JP5567376B2 - Thermoplastic resin and method for producing the same - Google Patents

Description

  The present invention relates to a novel thermoplastic resin obtained by an enethiol reaction, a method for producing the same, a composition for obtaining the thermoplastic resin, a novel diallyl compound useful for obtaining the thermoplastic resin, and the like.

  Compounds having a fluorene skeleton are known to have excellent functions in optical properties, 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.

  In recent years, a compound having a 9,9-bisnaphthylfluorene skeleton has been developed as a new fluorene compound. For example, Japanese Patent Application Laid-Open No. 2007-99741 (Patent Document 3) discloses that 9,9-bis (hydroxynaphthyl) fluorene can be applied to a thermosetting resin (such as an epoxy resin). JP-A-2008-274250 (Patent Document 4) discloses a phenol resin using 9,9-bis (hydroxynaphthyl) fluorene as a phenol component.

  However, even a resin material having such a fluorene skeleton may still have insufficient improvement in optical properties (particularly refractive index). 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.

  On the other hand, in recent years, an ene / thiol-based curable composition in which a component having an ethylenically unsaturated group and a compound having a mercapto group are combined has been proposed. For example, JP-A-2006-89623 (Patent Document 5) discloses a cationic electrodeposition coating composition containing an unsaturated group and cationic group-containing epoxy resin and a thiol group and cationic group-containing epoxy resin. Yes. Japanese Patent Application Laid-Open No. 2008-13690 (Patent Document 6) discloses an electron beam curable composition containing a compound having an ethylenically unsaturated double bond and a polyfunctional thiol compound or a disulfide compound in a predetermined ratio. Has been. Furthermore, in JP2009-58582A (Patent Document 7), a photopolymerizable compound (such as a ring-opening addition reaction product of a carboxyl group-containing acrylic resin and an alicyclic epoxy compound having a polymerizable group), A photocurable resin composition containing a photopolymerization initiator and a thiol chain transfer agent (mercapto organic acid derivative and thioglycolic acid derivative) is disclosed.

  In addition, all of these documents disclose a composition for three-dimensionally cross-linking a resin using an enethiol reaction, and do not disclose any thermoplastic resin using an enethiol reaction. .

JP 2002-284864 A (Claims) JP 2002-284834 A (Claims) JP 2007-99741 A (Claims) JP 2008-274250 A (Claims) JP 2006-89623 A (Claims) JP 2008-13690 A (Claims) JP 2009-58582 A (Claims)

  Accordingly, an object of the present invention is to provide a novel thermoplastic resin having a 9,9-bis-fused polycyclic arylfluorene skeleton, a production method thereof, and a composition (enthiol reaction composition) for obtaining the thermoplastic resin. It is to provide.

  Another object of the present invention is to provide a thermoplastic resin having a high refractive index obtained by an enethiol reaction, a method for producing the same, and a composition for obtaining the thermoplastic resin.

  Still another object of the present invention is to provide a novel diallyl ether compound useful as the thermoplastic resin raw material.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a compound having two 9,9-bis-fused polycyclic arylfluorene skeletons and two ethylenically unsaturated bonds (particularly allyl groups) in the molecule ( In particular, if a diallyl compound) is reacted with a dithiol compound in the presence of a photopolymerization initiator or the like, an enethiol reaction occurs in preference to a three-dimensional crosslinking reaction by an ethylenically unsaturated bond. The present inventors have found that a novel thermoplastic resin having excellent characteristics such as refractive index can be obtained, and completed the present invention.

  That is, the thermoplastic resin of the present invention is a thermoplastic resin obtained by an enethiol reaction of a fluorene compound having a 9,9-bis condensed polycyclic aryl fluorene skeleton and two ethylenically unsaturated bonds with a dithiol compound. . The fluorene compound may be a diallyl compound having a 9,9-bis-fused polycyclic aryl fluorene skeleton (for example, a diallyl ether compound). The fluorene compound may typically be a diallyl ether compound represented by the following formula (1).

Wherein ring Z is a condensed polycyclic arene ring, R ¹ and R ² are the same or different substituents, k is an integer of 0-4, m is an integer of 0-4, R ³ is an alkylene group, n Represents an integer of 0 or more.)
In the formula (1), the ring Z may be a naphthalene ring. In the formula (1), n may be 0 from the viewpoint of improving the refractive index.

  The dithiol compound may contain an aliphatic dithiol compound (for example, alkanedithiol).

  In the present invention, the thermoplastic resin is produced by subjecting the fluorene compound (9,9-bis-fused polycyclic aryl fluorene skeleton and fluorene compound having two ethylenically unsaturated bonds) to a dithiol compound, and an thiol reaction. The method of doing is also included. In such a method, since an enethiol reaction can be used, the polymerization can proceed under mild conditions regardless of a polymerization method such as melt polymerization. In the method, typically, a composition containing the fluorene compound, the dithiol compound and a photopolymerization initiator may be irradiated with light to cause an enethiol reaction.

