addition, since it did not fuse at 150 ° C., the viscosity could not be measured. The epoxy equivalent was 312 g / eq.

(Example 3)
85.4 g (0.138 mol) of the compound obtained in Example 1, 25.9 g (0.359 mol) of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), p-toluenesulfonic acid (manufactured by Kishida Chemical Co., Ltd.) 3.28 g (0.017 mol), toluene 135 g (1.463 mol), and methoquinone (manufactured by Kishida Chemical Co., Ltd.) 0.3 g (0.002 mol) were charged, and the theoretical dehydration amount was refluxed at 100 ° C. to 115 ° C. The dehydration esterification reaction was performed until obtained. Thereafter, the reaction solution was neutralized with alkali and washed with 20% saline. After washing, toluene was removed to obtain a viscous product. Furthermore, as a result of ¹ H-NMR analysis of the resulting viscous product, it was confirmed that it was the target diacrylate (the following formula).

¹ H-NMR (400 MHz, CD ₂ Cl ₂ , δ):
1.3 ppm (d, 6H), 3.6-4.3 ppm (m, 4H), 5.8 ppm (d, 2H), 6.1 ppm (t, 2H), 6.3 ppm (d, 2H), 6 .9 ppm (d, 2H), 7.0-7.6 ppm (m, 20H), 7.8 ppm (s, 2H).

  The HPLC purity of the resulting viscous product was 12.6% of the compound (monoacrylate form) obtained by adding one acrylic acid to BOPPF-PO, 86.9% of the desired product (formula below), The multimer of impurities in which one or two acrylic acids were added to a plurality of molecules was 0.5%. The resulting viscous material has a refractive index of 1.633, a heating residue of 82.5%, a HAZE of 61.9, a hue (APHA) of 183, and an L * of 95. .9, a * was 4.4, and b * was 8.4.

Example 4
43 g of 1,4-cyclohexanedicarboxylic acid, 124 g of the compound obtained in Example 1, 34 g of ethylene glycol, 0.03 g of calcium acetate as a catalyst, and 0.01 g of manganese acetate were put into a reaction vessel and stirred at 200 ° C. The mixture was gradually heated to 250 ° C. to carry out the esterification reaction. After water generated from the reaction is extracted out of the system, 0.05 g of germanium oxide as a polymerization catalyst and 0.05 g of trimethyl phosphate are added, the temperature is increased and the pressure is reduced, and the generated ethylene glycol is extracted. However, the heating bath temperature was 290 ° C. and the degree of vacuum was 300 Pa. The reaction was performed in this state for 8 hours, and the reaction product was extruded into water to obtain a polyester having a refractive index of 1.615, a glass transition temperature (Tg) of 120 ° C., and a weight average molecular weight of 45,000.

Claims (5)

A compound represented by the following formula (1 A ).

(In the formula, R ¹ represents a cyano group, a halogen atom or an alkyl group , R ³ represents a C _6-10 aryl group , k is an integer of 0 to 4, and m is an integer of 1 or more.) The compound according to claim 1 , wherein m is 1 to 4 in the formula (1 A ). The compound according to claim 1 or 2 , wherein in the formula (1 A ) , m is 1 to 2, and R ³ is a phenyl group. The compound according to any one of claims 1 to 3 , which is 9,9-bis [4- (2-hydroxypropoxy) -3-phenylphenyl] fluorene. Polyester which uses the diol component comprised with the compound in any one of Claims 1-4 , and the dicarboxylic acid component as a polymerization component.