JP4369741B2 - Fluorene resin composition and molded article thereof - Google Patents

Description

  The present invention provides a resin composition useful for further improving the properties (particularly optical properties such as refractive index) of a resin containing a fluorene skeleton (9,9-bisphenylfluorene skeleton), and the resin composition. It relates to the formed body.

  It is known that a compound having a fluorene skeleton (9,9-bisphenylfluorene skeleton) has an excellent function in optical characteristics, heat resistance and the like. For example, since a resin material containing a fluorene skeleton has excellent characteristics such as a high refractive index and a low birefringence, it is used as an optical resin material for high refractive index lenses. As a method for expressing the excellent function of such a fluorene skeleton in a resin and making it moldable, a fluorene compound having a reactive group (hydroxyl group, amino group, etc.), such as bisphenol fluorene (BPF), biscresol fluorene, etc. In general, a method in which (BCF), bisaminophenylfluorene (BAFL), bisphenoxyethanol fluorene (BPEF), or the like is used as a constituent component of a resin and a fluorene skeleton is introduced into a part of the skeleton structure of the resin.

  For example, JP-A-2002-284864 (Patent Document 1) discloses a molding material composed of a polyester-based resin having a 9,9-bisphenylfluorene skeleton. JP 2002-284834 A (Patent Document 2) discloses a polyurethane resin having a 9,9-bisphenylfluorene skeleton and crosslinked with a crosslinking agent. In these documents, 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (bisphenoxyethanol) are used as part of the diol component constituting the resin. Fluorene skeleton is introduced into the resin by using fluorene).

However, even with a resin material having such a fluorene skeleton, the improvement in optical characteristics (particularly the refractive index) is still insufficient. In particular, as a molded body (for example, an optical lens device) is made thinner and smaller, a resin material having even more excellent optical characteristics (such as a refractive index) is required.
JP-A-2002-284864 (Claim 1, Example) JP 2002-284834 A (Claim 1, Example)

  Therefore, an object of the present invention is to provide a resin composition and a molded product thereof that can further improve the excellent properties (particularly optical properties such as refractive index) of the fluorene skeleton (9,9-bisphenylfluorene skeleton). There is to do.

  Another object of the present invention is to provide a method capable of simply and reliably improving the refractive index of a resin (or resin composition) containing a fluorene skeleton or a molded product thereof.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a compound having a fluorene skeleton (9,9-bisphenylfluorene skeleton) (particularly a resin containing this compound as a constituent component of the resin) and sulfur-containing compounds It has been found that by combining a compound with a compound to constitute a resin composition, characteristics such as optical characteristics (such as refractive index) can be further improved easily and reliably, and the present invention has been completed.

  That is, the resin composition of the present invention is composed of a resin component composed of a compound having a fluorene skeleton represented by the following formula (1) and a sulfur-containing compound.

(In the formula, R ^{1 to} R ⁴ are the same or different and represent a non-reactive group or reactive group. However, R ¹ and R ² are at least reactive groups. K1 and k2 are the same or different. An integer of 1 to 5 and m1 and m2 are the same or different and represent an integer of 0 or 1 to 4).
In the formula (1), the reactive group may be a hydroxyl group, an amino group, or a group obtained through these active hydrogens. In the compound having a specific fluorene skeleton, for example, in the formula (1), the groups R ¹ and R ² are the same or different, and an alkyl group, an aryl group, an aralkyl group, a hydroxyl group, an amino group, or a group — [X— (R ⁵ O) nY] (wherein R ⁵ is an alkylene group, the group X is an oxygen atom or an imino group, and the group Y is a hydrogen atom, a glycidyl group or (meth)). An acryloyl group, and n represents an integer of 0 or 1. However, when n is 0, Y is not a hydrogen atom), and the groups R ¹ and R ² are at least a hydroxyl group, an amino group, or the above-mentioned group - include ^{[X- (R 5 O) n} -Y], k1 and k2 is 1-3, and the like compounds m1 and m2 is 0.

  The resin component was composed of a resin obtained by polymerizing the compound represented by the formula (1) as a monomer component (that is, a resin in which a 9,9-bisphenylfluorene skeleton was introduced into the resin skeleton). A resin component etc. can be illustrated. Such a resin component may be composed of a polyester resin, a polyurethane resin, a polycarbonate resin, an acrylic resin, a polyimide resin, or the like.

  The sulfur-containing compound has the formula [A- (J) q] (wherein A represents a group selected from a hydrocarbon group and a heterocyclic group, J represents a sulfur-containing group, and q represents 1 or more. An organic compound having at least a unit represented by the following formula: Such sulfur-containing organic compounds include, for example, mercaptoarenes, alkylthioarenes, arylthiocarboxylic acids, arylthio (meth) acrylates, diaryl sulfides, diaryl disulfides, alkyl-aryl sulfones, arenesulfonyl halides, sulfur It may be a containing cyclic organic compound, a sulfur containing heterocyclic compound, a sulfur containing aliphatic compound, or the like. Examples of the diaryl sulfides include diphenyl sulfides represented by the following formula (2).

(Wherein R ⁶ and R ⁷ represent a substituent, Z ¹ and Z ² are the same or different and represent a hydrogen atom, a vinyl group, a (meth) acryl group or a glycidyl group, and r1, r2, p1 and p2) Are the same or different and represent 0 or an integer of 1 to 5, provided that r1 + p1 and r2 + p2 are 0 or an integer of 1 to 5.)
Preferred sulfur-containing compounds (sulfur-containing organic compounds) include compounds in which Z ¹ and Z ² are (meth) acryloyl groups or glycidyl groups and p1 and p2 are 1 in the formula (2). . The ratio of the sulfur-containing compound may be about 3 to 50 parts by weight with respect to 100 parts by weight of the resin component.

  In the present invention, the characteristics of the fluorene skeleton can be further improved by combining a compound having a fluorene skeleton and a sulfur-containing compound. Therefore, the present invention adds the sulfur-containing compound to the resin component composed of the compound having a fluorene skeleton represented by the above formula (1), whereby the resin composition (or the resin composition composed of the resin component). The method of improving the refractive index of a thing or its molded object is also included. Furthermore, this invention also includes the molded object formed with the said resin composition.

  In the present specification, the “non-reactive group” means a group that is non-reactive with respect to reactions such as ester bond forming reaction, urethane bond forming reaction, amide bond forming reaction, and imide bond forming reaction.

  In the resin composition (and its molded product) of the present invention, a compound having a fluorene skeleton (9,9-bisphenylfluorene skeleton) (particularly a resin containing this compound as a monomer component) and a sulfur-containing compound are included. Since they are combined, the excellent properties (particularly optical properties such as refractive index) of the fluorene skeleton (9,9-bisphenylfluorene skeleton) can be further improved. Moreover, in this invention, the refractive index of resin (or resin composition) containing a fluorene skeleton or its molded object can be improved simply and reliably by the method of adding a sulfur containing compound.

  The resin composition of the present invention is composed of a resin component composed of a compound having a fluorene skeleton (9,9-bisphenylfluorene skeleton) and a sulfur-containing compound.

[Resin component]
(Compound having a fluorene skeleton)
A compound having a fluorene skeleton (hereinafter sometimes simply referred to as a fluorene compound) is represented by the following formula (1).

(Wherein R ^{1 to} R ⁴ are the same or different and represent a non-reactive group or a reactive group. K1 and k2 are the same or different and represent an integer of 1 to 5, and m1 and m2 are the same or different. 0 or an integer of 1 to 4 is shown.)
The non-reactive group is not particularly limited, for example, an alkyl group (a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, s- butyl group, C _1-20 alkyl group such as t- butyl group, Preferably a C _1-8 alkyl group, more preferably a C _1-6 alkyl group, etc., a cycloalkyl group (C _5-10 cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, etc., preferably a C _5-8 cycloalkyl group) group, more preferably such C _5-6 cycloalkyl group), an aryl group [phenyl group, alkylphenyl group (methylphenyl group (tolyl group), C _6-10 aryl group such as a dimethylphenyl group (xylyl), etc.) , preferably C _6-8 aryl group, especially phenyl group), a hydrocarbon such as an aralkyl group (a benzyl group and C _6-10 aryl -C _1-4 alkyl group such as a phenethyl group) Containing group; (such as C _1-4 alkoxy group such as methoxy group) alkoxy group; (C _1-6 acyl group such as acetyl group) an acyl group; an alkoxycarbonyl group (C _1-4 alkoxycarbonyl such as methoxycarbonyl group N, N-disubstituted amino group [for example, an amino group substituted with a hydrocarbon group (such as N, N-diC _1-6 alkylamino group such as dimethylamino group)]; halogen atom (fluorine) Atom, chlorine atom, etc.); nitro group; cyano group and the like.

Examples of the reactive group include a group containing active hydrogen (active hydrogen-containing group), a group obtained through this active hydrogen-containing group, and the like. Examples of the active hydrogen-containing group include a hydroxyl group, an amino group, and an N-monosubstituted amino group [for example, an amino group substituted with a hydrocarbon group (an N-monoC _1-6 alkylamino group such as a methylamino group) )], A carboxyl group, and the like, and are usually a hydroxyl group, an amino group, or an N-monosubstituted amino group (particularly, a hydroxyl group or an amino group).

Examples of the group obtained through the active hydrogen-containing group include groups obtained through the active hydrogen of the active hydrogen-containing group (particularly hydroxyl group and amino group). Such a group is not particularly limited, but is a group obtained through an active hydrogen of a hydroxyl group or an amino group, for example, a group — [X— (R ⁵ O) nY] (wherein R ⁵ is an alkylene group). The group X is an oxygen atom (ether group) or an imino group, the group Y is a hydrogen atom, a glycidyl group or a (meth) acryloyl group, and n represents 0 or an integer of 1 or more, provided that and when n is 0, Y is not a hydrogen atom).

The alkylene group represented by the group R ⁵ is not particularly limited, and examples thereof include C _2-4 alkylene groups (ethylene group, trimethylene group, propylene group, butane-1,2-diyl group, etc.) In particular, C _2-3 alkylene groups (particularly ethylene groups and propylene groups) are preferred. R ⁵ may be the same or different alkylene group in the corresponding active hydrogen-containing group R ¹ (or R ² ), but is usually the same.

  The substitution number (or addition number) n of the alkyleneoxy unit is the same or different and can be selected from the range of 0 or about 1 to 15, for example, 0 or 1 to 12, preferably 0 or 1 to 8, more preferably It may be 0 or 1-6, especially 0 or about 1-4. In addition, when n is 2 or more, the polyalkoxy group (polyalkyleneoxy group) may be composed of the same alkylene group, and is composed of different types of alkylene groups (for example, ethylene group and propylene group). Usually, it is often composed of the same alkylene group.

The groups R ¹ and R ² are usually often at least reactive groups. For example, when k1 and k2 are 2, 1 or 2 groups of the two groups R ¹ are reactive groups, and 1 or 2 groups of the two groups R ² are reactive groups.

Preferred groups R ¹ (or R ² ) include an alkyl group (C _1-6 alkyl group), a cycloalkyl group (C _5-8 cycloalkyl group), an aryl group (C _6-10 aryl group), an aralkyl group ( C _6-8 aryl-C _1-2 alkyl group), alkoxy group (C _1-4 alkoxy group), hydroxyl group, amino group, N-monosubstituted amino group (N—C _1-4 alkylamino group), group ^{- [X- (R 5 O)} n-Y] are included. In particular, an alkyl group (C _1-4 alkyl group), an aryl group (C _6-8 aryl group), an aralkyl group (C _6-8 aryl-C _1-2 alkyl group), a hydroxyl group, an amino group, the group − [X— (R ⁵ O) nY] and the groups R ¹ and R ² contain at least a hydroxyl group, an amino group, or the group — [X— (R ⁵ O) nY]. Is preferred. The group R ¹ (or R ² ) may be substituted on the benzene ring alone or in combination of two or more. The groups R ¹ and R ² may be the same or different from each other, but are usually the same. Further, the groups R ¹ (or R ² ) may be different or the same in the same benzene ring.