  The present invention also includes a composition containing the fluorene compound (for example, a diallyl compound having a 9,9-bis-fused polycyclic aryl fluorene skeleton) and a dithiol compound. Such a composition is useful as a composition (enthiol reaction forming composition) for obtaining the thermoplastic resin. Such a composition may further contain a photopolymerization initiator.

  Moreover, the diallyl ether compound represented by the formula (1) is also included in the present invention. Such a diallyl ether compound can be used as a raw material for heat or a photocurable resin in addition to a compound for obtaining the thermoplastic resin (a compound for producing a thermoplastic resin by an enethiol reaction with a dithiol compound). .

  The thermoplastic resin of the present invention has a 9,9-bis condensed polycyclic aryl fluorene skeleton. Such a thermoplastic resin is obtained by an enethiol reaction, and is derived from a sulfur atom introduced into the resin skeleton and a 9,9-bis-fused polycyclic aryl fluorene skeleton, and has excellent characteristics such as a high refractive index. (In particular, optical characteristics). Moreover, since the novel diallyl ether compound of the present invention is useful as the above thermoplastic resin raw material and has a diallyl skeleton, it can also be used as various heat or photocurable resin raw materials. When such a diallyl ether compound is used, excellent properties such as a high refractive index and high heat resistance can be imparted to the resin (thermoplastic resin, heat or photocurable resin).

  The thermoplastic resin of the present invention is obtained by an enethiol reaction of a fluorene compound having a 9,9-bis-fused polycyclic aryl fluorene skeleton and two ethylenically unsaturated bonds with a dithiol compound.

(Fluorene compound)
In the fluorene compound, the two ethylenically unsaturated bonds (or unsaturated bond groups) may be a vinyl group, a (meth) acryloyl group or the like, and particularly preferably an allyl group. That is, the fluorene compound is preferably a diallyl compound (a diallyl compound having a 9,9-bis-fused polycyclic arylfluorene skeleton). When the fluorene compound having an allyl group is used, the cross-linking reaction of the fluorene compound itself can be suppressed in combination with the dithiol compound, and the enethiol reaction can proceed efficiently.

  Examples of diallyl compounds include diallyl ether compounds and diallyl ester compounds (such as diallyl ester compounds of dicarboxylic acids having a 9,9-bis-fused polycyclic arylfluorene skeleton). A preferred diallyl compound is a diallyl ether compound (for example, a diallyl ether compound of a diol having a 9,9-bis-fused polycyclic arylfluorene skeleton). Typical fluorene compounds include diallyl ether compounds represented by the following formula (1).

Wherein ring Z is a condensed polycyclic arene ring, R ¹ and R ² are the same or different substituents, k is an integer of 0-4, m is an integer of 0-4, R ³ is an alkylene group, n Represents an integer of 0 or more.)
In the above formula (1), the condensed polycyclic arene ring represented by ring Z is a condensed bicyclic arene (for example, C _8-20 condensed bicyclic hydrocarbon such as naphthalene, preferably C _10-16. Examples thereof include fused bicyclic to tetracyclic arene rings such as fused bicyclic arene rings and fused tricyclic arene rings (for example, anthracene and phenanthrene). Preferred examples of the condensed polycyclic arene ring include a naphthalene ring and an anthracene ring, and a naphthalene ring is particularly preferable. The two rings Z may be the same or different rings, and may usually be the same ring.

In the formula (1), the substituent represented by the group R ¹ is not particularly limited as long as it is a non-reactive substituent. For example, 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 (C _6-10 aryl group such as a phenyl group)] and the like, and is often 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 substituent R ² include an alkyl group (eg, a C _1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group, preferably C _{1. -8} alkyl groups, more preferably C _1-6 alkyl groups, etc., cycloalkyl groups (C _5-10 cycloalkyl groups such as cyclohexyl groups, preferably C _5-8 cycloalkyl groups, more preferably C _{5 -6} cycloalkyl groups, etc.), aryl groups (eg C _6-14 aryl groups such as phenyl, tolyl, xylyl, naphthyl, etc., preferably C _6-10 aryl groups, more preferably C _6-8 aryl) hydrocarbon group such as group); an alkoxy group (methoxy group, an ethoxy group, a propoxy group, C _1-12 alkoxy group such as butoxy, The Mashiku _{C 1-8} alkoxy group, more preferably a _{C 1-6} alkoxy group), etc. cycloalkoxy _{(C 5-10} cycloalkoxy group), an aryloxy group _{(C 6-10} aryloxy group), etc. -OR ⁴ [wherein R ⁴ represents a hydrocarbon group (such as the hydrocarbon group exemplified above). ]; _{(C 1-20} alkylthio group such as methylthio group, preferably a _{C 1-8} alkylthio group, more preferably a _{C 1-6,} etc. alkylthio group) alkylthio group in the radical -SR ⁴ (wherein such, ^{R 4} is the An acyl group (such as a C _1-6 acyl group such as an acetyl group); an alkoxycarbonyl group (such as a C _1-4 alkoxy-carbonyl group such as a methoxycarbonyl group); a halogen atom (a fluorine atom, a chlorine atom, A nitro group; a cyano group; a carboxyl group; an amino group; a carbamoyl group; a substituted amino group (for example, a dialkylamino group such as a dimethylamino group); a sulfonyl group; Substituents [eg, alkoxyaryl groups (eg, C _1-4 alkoxy C _{6 10} aryl group), alkoxycarbonylaryl group (for example, C _1-4 alkoxy-carbonyl C _6-10 aryl group such as methoxycarbonylphenyl group)] and the like.

Of these, typically, the group R ² is a hydrocarbon group, —OR ⁴ (wherein R ⁴ represents a hydrocarbon group), —SR ⁴ (wherein R ⁴ is the same as defined above). ), An acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a substituted amino group, and the like.

Preferred group R ² includes a hydrocarbon group [eg, alkyl group (eg, C _1-6 alkyl group), cycloalkyl group (eg, C _5-8 cycloalkyl group), aryl group (eg, C _6-10 Aryl group), aralkyl group (for example, C _6-8 aryl-C _1-2 alkyl group and the like), alkoxy group (C _1-4 alkoxy group and the like) and the like. In particular, R ² represents a hydrocarbon group (particularly an alkyl group) such as an alkyl group [C _1-4 alkyl group (particularly methyl group)] or an aryl group [eg C _6-10 aryl group (particularly phenyl group)]. Group). R ² may be the same or different groups in the same or different rings Z.

In the formula (1), the substitution number m of the group R ² may be 0 to 4, preferably 0 to 2, and more preferably 0 to 1 (for example, 0).

In the formula (1), the alkylene group represented by the group R ³ is not particularly limited, and examples thereof include a C _2-10 alkylene group (for example, ethylene group, trimethylene group, propylene group, butane-1,2- C _2-6 alkylene group such as diyl group and hexylene group) can be exemplified, and C _2-4 alkylene group (particularly, C _2-3 alkylene group such as ethylene group and propylene group) is particularly preferable. R ³ may be the same or different alkylene groups (that is, when m is plural, R ² may be the same or different). That is, when n is 2 or more, the polyalkoxy (polyoxyalkylene) group [— (OR ³ ) _n —] may be composed of the same oxyalkylene group, and a plurality of oxyalkylene groups (for example, oxy Ethylene group and oxypropylene group). R ³ may be the same or different groups in different benzene rings.

The number (addition mole number) n of oxyalkylene groups (OR ³ ) can be selected, for example, from a range of about 0 to 15, for example, 0 to 10 (for example, 1 to 10), preferably 0 to 8 (for example, 1-8), more preferably 0-6 (eg 1-6), in particular 0-4 (eg 1-4), usually 0-2 (eg 1-2) Also good. In particular, when obtaining a thermoplastic resin having a higher refractive index, a compound in which n is 0 may be preferably used.

In addition to the method described later, the compound in which n is 1 or more includes the compound corresponding to the oxyalkylene group (OR ³ ) in addition to the compound in which n is 0 [for example, alkylene oxide (for example, ethylene oxide, propylene oxide, etc. C _2-4 alkylene oxide), alkylene carbonate (for example, C _2-4 alkylene carbonate such as ethylene carbonate) and the like] can also be obtained.

Incidentally, group ^- substituted position relative ring Z of _{[O- (OR 3) n -CH} 2 -CH = CH 2] is not particularly limited, the fused polycyclic arene ring Z, attached to the 9-position of fluorene In many cases, the hydrocarbon ring is substituted with a hydrocarbon ring different from the hydrocarbon ring. For example, when ring Z is a naphthalene ring, the substitution position of the group — [O— (OR ³ ) _n —CH ₂ —CH═CH ₂ ] is often the 5th to 8th positions.

Representative examples of the compound represented by the formula (1) include 9,9-bis (allyloxynaphthyl) fluorene [eg, 9,9-bis (6-allyloxy-2-naphthyl) fluorene]. In the formula (1), a compound in which n is 0; 9,9-bis (allyloxyalkoxynaphthyl) fluorene {for example, 9,9-bis [6- (2-allyloxyethoxy) -2-naphthyl] fluorene In the above formula (1) such as 9,9-bis [(allyloxy C _2-4 alkoxy) naphthyl] fluorene etc.], n is 1 or more (for example, 1 to 4) and the like.

  Fluorene compounds may be used alone or in combination of two or more. That is, when two or more kinds are combined, a thermoplastic resin into which a plurality of fluorene compound-derived skeletons are introduced is obtained.

  As the fluorene compound, a compound synthesized by a conventional method may be used. For example, the compound represented by the formula (1) can be obtained by allylating the compound represented by the following formula (1A) by a conventional method. Typically, it may be obtained by reacting a compound represented by the following formula (1A) with an allyl halide (for example, allyl bromide).

(In the formula, Z, R ¹ , R ² , R ³ , k, m and n are the same as above.)
Although the ratio of allyl halide is not particularly limited, it is, for example, 2 to 10 mol, preferably 2.1 to 8 mol, more preferably 2.2 to 1 mol with respect to 1 mol of the compound represented by the formula (1A). About 5 mol may be sufficient.