Incidentally, the substitution position of group R ¹ (or R ²⁾ is not particularly limited, may be selected from 2 to 6-position of the phenyl group substituted at position 9 of the fluorene. Usually, one reactive group (hydroxyl group, amino group, said group-[X- (R ⁵ O) nY] etc.) is substituted at the 9-position of fluorene at the 4-position (ie phenyl group) May be substituted at the 4-position).

The preferable substitution numbers k1 and k2 are 1 to 4, more preferably 1 to 3 (particularly 1 to 2). The number of preferred reactive groups in each group R ^1, R ^2, 1 to 3, in particular 1 to 2. The substitution numbers k1 and k2 may be different but are usually the same in many cases.

The groups R ³ and R ⁴ are usually alkyl groups (C _1-4 alkyl groups, especially methyl groups). The groups R ³ and R ⁴ may be different from each other or the same. Further, the groups R ³ (or R ⁴ ) may be different or the same in the same benzene ring. In addition, the bonding position (substitution position) of the group R ³ (or R ⁴ ) with respect to the benzene ring constituting the fluorene skeleton is not particularly limited. Preferred substitution numbers m1 and m2 are 0 or 1, in particular 0. The substitution numbers m1 and m2 may be different but are usually the same.

  Specific fluorene compounds include, for example, 9,9-bis (hydroxyphenyl) fluorenes or derivatives thereof, 9,9-bis (aminophenyl) fluorenes or derivatives thereof, and the like.

(1) 9,9-bis (hydroxyphenyl) fluorenes or derivatives thereof (1a) 9,9-bis (hydroxyphenyl) fluorenes include 9,9-bis (monohydroxyphenyl) fluorenes, 9,9 -Bis (dihydroxyphenyl) fluorenes, 9,9-bis (trihydroxyphenyl) fluorenes and the like are included.

Examples of 9,9-bis (monohydroxyphenyl) fluorenes include 9,9-bis (hydroxyphenyl) fluorene [9,9-bis (4-hydroxyphenyl) fluorene (bisphenolfluorene, BPF) and the like], substitution 9,9-bis (hydroxyphenyl) fluorene having a group {for example, 9,9-bis (alkyl-hydroxyphenyl) fluorene [9,9-bis (4-hydroxy-3-methylphenyl) fluorene (biscresol fluorene, BCF), 9,9-bis (4-hydroxy-3-ethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-butylphenyl) fluorene, 9,9-bis (3-hydroxy-2-methyl) Phenyl) fluorene, 9,9-bis (2-hydroxy-4-methylphenyl) phenyl Oren such as 9,9-bis (C _1-4 alkyl - hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-2 , 6-Dimethylphenyl) fluorene, 9,9-bis (diC _1-4 alkyl-hydroxyphenyl) fluorene, such as 9,9-bis (4-hydroxy-3,5-di-t-butylphenyl) fluorene, etc. 9,9-bis (C _5-8 cycloalkyl-monohydroxyphenyl) such as 9,9-bis (cycloalkyl-hydroxyphenyl) fluorene [9,9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene] ) Fluorene, etc.], 9,9-bis (aryl-hydroxyphenyl) fluorene [eg, 9,9-bis (4-hydroxy-3) Such as phenyl) fluorene 9,9-bis (C _6-8 aryl - hydroxyphenyl) fluorene, etc.], 9,9-bis (aralkyl - hydroxyphenyl) fluorene [e.g., 9,9-bis (4-hydroxy - 9,9-bis (C _6-8 aryl C _1-2 alkyl-hydroxyphenyl) fluorene etc.] such as 3-benzylphenyl) fluorene] and the like.

As 9,9-bis (dihydroxyphenyl) fluorenes, fluorenes corresponding to the 9,9-bis (monohydroxyphenyl) fluorenes, for example, 9,9-bis (dihydroxyphenyl) fluorene [9,9- Bis (3,4-dihydroxyphenyl) fluorene (biscatecholfluorene (BCAF)), 9,9-bis (2,4-dihydroxyphenyl) fluorene, 9,9-bis (2,5-dihydroxyphenyl) fluorene, etc.] 9,9-bis (dihydroxyphenyl) fluorene having a substituent {for example, 9,9-bis (alkyl-dihydroxyphenyl) fluorene [9,9-bis (3,4-dihydroxy-5-methylphenyl) fluorene, 9,9-bis (3,4-dihydroxy-6-methylphenyl) fluore 9,9-bis such (C _1-4 alkyl - dihydroxyphenyl) fluorene, 9,9-bis (2,4-dihydroxy-3,6-dimethylphenyl) fluorene such as 9,9-bis (di C _{1 -4} alkyl-dihydroxyphenyl) fluorene, etc.], 9,9-bis (alkoxy-dihydroxyphenyl) fluorene [e.g., 9,9- such as 9,9-bis (3,4-dihydroxy-5-methoxyphenyl) fluorene. Bis (C _1-4 alkoxy-dihydroxyphenyl) fluorene and the like], 9,9-bis (aryl-dihydroxyphenyl) fluorene [eg, 9,9-bis (3,4-dihydroxy-5-phenylphenyl) fluorene and the like 9,9-bis (C _6-8 aryl-dihydroxyphenyl) fluorene and the like] and the like}.

  The 9,9-bis (trihydroxyphenyl) fluorenes include fluorenes corresponding to the 9,9-bis (mono or dihydroxyphenyl) fluorenes such as 9,9-bis (2,4,6-triene). 9,9-bis (trihydroxy) such as hydroxyphenyl) fluorene, 9,9-bis (2,4,5-trihydroxyphenyl) fluorene, 9,9-bis (3,4,5-trihydroxyphenyl) fluorene Phenyl) fluorene and the like.

  Note that bis (monohydroxyphenyl) fluorenes can be prepared by various synthesis methods, for example, (a) a method of reacting a fluorenone with a phenol in the presence of hydrogen chloride gas and mercaptocarboxylic acid (reference [J. Appl. Polym. Sci., 27 (9), 3289, 1982], JP-A-6-145087, JP-A-8-217713), (b) 9-fluorenone in the presence of an acid catalyst (and alkyl mercaptan) A method of reacting alkylphenols (JP 2000-26349 A), (c) a method of reacting fluorenones and phenols in the presence of hydrochloric acid and thiols (such as mercaptocarboxylic acid) (JP 2002-47227 A). (D), (d) in the presence of sulfuric acid and thiols (such as mercaptocarboxylic acid), fluorenones and phenols are reacted to form hydrocarbons It can be produced using a method of producing bisphenol fluorene by crystallization with a crystallization solvent composed of a kind and a polar solvent (Japanese Patent Laid-Open No. 2003-221352).

  In addition, 9,9-bis (di- or trihydroxyphenyl) fluorenes can be obtained by using the corresponding polyhydric alcohols (dihydroxy) instead of phenols in the above-mentioned 9,9-bis (monohydroxyphenyl) fluorenes production method. Phenols and trihydroxyphenols). Among these methods, in particular, when the method (c) using hydrochloric acid or the method (d) using a specific crystallization solvent is applied, a product with higher yield and purity may be obtained. Many.

  (1b) As derivatives of 9,9-bis (hydroxyphenyl) fluorenes, alkylene oxide adducts of 9,9-bis (hydroxyphenyl) fluorenes, 9,9-bis (hydroxyphenyl) fluorenes or alkylenes thereof Examples thereof include glycidyl ethers of oxide adducts, 9,9-bis (hydroxyphenyl) fluorenes, and (meth) acrylates of alkylene oxide adducts thereof.

(Alkylene oxide adduct)
Examples of alkylene oxide adducts of 9,9-bis (hydroxyphenyl) fluorenes include bis (mono to trihydroxyphenyl) fluorenes exemplified above as alkylene oxides (C _2-4 alkylene oxides, particularly C _2-3 alkylene oxides). ) Is added. The number of added alkylene oxide units (n in the above formula) is the same as described above (for example, 1 to 12, preferably 1 to 8, more preferably 1 to 6, particularly about 1 to 4), and is not particularly limited. Hereinafter, as an example, a compound in which n is 1 or 2 is illustrated.

Representative alkylene oxide adducts include, for example, 9,9-bis (hydroxyalkoxyphenyl) fluorene [eg, 9,9-bis [4- (2-hydroxyethoxy) -phenyl] fluorene (bisphenoxyethanol fluorene, BPEF). ), 9,9-bis [9,9-bis (2-hydroxyC _2-4 alkoxy) phenyl] fluorene such as 4- (3-hydroxypropoxy) -phenyl] fluorene], 9,9 having a substituent -Bis (hydroxyalkoxyphenyl) fluorene {for example, 9,9-bis (hydroxyC) such as 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene (biscresol ethanolfluorene, BCEF) _2-4-alkoxy -C _1-4 alkylphenyl) fluorene, 9,9-bi [(2-hydroxyethoxy) -3,5-dimethylphenyl] fluorene such as 9,9-bis (hydroxy C _2-4 alkoxy - di C _1-4 alkyl phenyl) fluorene, 9,9-bis [4- ( 9,9-bis [(2-hydroxyC _2-4 alkoxy) -C _6-8 arylphenyl] fluorene, such as 2-hydroxyethoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2 9,9- such as 9,9-bis [(2-hydroxyC _2-4 alkoxy) -C _6-8 aryl C _1-2 alkylphenyl] fluorene etc.} such as -hydroxyethoxy) -3-benzylphenyl] fluorene -Bis [mono (hydroxyalkoxy) phenyl] fluorenes, 9,9-bis [di or tri (hydroxyalkoxy) phenyl] fluorenes corresponding to these compounds {E.g., 9,9-bis [3,4-di (2-hydroxyethoxy) phenyl] fluorene such as 9,9-bis [di (2-hydroxy-C _2-4 alkoxy) phenyl] fluorene}, such as 9 , 9-bis [mono to tri (hydroxyalkoxy) phenyl] fluorenes; compounds corresponding to these compounds, wherein two alkylene oxide units are added to the hydroxyl group {for example, 9,9-bis {4- [2- 9,9-bis [2- (2- _{hydroxyC 2-4} alkoxy) C _2-4 alkoxyphenyl] fluorene, such as (2-hydroxyethoxy) ethoxy] phenyl} fluorene, 9,9-bis {3,4- di [2- (2-hydroxyethoxy) ethoxy] phenyl} fluorene such as 9,9-bis {di [2- (2-hydroxy-C _2-4 alkoxy) C _2-4 alkoxy 9,9-bis [mono to tri (hydroxypolyalkoxy) phenyl] fluorenes such as 9,9-bis [mono to tri (hydroxydialkoxy) phenyl] fluorenes, etc.}. .

In addition, although the manufacturing method of the alkylene oxide adduct of 9,9-bis (monohydroxyphenyl) fluorene is not specifically limited, For example, 9,9-bis (hydroxyphenyl) fluorene and corresponding alkylene oxide (C _2-4 alkylene oxide) or alkylene carbonate (C _2-4 alkylene carbonate), if necessary, in the presence of a catalyst (such as a base catalyst) or a phenoxy C _2-4 alcohol corresponding to fluorenone It may be produced by a method of reacting with (for example, JP-A-11-349657). Moreover, the alkylene oxide adduct of 9,9-bis (di or trihydroxyphenyl) fluorenes is replaced with 9,9-bis (hydroxyphenyl) fluorenes or phenoxy C _2-4 alcohols in the above production method. The corresponding alcohols [9,9-bis (di or trihydroxyphenyl) fluorenes, di or tri (hydroxy C _2-4 alkoxy) benzenes, etc.] can be used.