  In addition, in order to trap (capture) by-produced hydrogen halide, the allylation reaction using allyl halide may be performed in the presence of a base.

  The allylation reaction may be performed in a solvent. It does not specifically limit as a solvent, The below-mentioned solvent etc. can be used. The reaction temperature and reaction time can be selected as appropriate.

Moreover, in the said Formula (1), in order to obtain efficiently the compound whose n is 1 or more, manufacturing by the said method is preferable, but n is 0 as a compound represented by the said Formula (1A). And a compound in which n is 0 in the formula (1) is generated, and then the compound (a compound in which n is 0 in the formula (1)) and an alkylene group R ³ (or It can also be produced by reacting a compound corresponding to the oxyalkylene group OR ³ ).

Examples of the compound corresponding to the alkylene group R ³ include alkylene oxide (C _2-4 alkylene oxide such as ethylene oxide, propylene oxide and butylene oxide, especially C _2-3 alkylene oxide) and alkylene carbonate (ethylene carbonate, propylene carbonate, butylene). C _2-4 alkylene carbonates such as carbonate, especially C _2-3 alkylene carbonates), haloalkanols (for example, halo C _2-6 alkanols such as 3-chloropropanol) and the like. These compounds may be used alone or in combination of two or more. When alkylene oxide or alkylene carbonate is reacted, a (poly) oxyalkylene unit can be introduced through the hydroxyl group of the compound represented by the formula (1) (a compound in which n is 0). When using an alkylene carbonate, an oxyalkylene unit (alkoxy unit) is introduced by decarboxylation after the addition of the alkylene carbonate.

(Dithiol compound)
As a dithiol compound, if it is a compound which has two thiol groups (mercapto group) in a molecule | numerator, it will not specifically limit, For example, an aliphatic dithiol compound, an aromatic dithiol compound, etc. are contained. The dithiol compound may be a compound having two thiol groups on the same carbon atom (geminal dithiol compound) or a compound having two thiol groups on different carbon atoms.

  The dithiol compounds may be used alone or in combination of two or more. That is, when two or more types are combined, a thermoplastic resin into which a plurality of dithiol compound-derived skeletons are introduced is obtained.

Examples of the aliphatic dithiol compound include alkanedithiol (or dimercaptoalkane, for example, methanedithiol, 1,2-ethanedithiol, 1,1-zircaptoethane, 1,2-propanedithiol, 1,3-propanedithiol. 1,1-zircaptopropane, 2,2-zircaptopropane, 1,4-butanedithiol, 1,1-dimercaptobutane, 2,2-dimethylpropane-1,3-dithiol, 1,1-dimercapto C _2-20 alkanedithiol, such as 2-methylpropane, 1,6-hexanedithiol, 1,8-octanedithiol, preferably C _2-10 alkanedithiol, more preferably C _2-6 alkanedithiol, especially C _{2 -4} alkanedithiol), polyalkanedithiol [or polythioki Sialkylene dithiols, for example poly C _2-10 alkane dithiols such as bis (2-mercaptoethyl) sulfide, 1,2-bis (2-mercaptoethylthio) ethane, preferably poly C _2-6 alkanedithiols, more preferably poly _{C 2-4} alkane thiols), dimercapto (poly) oxa alkanes [e.g., 1,5-dimercapto-3-oxa-pentane, 1,8-dimercapto-3,6, 3,4-dimethoxy Dimercaptomono to tetraoxa C _2-20 alkane such as butane-1,2-dithiol, preferably dimercaptomono to trioxa C _2-16 alkane, more preferably dimercaptomono or dioxa C _2-10 alkane], cycloalkane Dithiol (eg 1,4-dimer) Script cyclohexane, 1,3-dimercapto-cyclohexane, _{1,2-C 5-8} cycloalkyl alkanedithiols such dimercapto cyclohexane), di mercaptoalkyl Jiang [e.g., 2,5-bis (mercaptomethyl) -1,4 Dithian, 2,5-bis (2-mercaptoethyl) -1,4-dithian, 2,5-bis (mercaptomethyl) -1-thian, 2,5-bis (2-mercaptoethyl) -1-thian, etc. di (mercapto _{C 1-4} alkyl) Chiang, aliphatic polyols [particularly, (poly) alkanediol _{((poly) C 2-10} etc. alkanediol) aliphatic diols] with a mercapto fatty acids such as [for example, mercaptoacetic acid , 3-mercaptopropionic acid, 3-mercaptobutyric acid, 4-mercaptobutyric acid, etc. Acid (e.g., mercapto _{C 2-10} alkanoic acid, preferably a mercapto _{C 2-6} alkanoic acid, more preferably a mercapto _{C 2-4} alkanoic acid) diester {e.g. with, etc.], an alkane diol di (mercaptoalkanoates) [ For example, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), 1,4-butanediol bis (2-mercaptoacetate), 1,4-butanediol bis (3-mercaptoprote) C _2-10 alkanediol di (mercapto C _2-10 alkanoate) such as pionate), 1,6-hexanediol bis (3-mercaptopropionate), 1,4-bis (3-mercaptobutyryloxy) butane ), Preferably C _2-6 alkanediol di (Mercapto C _2-6 alkanoate), more preferably C _2-4 alkanediol di (such as mercapto C _2-4 alkanoate)} and the like.