(Glycidyl ether)
Examples of the glycidyl ethers of 9,9-bis (hydroxyphenyl) fluorenes include the glycidyl ethers of the 9,9-bis (hydroxyphenyl) fluorenes exemplified above.

As typical glycidyl ethers of 9,9-bis (hydroxyphenyl) fluorenes, for example, 9,9-bis (glycidyloxyphenyl) fluorene [for example, 9,9-bis (4-glycidyloxyphenyl) fluorene ( Bisphenol fluoreneglycidyl ether, BPFG)], 9,9-bis (glycidyloxyphenyl) fluorene having a substituent {for example, 9,9-bis (alkyl-glycidyloxyphenyl) fluorene [9,9-bis (4 9,9-bis (C _1-4 ) such as -glycidyloxy-3-methylphenyl) fluorene (biscresol fluorenediglycidyl ether, BCFG), 9,9-bis (4-glycidyloxy-3-ethylphenyl) fluorene Alkyl-glycidyloxyphenyl) fluoro And the like], 9,9-bis (dialkyl-glycidyloxyphenyl) fluorene [9,9-bis (4-glycidyloxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-glycidyloxy-2) , 6-Dimethylphenyl) fluorene, 9,9-bis (4-glycidyloxy-3,5-di-t-butylphenyl) fluorene, etc. 9,9-bis (diC _1-4 alkyl-glycidyloxyphenyl) Fluorene etc.], 9,9-bis (cycloalkyl-glycidyloxyphenyl) fluorene [9,9-bis (4-glycidyloxy-3-cyclohexylphenyl) fluorene etc., 9,9-bis (C _5-8 cycloalkyl) -Glycidyloxyphenyl) fluorene, etc.], 9,9-bis (arylglycidyloxyphenyl) fluorene [9,9-bis (4-glycidyloxy-3-phenylphenyl) fluorene such as 9,9-bis (C _6-8 aryl - glycidyloxyphenyl) fluorene, etc.], etc.}, etc. of 9,9-bis (mono Diglycidyl ethers of hydroxyphenyl) fluorenes; glycidyl ethers of 9,9-bis [di or tri (hydroxy) phenyl] fluorenes corresponding to these compounds {eg, 9,9-bis [di (glycidyloxy) phenyl] ] Tetraglycidyl ethers of 9,9-bis (dihydroxyphenyl) fluorenes such as fluorene [e.g., 9,9-bis [3,4-di (glycidyloxy) phenyl] fluorene (biscatecholfluorenetetraglycidyl ether) etc.] Etc.}.

As a typical glycidyl ether of an alkylene oxide adduct, glycidyl ether of an alkylene oxide adduct of the 9,9-bis (monohydroxyphenyl) fluorenes exemplified above, for example, 9,9-bis (glycidyloxyalkoxyphenyl) Fluorene [eg, 9,9-bis (glycidyloxy C _2-4 alkoxyphenyl) fluorene such as 9,9-bis (4-glycidyloxyethoxyphenyl) fluorene (bisphenoxyethanol fluorenediglycidyl ether, BPEFG)], substituted 9,9-bis (glycidyloxyalkoxyphenyl) fluorene having a group {for example, 9,9-bis (alkyl-glycidyloxyalkoxyphenyl) fluorene [for example, 9,9-bis (4-glycidyloxyethoxy-) 9,9-bis (C _1-4 alkylglycidyloxy C _2-4 alkoxyphenyl) fluorene such as 3-methylphenyl) fluorene, 9,9-bis (4-glycidyloxyethoxy-3,5-dimethylphenyl) fluorene 9,9-bis (diC _1-4 alkylglycidyloxy C _2-4 alkoxyphenyl) fluorene and the like], 9,9-bis (cycloalkylglycidyloxyalkoxyphenyl) fluorene [9,9-bis (4- 9,9-bis (C _5-8 cycloalkylglycidyloxy C _2-4 alkoxyphenyl) fluorene] such as glycidyloxyethoxy-3-cyclohexylphenyl) fluorene], 9,9-bis (arylglycidyloxyalkoxyphenyl) fluorene [ 9,9-bis (4-glycidyloxyethoxy-3-phenyl) Eniru) 9,9-bis fluorene (C _6-8 aryl glycidyloxy C _2-4 alkoxyphenyl) fluorene, etc.], corresponding to these compounds 9,9-bis (glycidyloxy polyalkoxy phenyl) fluorenes [ For example, 9,9-bis {[2- (2-glycidyloxy C _2-4 alkoxy) C ₂₋ such as 9,9-bis {4- [2- (2-glycidyloxyethoxy) ethoxy] phenyl} fluorene. ₄ alkoxy] phenyl} fluorene, etc.] such as 9,9-bis diglycidyl ethers of alkylene oxide adducts of (mono-hydroxyphenyl) fluorenes; corresponding to these compounds 9,9-bis [di- or tri (hydroxy) Glycidyl ethers of alkylene oxide adducts of phenyl] fluorenes {eg, 9,9-bis [3 4-di (2-glycidyloxy C _2-4 alkoxy) phenyl] tetraglycidyl ether of 9,9-bis [di (hydroxyalkoxy) phenyl] fluorenes such as fluorene, 9,9-bis {3,4-di 9,2-bis [di (hydroxypolyalkoxy) phenyl] fluorene tetraglycidyl ether, etc. such as [2- (2-glycidyloxy C _2-4 alkoxy) C _2-4 alkoxy] phenyl} fluorene, etc. .

  Glycidyl ether can be obtained by reacting 9,9-bis (hydroxyphenyl) fluorenes or an alkylene oxide adduct thereof with epichlorohydrin.

((Meth) acrylate)
Examples of the (meth) acrylate of 9,9-bis (hydroxyphenyl) fluorenes include the (meth) acrylates of the 9,9-bis (hydroxyphenyl) fluorenes exemplified above.

Typical (meth) acrylates of 9,9-bis (hydroxyphenyl) fluorenes include compounds in which the glycidyl group of the above-exemplified glycidyl ether is substituted with a (meth) acryloyl group, such as 9,9-bis (( (Meth) acryloyloxyphenyl) fluorene [e.g., 9,9-bis (4- (meth) acryloyloxyphenyl) fluorene, etc.], substituted 9,9-bis ((meth) acryloyloxyphenyl) fluorene {e.g. 9,9-bis (C _1- (9) -bis (alkyl- (meth) acryloyloxyphenyl) fluorene [e.g., 9,9-bis (3-methyl-4- (meth) acryloyloxyphenyl) fluorene] 9, such as ₄ alkyl-4- (meth) acryloyloxyphenyl) fluorene, etc.] Di (meth) acrylates of 9-bis (monohydroxyphenyl) fluorenes; (meth) acrylates of 9,9-bis [di or tri (hydroxy) phenyl] fluorenes corresponding to these compounds {e.g., 9,9 Tetra (9,9-bis (dihydroxyphenyl) fluorenes such as bis (di (meth) acryloyloxyphenyl) fluorene [9,9-bis (3,4-di (meth) acryloyloxyphenyl) fluorene etc.] Meth) acrylate, etc.}.

The (meth) acrylate of an alkylene oxide adduct of 9,9-bis (hydroxyphenyl) fluorene includes, for example, 9,9-bis ((meth) acryloyloxy C _2-4 alkoxy) phenyl) fluorene [eg, 9,9-bis (4- (2- (meth) acryloyloxyethoxy) phenyl) fluorene etc.], 9,9-bis ((meth) acryloyloxy C _2-4 alkoxy) phenyl) fluorene having a substituent [ For example, 9,9-bis (alkyl- (meth) acryloyloxy C _2-4 alkoxy) phenyl such as 9,9-bis (3-methyl-4- (2- (meth) acryloyloxyethoxy) phenyl) fluorene) Fluorene], 9,9-bis ((meth) acryloyloxypoly C _2-4 alkoxypheny) corresponding to these compounds E) alkylene oxide adducts of 9,9-bis (monohydroxyphenyl) fluorenes such as fluorene [e.g., 9,9-bis (4- (2- (meth) acryloyloxydiethoxy) phenyl) fluorene, etc.]. Di (meth) acrylates; (meth) acrylates of alkylene oxide adducts of 9,9-bis [di or tri (hydroxy) phenyl] fluorenes corresponding to these compounds {eg, 9,9-bis [3,4 9,9-bis [di (2- (meth) acryloyloxy C _2-4 alkoxy) phenyl] fluorene, such as di (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 9,9-bis {3, 9,9-Bis {di [[4] such as 4-di [2- (2- (meth) acryloyloxyethoxy) ethoxy] phenyl} fluorene Tetra (meta) of alkylene oxide adducts of 9,9-bis [di (hydroxy) phenyl] fluorenes such as 2- (2- (meth) acryloyloxy C _2-4 alkoxy) C _2-4 alkoxy] phenyl} fluorene ) Acrylate etc.}.

  In addition, although the manufacturing method of these (meth) acrylates is not specifically limited, For example, the corresponding 9, 9-bis (hydroxyphenyl) fluorene or its alkylene oxide adduct, (meth) acrylic acid or its derivative ( For example, (meth) acrylic acid halide such as (meth) acrylic acid chloride, (meth) acrylic acid lower alkyl ester such as methyl (meth) acrylate, etc.) is reacted in the presence of a catalyst as necessary. Can be manufactured.

(2) 9,9-bis (aminophenyl) fluorenes or derivatives thereof As 9,9-bis (aminophenyl) fluorenes, compounds corresponding to the 9,9-bis (hydroxyphenyl) fluorenes, Examples thereof include compounds in which the hydroxyl group of 9,9-bis (hydroxyphenyl) fluorenes is an amino group or an N-substituted amino group.

Typical 9,9-bis (aminophenyl) fluorenes include 9,9-bis (monoaminophenyl) fluorenes such as 9,9-bis (monoaminophenyl) fluorene [9,9-bis ( 4-aminophenyl) fluorene (bisaniline fluorene, etc.)], 9,9-bis (monoaminophenyl) fluorene having a substituent {for example, 9,9-bis (amino-alkylphenyl) fluorene [9,9-bis 9,9-bis (amino-C _1-4 alkylphenyl) fluorene such as (4-amino-3-methylphenyl) fluorene, 9,9-bis (3-amino-2-methylphenyl) fluorene, 9,9 -Bis (4-amino-3,5-dimethylphenyl) fluorene, 9,9-bis (4-amino-2,6-dimethylphenyl) fluorene, 9 9,9-bis (amino-diC _1-4 alkylphenyl) fluorene such as 9-bis (4-amino-3,5-di-t-butylphenyl) fluorene], these 9,9-bis (Amino-alkylphenyl) fluorene alkyl group is a cycloalkyl group (C _5-8 cycloalkyl group) or an aryl group (C _6-8 aryl group, etc.)}, corresponding to these compounds, amino 9,9-bis (monoaminophenyl) fluorenes whose group is an N-monosubstituted amino group (for example, N—C _1-4 alkylamino group).

  The 9,9-bis (aminophenyl) fluorene derivatives include alkylene oxide adducts of the 9,9-bis (aminophenyl) fluorenes, glycidyl ethers of the alkylene oxide adducts, and the alkylene oxide adducts. (Meth) acrylate and the like.

  In addition, although the manufacturing method of 9,9-bis (aminophenyl) fluorene is not specifically limited, For example, in the manufacturing method of the said bis (hydroxyphenyl) fluorene, it replaces with phenol and uses corresponding aniline. Can be manufactured.

  In the resin composition of the present invention, the resin component only needs to have a unit of a compound having a fluorene skeleton represented by the formula (1). Resin component composed of a resin (in particular, a resin obtained by polymerizing a compound having a fluorene skeleton as a monomer component of the resin) contained as a monomer component (or polymerization component) (that is, a fluorene skeleton was introduced into the resin skeleton) Resin), or (ii) a resin component composed of a compound having a fluorene skeleton and a resin. In the present invention, any resin component (i) or (ii) can be used, but (i) a compound having a fluorene skeleton is included as a monomer component (or a polymerization component or a copolymerization component) of the resin. A resin component composed of a resin (in particular, a resin obtained by polymerizing a compound having a fluorene skeleton as a monomer component of the resin) can be suitably used.

  It does not specifically limit as resin which comprises a resin component (the said resin component (i) or (ii)), A usual thermoplastic resin and a thermosetting resin (or photocurable resin) can be used. The resins constituting the resin component may be used alone or in combination of two or more. Examples of thermoplastic resins include olefin resins (polyethylene, polypropylene, polymethylpentene, amorphous polyolefin, etc.), halogen-containing vinyl resins (chlorine-containing resins such as polyvinyl chloride, fluororesins, etc.), acrylic resins, and the like. Resin, styrene resin (polystyrene, acrylonitrile-styrene resin, etc.), polycarbonate resin (bisphenol A type polycarbonate, etc.), polyester resin (polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene naphthalate, etc.) Arylate resins, polyarylate resins, liquid crystal polyesters, etc.), polyacetal resins, polyamide resins (polyamide 6, polyamide 66, polyamide 46) Polyamide 6T, polyamide MXD, etc.), polyphenylene ether resin (modified polyphenylene ether, etc.), polysulfone resin (polysulfone, polyether sulfone, etc.), polyphenylene sulfide resin (polyphenylene sulfide, etc.), polyimide resin (polyetherimide, polyamide, etc.) Imide, polyamino bismaleimide, bismaleimide triazine resin, etc.), polyether ketone resin (polyether ketone, polyether ether ketone, etc.), thermoplastic elastomer (polyamide elastomer, polyester elastomer, polyurethane elastomer, polystyrene elastomer, Polyolefin elastomers, polydiene elastomers, polyvinyl chloride elastomers, fluorine thermoplastic resins Sutoma), and the like. The thermoplastic resins may be used alone or in combination of two or more.

  Examples of the thermosetting resin include phenol resin, amino resin (urea resin, melamine resin, etc.), furan resin, unsaturated polyester resin, epoxy resin, thermosetting polyurethane resin, silicone resin, thermosetting polyimide system. Resins, diallyl phthalate resins, vinyl ester resins (resins obtained by reaction of epoxy resins with (meth) acrylic acid or derivatives thereof, resins obtained by reaction of polyhydric phenols with glycidyl (meth) acrylate, etc.), etc. Can be mentioned. In addition, the thermosetting resin (or photocurable resin) includes a polyfunctional (meth) acrylate [(meth) acrylate of the 9,9-bis (hydroxyphenyl) fluorenes, (poly) urethane (meth) acrylate]. , (Poly) ester (meth) acrylate, epoxy (meth) acrylate, etc.], vinyl ether (divinyl ether obtained by reaction of diol component and acetylene, etc.) and the like. Thermosetting resins may be used alone or in combination of two or more.

  Further, the thermosetting resin may contain an initiator, a reactive diluent, a curing agent, a curing accelerator, and the like depending on the type of the thermosetting resin (or photocurable resin). For example, the resin composition containing the epoxy resin or urethane resin may contain an amine-based curing agent or the like, and the resin composition containing the unsaturated polyester resin or vinyl ester resin may contain an initiator (peroxide resin). Oxides, etc.), polymerizable monomers (reactive diluents such as (meth) acrylic acid esters and styrene) and the like.

  The resin component (i) or the resin component (ii) may be used alone or in combination of two or more. For example, as a mode of combining the resin component (i), for example, a mode of combining a resin component (i) having a different fluorene skeleton, a mode of combining a resin component (i) having a different resin skeleton, a mode of combining these modes, etc. Is mentioned. Moreover, as an aspect which combines resin component (ii), the aspect which combines a different resin and a fluorene compound, the aspect which combines a resin and a different fluorene compound, the aspect which combines a different resin and a different fluorene compound, etc. are mentioned. Furthermore, the resin component (i) may be combined with a resin having no fluorene skeleton.

  The resin component (i) included as the constituent component (monomer component) may be any resin as long as the resin skeleton is composed of a fluorene compound. (I-1) A resin polymerization component (for example, a diol component) It may be prepared by using a compound having a fluorene skeleton corresponding to this polymerization component (or monomer component) as a polyol component, a polyamine component such as a diamine component, or a polyglycidyl ether such as diglycidyl ether). . For example, a resin (polyester resin, polyurethane resin, epoxy resin, vinyl ester resin, (poly) urethane (meth) acrylate, (poly) ester (meth) acrylate), which uses a polyol component (particularly a diol component) as a polymerization component, In the vinyl ether, etc., a fluorene compound having a hydroxyl group [the 9,9-bis (hydroxyphenyl) fluorene or its alkylene oxide adduct, etc.] may be used for a part or all of the polyol component. In a resin (polyamide resin, polyimide resin, aniline resin, etc.) using a component (particularly a diamine component) as a polymerization component, a fluorene compound having an amino group in part or all of the polyamine component [9, 9- Bis (aminophenyl) full In the case of a resin (vinyl ester resin, epoxy (meth) acrylate, etc.) using an epoxy resin as a polymerization component (constituent component), an epoxy group may be added to a part or all of the epoxy resin. A fluorene compound having a glycidyl ether of 9,9-bis (hydroxyphenyl) fluorenes as exemplified above may be used.

  In addition, the resin component (i) may contain (i-2) a compound having a fluorene skeleton as a single polymerization component (monomer component, constituent component). For example, the 9,9-bis (hydroxyphenyl) fluorene glycidyl ether (diglycidyl ether, tetraglycidyl ether, etc.) may be used as an epoxy resin, and the 9,9- Bis (hydroxyphenyl) fluorene (meth) acrylates may also be used.

  In the resin component (i), fluorene compounds (fluorene compounds having a hydroxyl group, fluorene compounds having an amino group, etc.) may be used alone or in combination of two or more as a polymerization component (or constituent component).

  The resin (or resin component) constituting the preferred resin component is a polyester resin, polyurethane resin (thermoplastic or thermosetting polyurethane resin), polycarbonate resin, acrylic resin [polyfunctional (meth) acrylate (described above) A thermosetting or photocurable resin such as 9,9-bis (hydroxyphenyl) fluorene (meth) acrylate)], a polyimide resin (thermoplastic or thermosetting polyimide resin), and the like. Also, from the viewpoint of compatibility with a fluorene compound or a sulfur compound described later, a resin (thermoplastic resin) containing an aromatic ring (benzene ring), for example, an aromatic polycarbonate resin (such as bisphenol A polycarbonate), a polyester resin Resin [polyalkylene arylate resin; polyarylate resin using aromatic dicarboxylic acid (such as terephthalic acid) and aromatic diol (such as biphenol, bisphenol A, xylylene glycol, and these alkylene oxide adducts) as polymerization components, etc. ], A polysulfone resin (polysulfone, polyethersulfone, etc.) and a polyphenylene sulfide resin (polyphenylene sulfide, etc.) are also preferred.

  In the present invention, in particular, a resin obtained by polymerizing a compound having a fluorene skeleton (the compound represented by the formula (1)) as a monomer component of the resin, and the above preferred resins (for example, polyester-based resins, polyurethane-based resins) A resin component composed of a resin, a polycarbonate resin, an acrylic resin, a polyimide resin, or the like can be preferably used.

  Hereinafter, a resin (or resin component (i)) containing a compound having a fluorene skeleton as a monomer component (polymerization component, constituent component, copolymerization component) will be described in detail for typical resins.

(1) Polyester resin A polyester resin containing a compound having a fluorene skeleton as a polymerization component (particularly a polyester resin obtained by polymerizing a compound having a fluorene skeleton as a monomer component of the resin) is a fluorene compound having at least a hydroxyl group. (Polyol components such as the 9,9-bis (hydroxyphenyl) fluorenes or alkylene oxide adducts thereof, particularly diol components such as 9,9-bis (monohydroxyphenyl) fluorenes or alkylene oxide adducts thereof) and The polyester resin includes a saturated or unsaturated polyester resin and a polyarylate resin using an aromatic dicarboxylic acid as a polymerization component in addition to a saturated or unsaturated polyester resin.

The polyol component (particularly the diol component) of the polyester resin may be configured by combining the fluorene compound having a hydroxyl group and another diol component. Examples of such diol components (or diols) include alkylene glycols (eg, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, tetramethylene glycol, hexanediol, neopentyl glycol, octanediol, decane. Linear or branched C _2-12 alkylene glycols such as diols), (poly) oxyalkylene glycols (eg di to tetra C _2-4 alkylene glycols such as diethylene glycol, triethylene glycol, dipropylene glycol, etc.) Alicyclic diols (for example, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2,2-bis (4-hydroxycyclohexyl) propane and its alkylene oxide adducts 2,2-bis (4- (2-hydroxyethoxy) cyclohexyl) propane etc.)), aromatic diols (eg, biphenol, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), bisphenol AD, Examples thereof include bisphenol F and their alkylene oxide ( _C2-3 alkylene oxide) adducts (such as 2,2-bis (4- (2-hydroxyethoxy) phenyl) propane) and xylylene glycol). These diols may be used alone or in combination of two or more.

Preferred diols are linear or branched C _2-10 alkylene glycols, particularly C _2-6 alkylene glycols (eg, linear or branched chain such as ethylene glycol, propylene glycol, 1,4-butanediol). C _2-4 alkylene glycol). As the diol, at least ethylene glycol is often used. When such diols (for example, ethylene glycol) are used, the polymerization reactivity can be enhanced and flexibility can be imparted to the resin.

  The ratio (molar ratio) between the fluorene compound having a hydroxyl group (particularly 9,9-bis (monohydroxyphenyl) fluorene or its alkylene oxide adduct) and the diol is, for example, the former / the latter = 100 / 0 to 50/50, preferably 100/0 to 75/25 (for example, 100/0 to 70/30), more preferably about 100/0 to 90/10 (for example, 100/0 to 80/20). There may be.

  A polyol such as glycerin, trimethylolpropane, trimethylolethane, or pentaerythritol may be used in combination with the diol component as necessary.

Examples of the dicarboxylic acid component constituting the polyester resin include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, and derivatives capable of forming esters thereof [for example, acid anhydrides; acid halides (acid chlorides, etc.); Lower alkyl esters (such as C _1-2 alkyl esters)] and the like. These dicarboxylic acids can be used alone or in combination of two or more.

Examples of the aliphatic dicarboxylic acid include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, hexadecanedicarboxylic acid, and other saturated C _3-20 aliphatic dicarboxylic acids. Acids (preferably saturated C _3-14 aliphatic dicarboxylic acids, etc.); unsaturated C _4-20 aliphatic dicarboxylic acids (preferably unsaturated C _4-14 aliphatics, such as maleic acid, fumaric acid, citraconic acid, mesaconic acid) Dicarboxylic acid and the like); derivatives of these that can form esters. In the unsaturated polyester resin, the ratio of the aliphatic unsaturated dicarboxylic acid (maleic acid or its acid anhydride) is, for example, 10 to 100 mol%, preferably 30 to 100 mol%, based on the entire dicarboxylic acid component. More preferably, it may be about 50 to 100 mol% (for example, 75 to 100 mol%).