  The aliphatic dithiol compounds may be used alone or in combination of two or more.

Examples of aromatic dithiol compounds include dimercaptoarenes (eg, dimercapto C _6-12 arenes such as 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, preferably dimercapto C _{6. -10} arene, more preferably dimercapto C _6-8 arene, etc.), di (mercaptoalkyl) arene [for example, di (1,4-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene etc. Mercapto C _1-4 alkyl) arene, preferably di (mercapto C _1-4 alkyl) C _6-10 arene, more preferably di (mercapto C _1-2 alkyl) C _6-8 arene], di (mercaptoalkylaryl) ) Alkane [eg 2,2-bis (4-mercap) Methylphenyl) di propane (mercapto _{C 1-4} alkyl _{C 6-10 aryl) C 1-10} alkane, preferably di (mercapto _{C 1-2} alkyl _{C 6-10 aryl) C 1-6} alkane, di (Mercaptoaryl) sulfide [for example, di (mercaptoC _6-10 aryl) sulfide such as bis (4-mercaptophenyl) sulfide], di (mercaptoalkylaryl) sulfide [for example, bis (4-mercaptomethylphenyl) sulfide, etc. di (mercapto _{C 1-4} alkyl _{C 6-10} aryl) sulfide, di (mercaptomethyl aryl) ethers [such as di (mercapto _{C 6-10} aryl) ethers such as bis (4-mercapto-phenyl) ether, di (Mercaptoalkylaryl) ether For example, bis di (4-mercaptomethylphenyl) ether (mercapto _{C 1-4} alkyl _{C 6-10} aryl) ether, di (mercaptomethyl aryl) alkane [e.g., 2,2-bis (4-mercapto-phenyl) Di (mercapto C _6-10 aryl) C _1-10 alkanes such as propane, preferably di (mercapto C _6-10 aryl) C _1-6 alkanes], di (mercaptoaryl) alkanes [eg 2,2-bis Di (mercapto C _6-10 aryl) C _1-10 alkanes such as (4-mercaptophenyl) propane, preferably di (mercapto C _6-10 aryl) C _1-6 alkanes], heterocyclic aromatic dithiol compounds [ For example, thiophene dithiol (3,4-thiophene dithiol etc.)], fluore Such as dithiol compound having the skeleton.

Examples of the dithiol compound having a fluorene skeleton include a dithiol compound having a 9,9-bisphenylfluorene skeleton. Examples of such a dithiol compound include a compound represented by the following formula (2), a compound represented by the above formula (1A) and a mercaptocarboxylic acid {for example, mercapto fatty acid [for example, mercaptoacetic acid, 3-mercaptopropion] Mercaptoalkanoic acids such as acid, 3-mercaptobutyric acid, 4-mercaptobutyric acid (for example, mercapto C _2-10 alkanoic acid, preferably mercapto C _2-6 alkanoic acid, more preferably mercapto C _2-4 alkanoic acid) and the like] Etc.} and the like.

(Wherein R ¹ , R ² , R ³ , k, m and n are the same as above)
As a dithiol compound having a typical fluorene skeleton, 9,9-bis (mercaptophenyl) fluorene [eg, 9,9-bis (4-mercaptophenyl) fluorene], 9,9-bis (mercapto-alkylphenyl) Fluorene [e.g., 9,9-bis (mercapto-C) such as 9,9-bis (4-mercapto-3-methylphenyl) fluorene, 9,9-bis (4-mercapto-3,5-dimethylphenyl) fluorene _1-4 alkylphenyl) fluorene, etc.], 9,9-bis (mercapto-arylphenyl) fluorene [for example, 9,9-bis (mercapto) such as 9,9-bis (4-mercapto-3-phenylphenyl) fluorene. -C _6-10 aryl phenyl) said expression such as fluorene] in (2), n is Compound is; 9,9-bis (mercaptomethyl alkoxyphenyl) fluorene {e.g., 9,9-bis [4- (2-mercaptoethyl) phenyl] fluorene such as 9,9-bis [(mercapto _{C 2-4} alkoxy ) Phenyl] fluorene etc.}, 9,9-bis (mercaptoalkoxy-alkylphenyl) fluorene {e.g. 9,9-bis [4- (2-mercaptoethoxy) -3-methylphenyl] fluorene, 9,9-bis 9,9-bis [(mercapto C _2-4 alkoxy) -C _1-4 alkylphenyl] fluorene and the like such as [4- (2-mercaptoethoxy) -3,5-dimethylphenyl] fluorene} In 2), the compound etc. whose n is 1 or more (for example, 1-4) are mentioned.

  The compound represented by the formula (2) may be a commercially available product, or a compound synthesized by a conventional method (for example, the method described in JP-A-2002-338540). Also good.