Examples of the alicyclic dicarboxylic acid include saturated alicyclic dicarboxylic acids (cyclopentane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, cycloheptane dicarboxylic acid, etc. C _3-10 cycloalkane-dicarboxylic acid), unsaturated alicyclic dicarboxylic acid (C _3-10 cycloalkene-dicarboxylic acid such as 1,2-cyclohexene dicarboxylic acid, 1,3-cyclohexene dicarboxylic acid, etc.); Cyclic alkane dicarboxylic acids (di- or tricyclo C _7-10 alkane-dicarboxylic acids such as bornane dicarboxylic acid, norbornane dicarboxylic acid, adamantane dicarboxylic acid), polycyclic alkene dicarboxylic acids (bornene dicarboxylic acid, norbornene dicarboxylic acid, etc. di- or tricyclic C _7-10 A Ken - dicarboxylic acid), etc. These esters can form derivatives can be exemplified.

Aromatic dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid (2,6-naphthalenedicarboxylic acid, etc.), 4,4'-diphenyldicarboxylic acid, diphenylether-4,4'-dicarboxylic acid, 4 , 4′-diphenylmethane dicarboxylic acid, aromatic C _8-16 dicarboxylic acid such as 4,4′-diphenyl ketone dicarboxylic acid; and ester-forming derivatives thereof.

  The dicarboxylic acid may be used in combination with a polyvalent carboxylic acid such as trimellitic acid or pyromellitic acid, if necessary.

The dicarboxylic acid component is usually at least one selected from aliphatic dicarboxylic acids and alicyclic dicarboxylic acids, in particular, aliphatic dicarboxylic acids (saturated aliphatic dicarboxylic acids or derivatives capable of forming esters thereof, particularly adipic acid, Saturated C _3-14 aliphatic dicarboxylic acids such as suberic acid and sebacic acid) and alicyclic dicarboxylic acids (C _5-10 cycloalkane dicarboxylic acids such as cyclohexane dicarboxylic acid) are preferred.

  In the polyarylate-based resin, a dicarboxylic acid component containing at least an aromatic dicarboxylic acid is used, and the aromatic dicarboxylic acid may be used in combination with another dicarboxylic acid (aliphatic dicarboxylic acid and / or alicyclic dicarboxylic acid). Good. The ratio of the aromatic dicarboxylic acid to the other dicarboxylic acid is, for example, the former / the latter (molar ratio) = 100/0 to 10/90, preferably 100/0 to 30/70, more preferably 100/0 to 50. It may be about / 50.

  In the polyester resin, the ratio (molar ratio) between the dicarboxylic acid component and the polyol component (diol component, 9,9-bis (monohydroxyphenyl) fluorene or its alkylene oxide adduct and diol) is usually the former. / The latter = 1.5 / 1 to 0.7 / 1, preferably 1.2 / 1 to 0.8 / 1 (particularly 1.1 / 1 to 0.9 / 1).

The weight average molecular weight Mw (polystyrene conversion) of the polyester resin is not particularly limited, and is, for example, 100 to 50 × 10 ⁴ , preferably 500 to 30 × 10 ⁴ (for example, 1000 to 20 × 10 ⁴ ), and more preferably 3000. About 30 × 10 ⁴ . In the case of an unsaturated polyester resin, the molecular weight per double bond may be 300 to 1000, preferably 350 to 800, and more preferably about 400 to 700. The terminal group of the polyester resin may be a hydroxyl group or a carboxyl group, and may be protected by a protecting group as necessary.

  The polyester resin is prepared by a conventional method, for example, a direct polymerization method (direct esterification method) or a transesterification method, and a polyol component (particularly a diol component) composed of a fluorene compound having a hydroxyl group and the dicarboxylic acid component. Can be produced by a condensation reaction.

(2) Polyurethane resin The polyol component (diol component) constituting the polyurethane resin containing a compound having a fluorene skeleton as a polymerization component (monomer component) is a fluorene compound having a hydroxyl group (9,9-bis ( Monohydroxyphenyl) fluorenes or alkylene oxide adducts thereof) may be used alone or together with the diols exemplified in the section of the polyester resin together with the hydroxyl group-containing fluorene compound. Furthermore, a diol component containing the fluorene compound having a hydroxyl group as a structural unit, for example, a polyester diol produced by a reaction between a diol component composed of 9,9-bis (monohydroxyphenyl) fluorenes and a dicarboxylic acid component, Polyether diols produced by the reaction of diol components composed of 9,9-bis (monohydroxyphenyl) fluorenes and alkylene oxides can also be used as the diol components of polyurethane resins. A diol component can also be used individually or in combination of 2 or more types. If necessary, the diol component may be used in combination with a polyol component such as triol.

  In the polyol component (diol component), the content of the hydroxyl group-containing fluorene compound (9,9-bis (monohydroxyphenyl) fluorene or its alkylene oxide adduct) is, for example, the entire polyol component (diol component). It may be 10 to 100 mol%, preferably 20 to 80 mol%, more preferably about 30 to 70 mol%.

As the diisocyanate compound constituting the polyurethane resin, aromatic diisocyanate [paraphenylene diisocyanate, tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), naphthalene diisocyanate (NDI), bis ( Isocyanatophenyl) methane (MDI), toluidine diisocyanate (TODI), 1,2-bis (isocyanatophenyl) ethane, 1,3-bis (isocyanatophenyl) propane, 1,4-bis (isocyanatophenyl) butane , Polymeric MDI, etc.], alicyclic diisocyanates [cyclohexane 1,4-diisocyanate, isophorone diisocyanate (IPDI), hydrogenated XDI, hydrogenated MDI, etc.], fat Diisocyanate diisocyanate compounds such as [hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMDI), lysine diisocyanate (LDI), etc.] and the like. These diisocyanate compounds can be used alone or in combination of two or more. If necessary, these diisocyanate compounds may be polyisocyanate compounds (for example, aliphatic triisocyanates such as 1,6,11-undecane triisocyanate methyloctane and 1,3,6-hexamethylene triisocyanate; bicycloheptane triisocyanate). Triisocyanate compounds such as alicyclic triisocyanates, etc.), monoisocyanate compounds (C _1-6 alkyl isocyanates such as methyl isocyanate; C _5-6 cycloalkyl isocyanates such as cycloalkyl isocyanate; C _6- such as phenyl isocyanate) ₁₀ aryl isocyanate and the like). The isocyanate compound includes derivatives such as multimers and modified products of the polyisocyanate compound.

  The polyurethane-based resin is used in a conventional manner, for example, 0.7 to 2.5 mol, preferably 0.8 to 2.2 mol, more preferably 0.9 to 2 mol per mol of the polyol component (diol component). It can be obtained by using it at a ratio of about 2 mol and urethanizing it. In addition, when a diisocyanate component of about 0.7 to 1.1 mol is used with respect to 1 mol of a diol component, a thermoplastic resin can be obtained, and an excess mol (for example, about 1.5 to 2.2 mol) is obtained. When a diisocyanate component is used, a thermosetting resin having a free isocyanate group at the terminal can be obtained.

(3) Polycarbonate-based resin As a polycarbonate-based resin containing a compound having a fluorene skeleton as a polymerization component, according to a conventional method, for example, a fluorene compound having at least the hydroxyl group (particularly 9,9-bis (monohydroxyphenyl)) Reaction of polyol component (particularly diol component) and phosgene (phosgene method) composed of fluorenes or alkylene oxide adducts thereof, or polyol component (diol component) composed of fluorene compound having hydroxyl group And a polycarbonate resin obtained by a reaction (transesterification method) of the ester with carbonate.

  The polyol component (diol component) may be composed of a fluorene compound having a hydroxyl group alone. The fluorene compound having a hydroxyl group and other diols (the diols exemplified in the above-mentioned polyester-based resin, particularly aromatic diols) Or an alicyclic diol). Other diols can be used alone or in combination of two or more. Among other diols, aromatic diols such as bisphenols such as bisphenol A, AD, and F are particularly preferable. The ratio between the fluorene compound having a hydroxyl group and the diol can be selected from the same range as in the case of the polyester resin.

The molecular weight of the polycarbonate resin is not particularly limited. For example, the weight average molecular weight is 1 × 10 ^{3 to} 100 × 10 ⁴ (for example, 1 × 10 ^{4 to} 100 × 10 ⁴ ), preferably 5 × 10 ³ to 50 × 10 ^4. (For example, 1 × 10 ⁴ to 50 × 10 ⁴ ), more preferably about 1 × 10 ^{4 to} 25 × 10 ⁴ (for example, 1 × 10 ⁴ to 10 × 10 ⁴ ).

(4) Acrylic resin A monomer of acrylic resin (a (meth) acrylic monomer having a fluorene skeleton) is obtained by a reaction between the hydroxyl group-containing fluorene compound and a carboxyl group-containing polymerizable monomer. May be obtained. As the polymerizable monomer having a carboxyl group, an unsaturated monocarboxylic acid, particularly (meth) acrylic acid, can be used, and cinnamic acid, crotonic acid, sorbic acid, maleic acid monoalkyl esters (monomethyl malate, etc.) Etc. may be used. Further, reactive derivatives such as acid chloride and C _1-2 alkyl ester may be used in place of the unsaturated carboxylic acid. These monomers may be used alone or in combination of two or more.

The acrylic resin is a homopolymer or copolymer of the (meth) acrylic monomer having the fluorene skeleton, and a copolymer of the (meth) acrylic monomer having the fluorene skeleton and another copolymerizable monomer. It may be a polymer. Examples of the copolymerizable monomer include carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; (meth) acrylic acid esters [(meth) methacrylic acid such as methyl (meth) acrylate ) Acrylic acid C _1-6 alkyl ester, etc.]; Vinyl cyanides such as (meth) acrylonitrile; Aromatic vinyl monomers such as styrene; Carboxylic acid vinyl esters such as vinyl acetate; α- such as ethylene and propylene Examples include olefins. These copolymerizable monomers can be used alone or in combination of two or more.

  In addition, a monomer having a plurality of (meth) acryloyl groups [for example, (meth) acrylates of the 9,9-bis (hydroxyphenyl) fluorenes exemplified above (di (meth) acrylate, tetra (meth) acrylate, etc.)] Etc.] itself may be used as an acrylic resin (that is, thermosetting acrylic resin, oligomer (resin precursor)).

(5) Polyimide resin (thermoplastic or thermosetting polyimide resin)
The polyamine component (diamine component) constituting the polyimide resin is a fluorene compound having an amino group [9,9-bis (aminophenyl) fluorenes such as 9,9-bis (monoaminophenyl) fluorenes in particular]. May be used alone or in combination with a diamine component (diamine). Examples of diamines include chain C _2-14 aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, hexamethylenediamine, and dodecanediamine; Cyclic C _6-14 amines such as isophoronediamine, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, bis (4-amino-3-methyldicyclohexyl) methane; metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldiphenylmethane, etc. C _6-20 aromatic diamine; C _{7 - 14} aromatic aliphatic diamines such as m- xylylenediamine, diamino phenyl ether, 2,2-bis (3,4-di Minofeniru) bis (di-aminophenyl) alkanes such as propane can be exemplified. Diamines can be used alone or in combination of two or more.

  The ratio between the fluorene compound having an amino group and the diamine is the former / the latter (molar ratio) = 100/0 to 5/95, preferably 90/10 to 10/90, more preferably 80/20 to 20/80. Degree.