Moreover, as a typical diester of the compound represented by the formula (1A) and mercaptocarboxylic acid, for example, 9,9-bis (mercaptoacyloxyphenyl) fluorene {for example, 9,9-bis [4- ( 9,9-bis (mercapto C _2-10 acyloxyphenyl) fluorene such as 2-mercaptoethylcarbonyloxy) phenyl] fluorene, 9,9-bis [4- (3-mercaptopropylcarbonyloxy) phenyl] fluorene, preferably 9,9-bis (mercapto _{C 2-6} alkanoyloxy phenyl) fluorene, and more preferably 9,9-bis (mercapto _{C 2-4} alkanoyloxy phenyl) fluorene}, 9,9-bis (mercaptomethyl acyloxyalkyl - alkylphenyl) Fluorene {eg, 9,9-bis [4- 2-mercaptoethylcarbonyloxy) -3-methylphenyl] fluorene, 9,9-bis [4- (3-mercaptopropylcarbonyloxy) -3-methylphenyl] fluorene, 9,9-bis [4- (3- mercaptopropyl-carbonyloxy) -3,5-dimethylphenyl] fluorene such as 9,9-bis (mercapto _{C 2-10} acyloxy - alkylphenyl) fluorene, preferably 9,9-bis (mercapto _{C 2-6} alkanoyloxy - C _1-4 alkyl phenyl) fluorene, and more preferably 9,9-bis (mercapto _{C 2-4} alkanoyloxy _{-C 1-4} alkylphenyl) fluorene}, 9,9-bis (mercaptomethyl acyloxyalkyl - aryl phenyl) fluorene { For example, 9,9-bis [4- (3-merca Hept propyl carbonyloxy) -3-phenyl phenyl] fluorene such as 9,9-bis (mercapto _{C 2-10} acyloxy - aryl phenyl) fluorene, preferably 9,9-bis (mercapto _{C 2-6} alkanoyloxy -C _{6 -10} aryl phenyl) fluorene, and more preferably in the 9,9-bis (the expression, such as mercapto _{C 2-4} alkanoyloxy _{-C 6-8} aryl phenyl) fluorene} (1A), compounds wherein n is 0 and mercapto Diesters with carboxylic acids; 9,9-9,9-bis (mercaptoacyloxyalkoxyphenyl) fluorene {e.g., 9,9-bis [4- (2- (3- (mercaptopropylcarbonyloxy) ethoxy) phenyl] fluorene, etc. - bis (mercapto _{C 2-10} Ashiruo Shi alkoxyphenyl) fluorene, preferably 9,9-bis (mercapto _{C 2-6} alkanoyloxy _{C 2-4} alkoxyphenyl) fluorene, and more preferably 9,9-bis (mercapto _{C 2-4} alkanoyloxy _{C 2-4} Alkoxyphenyl) fluorene}, 9,9-bis (mercaptoacyloxy-alkylphenyl) fluorene {eg, 9,9-bis [4- (2- (3-mercaptopropylcarbonyloxy) ethoxy) -3-methylphenyl] fluorene 9,9-bis [mercapto C _2-10 acyloxyalkoxy-alkylphenyl) such as 9,9-bis [4- (2- (3-mercaptopropylcarbonyloxy) ethoxy) -3,5-dimethylphenyl] fluorene Fluorene, preferably 9,9-bis (me Lucapto C _2-6 alkanoyloxy C _2-4 alkoxy-C _1-4 alkylphenyl) fluorene, more preferably 9,9-bis (mercapto C _2-4 alkanoyloxy C _2-4 alkoxy-C _1-4 alkylphenyl) ) Fluorene}, 9,9-bis (mercaptoacyloxyalkoxy-arylphenyl) fluorene {eg, 9,9-bis [4- (2- (3-mercaptopropylcarbonyloxy) ethoxy) -3-phenylphenyl] fluorene, etc. 9,9-bis (mercapto C _2-10 acyloxyalkoxy-arylphenyl) fluorene, preferably 9,9-bis (mercapto C _2-6 alkanoyloxy C _2-4 alkoxy-C _6-10 arylphenyl) fluorene, More preferably, 9,9-bis (me In the above formula (1A) such as lucapto C _2-4 alkanoyloxy C _2-4 alkoxy-C _6-8 arylphenyl) fluorene}, a compound in which n is 1 or more (for example, 1 to 4), mercaptocarboxylic acid, Of diesters.

  The compound represented by the compound represented by the formula (1A) and the diester of mercaptocarboxylic acid may use a commercially available product, and is represented by a conventional method (for example, the formula (1A). A compound synthesized by a thioester formation reaction of a compound with a mercaptocarboxylic acid or a derivative thereof (acid halide, lower alkyl ester, etc., for example, a method described in JP-A-8-59775) may be used.

  Aromatic dithiol compounds may be used alone or in combination of two or more.