  Examples of the raw material polycarboxylic acids include tetracarboxylic acids or derivatives thereof, such as pyromellitic acid or anhydrides thereof, biphenyltetracarboxylic acid or anhydrides thereof, benzophenone tetracarboxylic acid or anhydrides thereof, and 2,2-bis (3 , 4-Dicarboxyphenyl) propane and other bis (dicarboxyphenyl) alkanes or anhydrides thereof, bis (carboxyphenyl) fluoroalkanes such as 2,2-bis (3,4-carboxyphenyl) hexafluoropropane, bismaleimide Etc. can be exemplified. These polycarboxylic acids can be used alone or in combination of two or more.

  The resin component (ii) can be produced or prepared by mixing a compound having a fluorene skeleton and a resin. Moreover, in preparation of the resin composition of this invention, it can also manufacture or prepare by mixing the compound which has fluorene skeleton, resin, and a sulfur containing compound. The mixing method is not particularly limited, for example, melt kneading using a mixing means such as a blender such as a ribbon blender, a tumble mixer, a Henschel mixer, or a kneading machine such as an open roller, a kneader, a Banbury mixer, or an extruder. The method by can be used. These mixing methods may be used alone or in combination of two or more.

  In the resin component (ii), the proportion of the compound having a fluorene skeleton is, for example, 1 to 80 parts by weight, preferably 5 to 60 parts by weight, and more preferably 20 to 60 parts by weight with respect to 100 parts by weight of the resin. It may be a degree.

(Sulfur-containing compounds)
The sulfur-containing compound may be a compound containing a sulfur-containing group in the molecule, and may be an inorganic or organic compound. However, in the present invention, a sulfur-containing organic compound having a sulfur-containing group can be preferably used.

  Examples of the sulfur-containing organic compound include, for example, the formula [A- (J) q] (wherein A represents a group selected from a hydrocarbon group and a heterocyclic group, J represents a sulfur-containing group, and q represents 1). A compound having at least a unit represented by:

Examples of the alicyclic hydrocarbon corresponding to the alicyclic hydrocarbon group include C _5-10 cycloalkane (eg, C _5-8 cycloalkane) such as cyclohexane, C _5-10 cycloalkene such as cyclohexene (eg, C ₅ Monocyclic hydrocarbons such as _5-8 cycloalkenes; bi- or tricycloalkanes (C _6-16 bi- or tricycloalkanes such as norbornane, adamantane, decalin), bi- or tricycloalkenes (C _6- such as norbornene) ₁₆ bi- or tricycloalkene) and the like. Examples of the aromatic hydrocarbon corresponding to the aromatic hydrocarbon group include C _6-10 aromatic hydrocarbons such as benzene and naphthalene (particularly benzene).

  The heterocyclic ring corresponding to the heterocyclic group (or heterocyclic skeleton or heterocyclic ring) includes a heterocyclic ring containing at least one hetero atom selected from an oxygen atom and a nitrogen atom (especially a 5- or 6-membered heterocyclic ring). ), For example, saturated or unsaturated oxygen-containing rings such as oxacyclohexane ring and pyran ring (especially 5- or 6-membered ring); saturated or unsaturated nitrogen-containing rings such as pyrrole ring and pyridine ring (especially 5- or 6-membered ring) And oxygen- and nitrogen-containing saturated or unsaturated rings (especially 5 to 6 membered rings) such as morpholine rings.

Among these groups (or skeletons) A, from the viewpoint of compatibility with the resin component composed of the compound having the fluorene skeleton, an alicyclic hydrocarbon group (or alicyclic hydrocarbon skeleton), aromatic A hydrocarbon group (or an aromatic hydrocarbon skeleton) or the like is preferable, and an aromatic hydrocarbon group (particularly a C _6-10 aromatic hydrocarbon (particularly a phenyl group)) is particularly preferable.

Examples of the sulfur-containing group J include mercapto group (—SH), thio group (sulfide group, thioether group, —S—), polythio group [dithio group (—S—S—), trithio group (—S—). S—S—) and the like], sulfinyl group (—SO—), sulfonyl group (—SO ₂ —), sulfo group (—SO ₃ H), and the like. Preferred sulfur-containing groups include mercapto groups, thio groups, dithio groups, and sulfonyl groups. In addition, when the sulfur-containing group is a divalent group (thio group, sulfonyl group, etc.), the sulfur-containing group J may form a ring with the group A.

  The number q of the sulfur-containing groups is 1 or more, for example, 1 to 8, preferably 1 to 5, more preferably 1 to 3, particularly 1 or 2. Moreover, when q is plural (for example, 2), the sulfur-containing groups may be the same or different.

The sulfur-containing compound (sulfur-containing organic compound) may have a substituent. Examples of the substituent (non-sulfur-containing substituent) include a hydrocarbon group [alkyl group (C _1-10 alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, t-octyl group, etc.), trichloro Halo C _1-4 alkyl group such as methyl group, tribromomethyl group, etc.), cycloalkyl group (C _5-8 cycloalkyl group such as cyclohexyl group, norbornyl group, diammonyl group such as adamantyl group, etc.), Aryl groups (such as C _6-10 aryl groups such as phenyl groups), aralkyl groups (such as C _6-10 aryl-C _1-4 alkyl groups such as benzyl groups), etc., halogen atoms (fluorine atoms, chlorine atoms, bromines) Atoms, iodine atoms, etc.), cyano groups, nitro groups, acyl groups (formyl groups, acetyl groups and other C _1-6 acyl groups), heterocyclic groups (morpholino groups and other nitrogen sources) Child-containing ring groups, nitrogen- and oxygen-containing ring groups such as benzoxazolyl groups), carboxyl groups or derivatives thereof (halocarbonyl groups such as chlorocarbonyl groups, C _1-4 alkoxycarbonyl groups such as methoxycarbonyl groups) Etc.), hydroxyl group, amino group, substituted amino group (N, N-dialkylamino group such as N, N-dimethylamino group), cyclic ether group (such as glycidyl group), alkenyl group (C ₂ such as vinyl group) _-6 alkenyl group, preferably α-C _2-4 alkenyl group, especially vinyl group), (meth) acryloyl group and the like. These substituents may be contained in the sulfur-containing compound alone or in combination of two or more.

  These substituents are not particularly limited at the substitution position. Further, these substituents may be substituted independently for the sulfur-containing group J (for example, may be substituted for the group A), and constitute the sulfur-containing group J (or the sulfur-containing group). May be bonded to the group A and the sulfur-containing group J.

  Further, the sulfur-containing compound may be a metal complex (such as a thiolate complex) coordinated to a polyvalent metal (or polyvalent metal ion) such as copper or nickel, and such a metal complex forms a chelate. It may be. Furthermore, the sulfur-containing compound also includes a compound in which the sulfur-containing group (such as a mercapto group or a sulfo group) or the substituent (such as a carboxyl group) forms a salt. The salt is not particularly limited, and various salts, for example, metal salts (alkali metal salts such as sodium, alkaline earth metal salts), inorganic acid salts (hydrochlorides) depending on the types of sulfur-containing groups and substituents. Etc.), and quaternary ammonium salts (tetraalkyl ammonium salts, etc.).

  The sulfur-containing compound (sulfur-containing organic compound) only needs to have at least the unit represented by the above formula, and has a plurality (for example, 2 to 5, preferably 2 to 3, more preferably 2). Also good. The sulfur-containing compound is usually in a liquid form or a solid form.

  Typical sulfur-containing compounds (sulfur-containing organic compounds) include sulfur-containing compounds having an aromatic hydrocarbon group (or aromatic hydrocarbon skeleton), sulfur-containing cyclic organic compounds, sulfur-containing heterocyclic compounds, and sulfur-containing aliphatics. Compound etc. are mentioned.

  Examples of the sulfur-containing compound having an aromatic hydrocarbon group (or an aromatic hydrocarbon skeleton) include mercaptoarenes, alkylthioarenes, arylthiocarboxylic acids, arylthio (meth) acrylates, diaryl sulfides, diaryl disulfides, Alkyl-aryl sulfones, arenesulfonyl halides and the like are included.

Mercaptoarenes include mercaptoarenes (mercapto C _6-10 arenes such as thiophenol), mercaptoarenes having a substituent [for example, C _1-6 alkyl- such as alkyl-mercaptoarenes (pt-butylthiophenol). Mercapto C _6-10 arenes, preferably C _1-6 alkyl-mercaptobenzene), halo-thiophenols (halo-mercapto C _6-10 such as o-chlorothiophenol, p-chlorothiophenol, p- _{fluorothiophenol)} Monomercaptoarenes, such as arenes, preferably halo-mercaptobenzene), hydroxy-mercaptoarenes (such as hydroxy-mercapto C _6-10 arenes such as p-mercaptophenol), and the like, dimers corresponding to these monomercaptoarenes Mercapto array Emissions such (eg, C _1-6 alkyl, such as 4-t-butyl-1,2-dimercapto benzene - dimercapto C _6-10 arene, preferably C _1-6 alkyl - such dimercapto benzene), these mono Or a thiolate complex corresponding to dimercaptoarenes {eg, tetra-n-butylammonium bis [4-t-butyl-1,2-benzenedithiolate (2-)-S, S ′] caprate (1-), Copper chelate complexes corresponding to dimercaptoarenes such as tetra-n-butylammonium bis [4- (morpholinosulfonyl) -1,2-benzenedithiolate (2-)-S, S ′] caprate (1-) Tetra-n-butylammonium bis [4- (morpholinosulfonyl) -1,2-benzenedithiolate (2-)-S, S ′] nickelate (1-) Thiolate complexes formed with chelates such as nickel chelate complexes corresponding to dimercaptoarenes, etc.}.

Examples of the alkylthioarenes include alkylthioarenes (C _1-6 alkylthio C _6-10 arenes such as thioanisole, preferably C _1-4 alkylthiobenzene), substituted alkylthioarenes [halo-alkylthioarenes (2-chlorothiones). Halo-C _1-6 alkylthio C _6-10 arenes such as anisole, 4-bromothioanisole, preferably halo-C _1-4 alkylthiobenzene, more preferably halothioanisole), cyano-alkylthioarene (o- (methylthio) ) Cyano-C _1-6 alkylthio C _6-10 arenes such as benzonitrile, p- (methylthio) benzonitrile, preferably cyano-C _1-4 alkylthiobenzene, more preferably cyano-thioanisole), acyl-alkylthioarenes (O- (Methylthio) benz Aldehyde, p-(methylthio) benzaldehyde, p-(methylthio) C _1-6 acyl -C _1-6 alkylthio C _6-10 arene such as acetophenone, preferably C _1-4 acyl -C _1-4 alkyl thio benzene, further Mono (alkylthio) arenes such as C _1-4 acyl-thioanisole etc. are preferred.

Arylthiocarboxylic acids include arylthiocarboxylic acids [eg, (C _6-10 arylthio) C _1-6 alkanecarboxylic acids such as (phenylthio) acetic acid, preferably (C _6-10 arylthio) C _1-4 alkanecarboxylic acids, More preferably (phenylthio) C _1-4 alkanecarboxylic acid], arylthiocarboxylic acid having a substituent [for example, (haloC _6-10 arylthio) C _1-6 alkanecarboxylic acid such as 2,5-dichlorophenylthioglycolic acid Preferably (halo C _6-10 arylthio) C _1-4 alkanecarboxylic acid, more preferably (halophenylthio) C _1-4 alkanecarboxylic acid].

Examples of the arylthio (meth) acrylates include arylthio (meth) acrylate (thio (meth) acrylic acid C _6-10 aryl ester such as phenylthio (meth) acrylate), and a substituent (explained above) on the arylthio (meth) acrylate. Examples thereof include compounds substituted with a substituent.

Diaryl sulfides include diaryl sulfides (diC _6-10 aryl sulfides such as diphenyl sulfide), diaryl sulfides having substituents {nitro-diaryl sulfides (nitrophenyl phenyl sulfide, 2,4-dinitrophenyl phenyl sulfide, etc.) Mono or dinitro-diC _6-10 aryl sulfide, preferably mono or dinitro-diphenyl sulfide), hydroxy-alkyl-diaryl sulfides [eg bis (4-hydroxy-3-methylphenyl) sulfide, 4,4′-thiodi (2,6-dimethylphenol), 4,4′-thiodi (2-tert-butyl-6-methylphenol), 4,4′-thiodi (2,6-di-tert-butylphenol), 2,2 ′ -Thiodi (4-t-octylphenol) What hydroxy - mono- or di-C _1-10 alkyl - di C _6-10 sulfide, preferably hydroxy - mono- or di-C _1-8 alkyl - diphenyl sulfides, mercapto - diaryl sulfide [e.g., 4,4'-thiodi Mono such as benzenethiol or monomer such as dimercapto-diC _6-10 aryl sulfide, preferably dimercapto-diphenyl sulfide], (meth) acryloylthio-diaryl sulfide [eg, bis (4- (meth) acryloylthiophenyl) sulfide Or di (meth) acryloylthio-diC _6-10 aryl sulfide, preferably di (meth) acryloylthio-diphenyl sulfide], alkenylthio-diaryl sulfide [e.g. mono or bis (4-vinylthiophenyl) sulfide etc. di-C _2-6 alkenyl O - di C _6-10 aryl sulfide, preferably di alpha-C _2-4 alkenylthio - diphenylsulfide, Gurishijiruchio - diaryl sulfide [e.g., bis [4- (2,3-epoxypropyl) phenyl] sulfide Mono or di (glycidylthio) _{-diC 6-10} aryl sulfide, preferably di (glycidylthio) -diphenyl sulfide] and the like.

  Among the diaryl sulfides, preferred diaryl sulfides include diphenyl sulfides represented by the following formula (2).

(Wherein R ⁶ and R ⁷ represent a substituent, Z ¹ and Z ² are the same or different and represent a hydrogen atom, a vinyl group, a (meth) acryl group or a glycidyl group, and r1, r2, p1 and p2) Are the same or different and each represents 0 or an integer of 1 to 5, provided that r1 + p1 and r2 + p2 are 0 or an integer of 1 to 5.)
Examples of the substituent represented by R ⁶ and R ⁷ include the substituents exemplified above (for example, an alkyl group, a nitro group, a hydroxyl group, etc.). R ⁶ and R ⁷ may be the same or different. Moreover, when r1 or r2 is plural, R ⁶ or R ⁷ may be the same or different substituents. Preferred r1 or r2 is 0 to 3, preferably 0 to 2.

Z ¹ and Z ² may be the same or different. Moreover, when p1 or p2 is plural, Z ¹ or Z ² may be the same or different groups. Preferred p1 or p2 is 0-2, preferably 0-1, more preferably 1. Incidentally, the substitution position of group -SZ ¹ or -SZ ² is not particularly limited, can be substituted 2-6-position relative to the phenyl group, the preferred substitution position is 4-position.

Particularly preferred diphenyl sulfides are compounds in which, in the above formula (2), Z ¹ and Z ² are a (meth) acryloyl group or a glycidyl group, and p1 and p2 are 1, that is, bis ((meth) acryloyl) Thiophenyl) sulfide [said bis (4- (meth) acryloylthiophenyl) sulfide etc.], bis (glycidylthiophenyl) sulfide [said bis [4- (2,3-epoxypropylthio) phenyl] sulfide etc.] .

Examples of diaryl disulfides include diaryl disulfides (diC _6-10 aryl disulfides such as diphenyl disulfide), diaryl disulfides having substituents [halo-diaryl disulfides (eg, halo-diaryl such as 4,4′-dichlorodiphenyl disulfide). C _6-10 aryl disulfides, preferably halo-diphenyl disulfides), cyano-diaryl disulfides (for example, cyano-di C _6-10 aryl disulfides such as 2,2′-dithiodibenzonitrile, preferably cyano-diphenyl disulfide), etc. ] Etc. can be illustrated.

Alkyl-aryl sulfones include alkyl-aryl sulfones (C _1-6 alkyl-C _6-10 aryl sulfones such as methylphenyl sulfone, preferably C _1-4 alkyl-phenyl sulfones, haloalkyl-aryl sulfones (tribromomethyl Halo C _1-6 alkyl-C _6-10 aryl sulfone such as phenyl sulfone, preferably halo C _1-4 alkyl-phenyl sulfone), substituted alkyl-aryl sulfones [p- (methylsulfonyl) acetophenone, etc. C _1-6 alkyl- (C _1-6 acyl C _6-10 aryl) sulfone, preferably C _1-4 alkyl- (C _1-4 acylphenyl) sulfone] and the like can be exemplified.

Examples of the arene sulfonyl halides include arene sulfonyl halides (C _6-10 arene sulfonyl halides such as benzenesulfonyl chloride), arene sulfonyl halides having a substituent [for example, cyano C such as cyanoarene sulfonyl halide (p-cyanobenzenesulfonyl chloride). _6-10 arenesulfonyl halide, preferably cyanobenzenesulfonyl halide), nitroarenesulfonyl halide (nitro C _6-10 arenesulfonyl halide such as p-nitrobenzenesulfonyl chloride, preferably nitrobenzenesulfonyl halide) and the like.

Examples of sulfur-containing cyclic organic compounds include cyclic sulfides (for example, thiophenes), cyclic sulfoxides (for example, sulfolanes such as sulfolane, sulfolenes such as 3-sulfolene), thiazoles (1,2-benzisothiazole, etc.) Benzothiazoles) and the like. Examples of the thiophenes include thiophene, thiophene having a substituent [eg, acylthiophene (eg, C _1-6 acylthiophene such as 2-thiophenecarbaldehyde, 2-acetylthiophene, 2,5-diacetylthiophene, preferably Is C _1-4 acylthiophene), halocarbonylthiophene (such as thiophenecarbonyl halide such as 2-thiophenecarbonyl chloride), carboxythiophene (such as dicarboxythiophene such as 2,5-thiophenedicarboxylic acid), alkoxycarbonylthiophene (for example, C _1-6 alkoxycarbonylthiophene such as 2,5-bis (methoxycarbonyl) thiophene, preferably C _1-4 alkoxycarbonylthiophene, thiophene having a heterocyclic group (2,5-bis (2-benzo) Xazolyl) thiophene, 2,5-bis (5-t-butyl-2-benzoxoxazolyl) thiophene, etc.)] and the like.

Examples of the sulfur-containing heterocyclic compound include a nitrogen-containing 5-6 having a sulfur-containing group such as a sulfur-containing nitrogen ring compound {for example, halo C _1-6 alkylsulfonylpyridine [2-[(tribromomethyl) sulfonyl] pyridine and the like]. Member ring compounds, etc.}.

Examples of the sulfur-containing aliphatic compound include hydroxy-dialkyl sulfones [eg, hydroxy-diC _1-6 alkylsulfone such as 2- (methylsulfonyl) ethanol, preferably hydroxy-diC _1-4 alkylsulfone], thiocarboxylic esters (thiol esters) [e.g., D-3-S- (acetylthio) thio C _1-4 carboxylic acids such as 2-methylpropanoic acid - carboxy C _1-6 alkyl ester (preferably thioacetic acid - carboxy C _1-4 alkyl ester), bis ((meth) acryloylthio C _1-6 alkyl) sulfide such as bis (2-methacryloylthioethyl) sulfide (preferably bis ((meth) acryloylthio C _1-4 alkyl) sulfide) Etc.], dialkyl disulfides [for example, bis (dimethylaminoethyl) di DiC _1-4 alkylamino-diC _1-6 alkyl disulfide such as sulfide dihydrochloride or a salt thereof, preferably diC _1-2 alkylamino-diC _1-4 alkyl disulfide or a salt thereof]. .
The refractive index of the sulfur-containing compound is 1.4 or more, for example, 1.45 to 1.8, preferably 1.5 to 1.8 (1.55 to 1.75), more preferably 1.55 to 1. .75 (for example, 1.6 to 1.75), particularly 1.65 or more (for example, 1.65 to 1.75). In particular, by using a sulfur-containing compound having a relatively high refractive index [for example, 1.65 or more], it is often possible to improve the refractive index of the resin composition or its molded body easily and efficiently.

  The ratio of the sulfur-containing compound is 1 to 60 parts by weight, preferably 3 to 50 parts by weight, and more preferably about 5 to 30 parts by weight with respect to 100 parts by weight of the resin component.

  The resin composition of the present invention may contain a function developing agent in order to further develop the function. The function developing agent is not particularly limited, and examples thereof include a carbon material (carbon black, graphite, carbon fiber, activated carbon, fullerene, carbon nanotube, etc.), a colorant, and the like depending on the application of the molded body. A function expression agent may be individual or may combine 2 or more types.

  The colorant includes inorganic pigments and organic dyes and pigments. Examples of inorganic pigments include black pigments [carbon black (for example, acetylene black, lamp black, thermal black, furnace black, channel black, ketjen black, etc.)], white pigments [titanium-based white pigments (titanium dioxide, etc.), zinc White pigments (such as zinc oxide and zinc sulfide), complex white pigments (such as lithopone), extender pigments (such as magnesium silicate, calcium carbonate, barium sulfate, aluminum hydroxide, and bentonite)], yellow pigments such as chrome yellow, oxidation Examples include red pigments such as iron red, orange pigments such as molybdate orange, green pigments such as chrome green, blue pigments such as bitumen, purple pigments such as manganese violet, cadmium pigments, lead pigments, and cobalt pigments. . Organic dyes or pigments include azo dyes (Pigment Yellow, Hansa Yellow, Benzidine Yellow, Permanent Red, Brilliant Carmine 6B, etc.), phthalocyanine dyes (phthalocyanine blue, phthalocyanine green, etc.), lake dyes (lakes). Red, watch chan red, etc.), cyanine dyes, carbazole dyes, pyromethene dyes, anthraquinone dyes, naphthoquinone dyes, quinacridone dyes, perylene dyes, perinone dyes, iso Examples include indoline dyes, dioxazine dyes, selenium dyes and the like. These colorants can be used alone or in combination of two or more.

  The colorant is a functional dye or pigment (azo dye, pigment, phthalocyanine dye, cyanine dye, carbazole dye, pyromethene dye, etc.), for example, a color resist, a near infrared absorbing dye, You may use for uses, such as a carrier transport agent and the electrification transfer agent for solar cells.

  Depending on the molding purpose, the resin composition of the present invention may contain other components such as lubricants, stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers), release agents (natural waxes, synthetic waxes, Linear fatty acids and their metal salts, acid amides, esters, paraffins, etc.), antistatic agents, and colorants (colorants such as those exemplified above) may also be included. These other components may be used alone or in combination of two or more.

  Additives include fillers, flame retardants, plasticizers (polyols, polysulfides, urethane prepolymers, etc.), dispersants, flow regulators, leveling agents, antifoaming agents, surface modifiers (silane cups) Ring agent, titanium coupling agent, etc.), stress reducing agent (silicone oil, silicone rubber, various plastic powders, various engineering plastic powders, etc.), liquid rubber (carboxyl-terminated butadiene-acrylonitrile copolymer rubber, ethylene-vinyl acetate) Copolymer, etc.), heat resistance improver or water repellency improver (sulfur compound, polysilane, silicone resin, etc.) and the like. These additives can be used alone or in combination of two or more.