Preferred dithiol compounds include aliphatic dithiol compounds from the viewpoint of enethiol reactivity and the like. Therefore, the dithiol compound may contain at least an aliphatic dithiol compound. In particular, alkanedithiols (eg C _2-10 alkanedithiols such as 1,2-ethanedithiol, 1,3-propanedithiol, preferably C _2-6 alkanedithiols, especially C _2-4 alkanedithiols, etc.), polyalkanes Aliphatic dithiol compounds such as dithiols (eg, poly C _2-4 alkanedithiols such as bis (2-mercaptoethyl) sulfide, 1,2-bis (2-mercaptoethylthio) ethane) It is advantageous in that the content is large and the refractive index is increased.

  From the viewpoint of increasing the refractive index, an aromatic dithiol compound (for example, a dithiol compound having a 9,9-bisphenylfluorene skeleton) may be preferably used. Therefore, the dithiol compound may contain an aromatic dithiol compound. In addition, when an aliphatic dithiol compound is used, a high-strength thermoplastic resin excellent in moldability (film moldability, etc.) and improved in brittleness can be efficiently obtained by introducing an aliphatic skeleton.

  As will be described later, the thermoplastic resin of the present invention is a thermoplastic resin obtained by an enethiol reaction between the fluorene compound and the dithiol compound. That is, the thermoplastic resin of the present invention is not a resin cross-linked in a three-dimensional network, but has thermoplasticity despite the use of a fluorene compound having two ethylenically unsaturated bonds (particularly allyl groups). It is a polymer. For example, when the diallyl ether compound represented by the formula (1) is used as the fluorene compound, the diallyl ether compound represented by the formula (1) and the dithiol compound [that is, HS-X-SH (wherein , X represents a residue of a dithiol compound)], and the thermoplastic resin of the present invention obtained by the enethiol reaction is a thermoplastic resin having a repeating unit represented by the following formula (a).

(In the formula, X represents a residue of a dithiol compound, and Z, R ¹ , R ² , R ³ , k, m, and n are the same as described above.)
In the formula (a), X represents a residue of the dithiol compound, that is, a group obtained by removing two mercapto groups from the thiol compound.

  Although the molecular weight of the thermoplastic resin of this invention is not specifically limited, For example, even if it is a weight average molecular weight, 2000-500000, Preferably it is 3000-200000, More preferably, it is about 4000-100000 (for example, 4000-50000). It may be about 3000 to 30000 (for example, 3500 to 20000).

  Moreover, the glass transition temperature of the thermoplastic resin of the present invention may be, for example, about 40 to 250 ° C., preferably 50 to 200 ° C., and more preferably about 60 to 170 ° C. (for example, 70 to 150 ° C.).

  The thermoplastic resin of the present invention has a high refractive index. For example, the refractive index of the thermoplastic resin at a wavelength of 589 nm is 1.6 or more (for example, 1.62 to 1.8), preferably 1. .63 to 1.78, more preferably about 1.64 to 1.75 (for example, 1.65 to 1.72), and 1.65 or more (for example, 1.66 to 1.75, (Preferably 1.67 to 1.72, more preferably about 1.68 to 1.7).

  Since the thermoplastic resin of the present invention is a resin obtained by an enethiol reaction (that is, an addition reaction), it has not only optical characteristics but also various excellent characteristics as described above. For example, the thermoplastic resin of the present invention has a lower shrinkage rate than a resin obtained by radical polymerization. Further, since it can be produced without using a radical polymerization initiator or the like, it is a low-yellowing thermoplastic resin.

  Note that the thermoplastic resin of the present invention is a practical thermoplastic resin with little thiol odor derived from the remaining dithiol compound because the enethiol reaction can be selectively advanced efficiently.

(Production method)
The thermoplastic resin of the present invention can be produced by reacting a fluorene compound and a dithiol compound (enthiol reaction).

  In the enthiol reaction, the ratio (use ratio) of the fluorene compound and the dithiol compound is the former / the latter (molar ratio) = 1 / 0.7 to 0.7 / 1, preferably 1 / 0.8 to 0.8 /. 1, more preferably 1 / 0.9 to 0.9 / 1, particularly about 1 / 0.95 to 0.95 / 1, and may be used in equimolar (or almost equimolar). . In the present invention, the quantitative enethiol reaction between the fluorene compound and the dithiol compound can surely proceed, or the molar ratio of the fluorene compound to the dithiol compound is adjusted (for example, the reaction is carried out in an equimolar or almost equimolar amount). ), A thermoplastic resin with little thiol odor derived from the residual dithiol compound can be obtained.

  The reaction (enethiol reaction) between the fluorene compound and the compound represented by the formula (3) may be performed in the presence of a polymerization initiator. The polymerization initiator can be selected according to the type of ethylenically unsaturated bond (high radical polymerization reactivity, etc.) in the fluorene compound. For example, a thermal polymerization initiator {or a thermal radical generator, for example, a peroxide. [Dialkyl peroxides (di-t-butyl peroxide, dicumyl peroxide, etc.), diacyl peroxides (lauroyl peroxide, benzoyl peroxide, etc.), peracid esters, ketone peroxides, peroxycarbonate , Organic peroxides such as peroxyketals], azo compounds [for example, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (isobutyronitrile), 2, Azonitrile compounds such as 2′-azobis (2-methylbutyronitrile)], Initiator (photo-radical generator) and the like.