  Examples of the filler or filler include fine particles of oxide inorganic materials such as silica, alumina, zirconia, and mica, or non-oxide inorganic materials such as silicon carbide and silicon nitride. Depending on the application, metal powders such as aluminum, zinc and copper can be added.

  More specifically, the filler includes silica-based silica, quartz, novacurite, diatomaceous earth, etc .; synthetic amorphous silica; kaolinite, mica, talc, wollastonite, asbestos, calcium silicate, aluminum silicate Silicates such as: glass powder, glass spheres, hollow glass spheres, glass flakes, foam glass spheres and other glass bodies; boron nitride, boron carbide, aluminum nitride, aluminum carbide, silicon nitride, silicon carbide, titanium boride, nitriding Non-oxide inorganic substances such as titanium and titanium carbide; calcium carbonate; metal oxides such as zinc oxide, alumina, magnesia, titanium oxide, and beryllium oxide are included. The shape of the filler may be fibrous, needle-like (including whiskers), granular, scale-like or the like. Examples of fibrous fillers include carbon fibers, activated carbon fibers, glass fibers, aluminosilicate fibers, aluminum oxide fibers, silicon carbide fibers, metal fibers, boron fibers, potassium titanate fibers and other inorganic fibers, and aramid fibers. Etc. are also included. These fillers can be used alone or in combination of two or more.

  Examples of flame retardants include boric acid flame retardants, phosphorus flame retardants, boric acid flame retardants and other inorganic flame retardants other than the phosphorus flame retardants, nitrogen flame retardants, halogen flame retardants, and organic flame retardants. Includes flame retardants and colloidal flame retardants. The flame retardants may be used alone or in combination of two or more.

  Examples of the halogen-based flame retardant include tetrabromo bisphenol A derivative (TBA), tetrabromo bisphenol S derivative, hexabromobenzene, decabromodiphenyl ether, tetrabromoethane (TBE), tetrabromobutane (TBB), hexabromocyclodecane. Brominated flame retardants such as (HBCD), and chlorinated flame retardants such as chlorinated paraffin, chlorinated polyphenyl, chlorinated diphenyl, perchloropentacyclodecane, and chlorinated naphthalene. These halogen-based flame retardants exhibit even better flame retardant effects when used in combination with antimony trioxide or the like.

  Examples of phosphorus-based flame retardant compounds include ammonium phosphate, melamine phosphate, red phosphorus, phosphate ester, tricresyl phosphate, tri (β-chloroethyl) phosphate, tri (dichloropropyl) phosphate, tri (dibromopropyl) Examples include phosphate, 2,3-dibromopropyl-2,3-dichloropropyl phosphate, and the like.

  Examples of other inorganic flame retardants include inorganic substances such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, calcium hydroxide, barium hydroxide, basic magnesium carbonate, dolomite, tin oxide hydrate, and borax. Examples thereof include metal hydrates, zinc borate, barium metaborate, zinc carbonate, magnesium carbonate-calcium carbonate, barium carbonate, magnesium oxide, molybdenum oxide, zirconium oxide, tin oxide, and expanded graphite.

  In the present invention, even if the other component (function-expressing agent, additive, etc.) is a compound having an aromatic ring, it can be efficiently dispersed in the resin composition. Among the additives, examples of the compound having an aromatic ring include carbon materials (carbon materials) such as carbon black, graphite, carbon fibers (carbon fibers), activated carbon, fullerene, and carbon nanotubes, and color resists. Functional dyes and pigments such as coloring dyes (red, blue, green, etc.), near-infrared absorbing dyes, carrier transfer agents and electrification transfer agents for solar cells (phthalocyanine dyes, carbazole dyes, cyanine dyes) Azo dyes and pigments, pyromethene dyes and the like).

  The ratio of the function enhancer or additive is, for example, 0.1 to 40 parts by weight, preferably 0.5 to 20 parts by weight, and more preferably about 1 to 15 parts by weight with respect to 100 parts by weight of the resin component. May be.

  The resin composition of the present invention is a mixture of the resin component (resin component (i) or (ii)), a sulfur-containing compound, and, if necessary, other components (additives such as the function enhancer, solvent, etc.). Can be produced or prepared. The mixing method is not particularly limited, for example, melt kneading using a mixing means such as a blender such as a ribbon blender, a tumble mixer, a Henschel mixer, or a kneading machine such as an open roller, a kneader, a Banbury mixer, or an extruder. The method by can be used. These mixing methods may be used alone or in combination of two or more.

  Moreover, the form of the coating liquid which mixed the solvent may be sufficient as a resin composition. The solvent that constitutes the coating solution is not particularly limited, and depending on the thermoplastic resin, conventional solvents such as hydrocarbons (aliphatic hydrocarbons such as pentane and hexane, alicyclic hydrocarbons such as cyclohexane, etc.) , Aromatic hydrocarbons such as toluene and xylene), halogenated solvents (haloalkanes such as dichloromethane, haloarenes such as monochlorobenzene), alcohols (alkyl alcohols such as methanol, ethanol, propanol, etc.), diols (Alkane diols such as ethylene glycol and propylene glycol, (poly) oxyalkylene glycols such as diethylene glycol and polyoxyethylene glycol), ethers (chain ethers such as diethyl ether, and cyclic ethers such as tetrahydrofuran) Etc.), esters (acetic esters such as ethyl acetate), ketones (dialkyl ketones such as acetone and ethyl methyl ketone, cyclic ketones such as cyclopentanone and cyclohexanone), glycol ether esters (ethylene) Glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, cellosolve acetate, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), carbitols (carbitol, etc.) and the like. These solvents may be used alone or in combination of two or more.

  The ratio of the solvent may be in a range that does not impair the coatability. The solvent content is 1 to 100 parts by weight, preferably 2 to 50 parts by weight, more preferably 3 to 30 parts by weight based on 1 part by weight of the resin composition. It may be about parts by weight.

  According to the form of the resin composition (resin pellets, coating liquid, etc.), the molded product of the present invention may be formed by a known molding method (for example, injection molding method, injection compression molding method, extrusion molding method, transfer molding method, blow molding method). The resin composition can be obtained by molding using a molding method, a pressure molding method, a casting molding method, or the like.

  In the resin composition of the present invention and the molded body thereof, a resin component (or fluorene compound) composed of a fluorene compound and the sulfur-containing compound (sulfur-containing organic compound) are combined, and a simple method of mixing them, The excellent properties (for example, optical properties such as refractive index) possessed by the fluorene compound (or 9,9-bisphenylfluorene skeleton) can be further improved or improved reliably and efficiently. Therefore, in the present invention, by adding (or mixing) a sulfur-containing compound to the resin component (fluorene compound), the optical property of the resin component (or a resin composition composed of the resin component or a molded product thereof) is obtained. Also included is a method of improving the optical characteristics (particularly the refractive index).

  The resin composition of the present invention and the molded product thereof have excellent properties (particularly, high optical properties such as a high refractive index and a low birefringence). Therefore, it can be suitably used for optical lenses, optical films, optical sheets, pickup lenses, holograms, liquid crystal films, organic EL (electroluminescence) films, and the like. In addition, the resin composition of the present invention or a molded product thereof (for example, a resin composition containing a function-expressing agent (pigment and the like) and a molded product thereof) includes a paint, an antistatic material, a charging tray, a conductive sheet, a protective film ( Electronic devices, protective films for liquid crystal members, etc.), optical discs, inkjet printers, digital paper, organic semiconductor lasers, thermal recording materials, hologram recording materials, dye-sensitized solar cells, EMI shield films, photochromic materials, organic EL elements, For organic photoreceptors, color filters, sliding members, automotive parts materials, aerospace materials, carrier transport agents, inks, adhesives, adhesives, building materials, interior materials, resin fillers, colored glass, light emitters, sensors, etc. It can be suitably used.

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

(Example 1)
1,4-cyclohexanedicarboxylic acid (CHDA) 1 mol, ethylene glycol (EG) 0.1 mol, and 9,9-bis {4- (2-hydroxyethoxy) phenyl} fluorene (BPEF) 0.9 mol A copolymer polyester was obtained by melt polymerization. The copolymer polyester had a weight average molecular weight (Mw) of 51,000 and a glass transition point (Tg) of 120 ° C.

  20 parts by weight of bis (4-methacryloylthiophenyl) sulfide (MPSMA, manufactured by Sumitomo Seika Co., Ltd.) is dry-blended with 100 parts by weight of the copolyester obtained by the above method, and the resin temperature is 190 using an extruder. Melt kneading was carried out at 0 ° C. to obtain resin pellets. Next, a plate (0.1 mm thick) was formed on the obtained pellets using a desktop hot press (resin temperature 200 ° C.). As a result of measuring the Abbe refractive index (manufactured by Atago Co., Ltd.) for the molded plate, the refractive index was 1.624.

(Example 2)
A plate was prepared in the same manner as in Example 1 except that 5 parts by weight of bis [4- (2,3-epoxypropylthiophenyl)] sulfide (MPG, manufactured by Sumitomo Seika Co., Ltd.) was used instead of 20 parts by weight of MPSMA. Molded. As a result of measuring the Abbe refractive index (manufactured by Atago Co., Ltd.) for the molded plate, the refractive index was 1.612.

(Comparative Example 1)
The copolymer polyester obtained in Example 1 was melt kneaded at a resin temperature of 190 ° C. using an extruder to obtain resin pellets. Next, a plate (0.1 mm thick) was formed on the obtained pellets using a desktop hot press (resin temperature 200 ° C.). As a result of measuring the Abbe refractive index (manufactured by Atago Co., Ltd.) for the molded plate, the refractive index was 1.607.

Claims (4)

A resin composition composed of a resin component composed of a compound having a fluorene skeleton represented by the following formula (1) and a sulfur-containing compound ,

Wherein the groups R ¹ and R ² are the same or different and are alkyl, aryl, aralkyl, hydroxyl, or groups — [X— (R ⁵ O) nY] (wherein R ⁵ Is an alkylene group, the group X is an oxygen atom, the group Y is a hydrogen atom, and n is an integer of 1 or more), and the groups R ¹ and R ² are at least a hydroxyl group or group - include ^{[X- (R 5 O) n} -Y], k1 and k2 are 1 to 3, m1 and m2 are 0)
The resin component is composed of a polyester resin obtained by polymerizing the compound represented by the formula (1) as a monomer component,
The sulfur-containing compound is a diphenyl sulfide represented by the following formula (2):

(Wherein R ⁶ and R ⁷ are the same or different and each represents an alkyl group, a nitro group or a hydroxyl group, Z ¹ and Z ² are the same or different and each represents a (meth) acryloyl group or a glycidyl group, and r 1 and r 2 are The same or different and 0 or an integer of 1 to 4 is shown, and p1 and p2 are 1. However, r1 + p1 and r2 + p2 are integers of 1 to 5.
The resin composition whose ratio of the said sulfur containing compound is 1-60 weight part with respect to 100 weight part of said resin components. The compound represented by the formula (1) is 9,9-bis (hydroxyphenyl) fluorene or an alkylene oxide adduct thereof, and the 9,9-bis (hydroxyphenyl) fluorene is 9,9-bis. (Hydroxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyphenyl) fluorene, 9,9-bis (cycloalkyl-hydroxyphenyl) fluorene, 9,9-bis (aryl-hydroxyphenyl) fluorene, or 9,9 The resin composition according to claim 1, which is bis (aralkyl-hydroxyphenyl) fluorene.   The resin composition according to claim 1, wherein the ratio of the sulfur-containing compound is 3 to 50 parts by weight with respect to 100 parts by weight of the resin component.   The molded object formed with the resin composition of Claim 1.