  In particular, in the present invention, a thermal polymerization initiator or a photopolymerization initiator (particularly, a photopolymerization initiator) is preferably used as a polymerization initiator in order to efficiently and selectively cause an enethiol reaction to obtain a thermoplastic resin. Can do. The polymerization initiators may be used alone or in combination of two or more.

  Examples of the photopolymerization initiator include benzoins (benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether); acetophenones (acetophenone, p-dimethylacetophenone, 2- Hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-phenyl-2 -Hydroxy-acetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, etc .; propiophenones (p-dimethylaminopropiophenone, 2-hydroxy-2- Butyl-propiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc.); butyrylphenones [1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl- 1-propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-propan-1-one, etc.] Aminoacetophenones [2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2; -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2-methyl-1-phenyl Pan-1-one, 2-diethylamino-2-methyl-1-phenylpropan-1-one, 2-methyl-2-morpholino-1-phenylpropan-1-one, 2-dimethylamino-2-methyl-1 -(4-methylphenyl) propan-1-one, 1- (4-butylphenyl) -2-dimethylamino-2-methylpropan-1-one, 2-dimethylamino-1- (4-methoxyphenyl)- 2-methylpropan-1-one, 2-dimethylamino-2-methyl-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-dimethylaminophenyl) -Butan-1-one etc.]; benzophenones (benzophenone, benzyl, N, N′-bis (dimethylamino) benzophenone (Michler's ketone), 3 N, N′-dialkylaminobenzophenone, such as 1,3-dimethyl-4-methoxybenzophenone); ketals (acetophenone dimethyl ketal, benzyldimethyl ketal, etc.); thioxanthenes (thioxanthene, 2-chlorothioxanthene, 2, 4-diethylthioxanthene); anthraquinones (2-ethylanthraquinone, 1-chloroanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, etc.); (thio) xanthones (thioxanthone, 2,4-dimethyl) Thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone); acridines (1,3-bis- (9-acridinyl) propane, 1,7-bis- (9-acrylic) Nyl) heptane, 1,5-bis- (9-acridinyl) pentane, etc.); triazines (2,4,6-tris (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6 -Bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, etc.); sulfides (eg benzyldiphenyl sulfide); acyl Examples include phosphine oxides (such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide); titanocene photopolymerization initiators; oxime esters. These photopolymerization initiators can be used alone or in combination of two or more.

  The photopolymerization initiator can be obtained as a commercial product, for example, trade names “Irgacure” “Darocur” (manufactured by Ciba Specialty Chemicals), trade name “Syracure” (manufactured by Union Carbide), and the like.

  The ratio of the polymerization initiator (such as the photopolymerization initiator) (or the ratio of the polymerization initiator in the composition containing the fluorene compound, the dithiol compound and the polymerization initiator) is based on 100 parts by weight of the total amount of the fluorene compound and the dithiol compound. For example, it can select from the range of about 0.1-15 weight part (for example, 0.2-10 weight part), for example, 0.3-10 weight part (for example, 0.5-7 weight part), Preferably May be about 0.7 to 5 parts by weight.

  In addition, you may combine a photoinitiator with a photosensitizer. Examples of the photosensitizer include conventional components such as tertiary amines [for example, trialkylamine, trialkanolamine (such as triethanolamine), ethyl N, N-dimethylaminobenzoate, N, N-dimethyl. Dialkylaminobenzoic acid alkyl esters such as amyl aminobenzoic acid, bis (dialkylamino) benzophenones such as 4,4-bis (dimethylamino) benzophenone (Michler's ketone), 4,4′-diethylaminobenzophenone], triphenylphosphine, etc. Examples include phosphine, toluidines such as N, N-dimethyltoluidine, anthracene such as 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. It is done. The photosensitizers may be used alone or in combination of two or more.

  The amount of the photosensitizer used is, for example, 0.1 to 150 parts by weight (for example, 1 to 100 parts by weight), preferably 5 to 75 parts by weight (for example, with respect to 100 parts by weight of the photopolymerization initiator). 10 to 50 parts by weight).

  In addition, you may perform reaction (ene thiol reaction) in a solvent. Examples of the solvent include alcohols (alkyl alcohols such as ethanol, propanol, and isopropanol, glycols such as ethylene glycol and propylene glycol), hydrocarbons (aliphatic hydrocarbons such as hexane, and alicyclic rings such as cyclohexane). Formula hydrocarbons, aromatic hydrocarbons such as toluene and xylene), halogenated hydrocarbons (methylene chloride, chloroform, etc.), ethers (chain ethers such as dimethyl ether, diethyl ether, dioxane, tetrahydrofuran, etc.) Cyclic ethers), esters (methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, ethyl butyrate, etc.), ketones (acetone, ethyl methyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-2-pyrrole) Cellosolves (methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc.), carbitols (methylcarbitol, ethylcarbitol, butylcarbitol, etc.), propylene glycol monoalkyl ethers (propylene glycol monomethyl ether, propylene glycol mono) Ethyl ether, propylene glycol mono n-butyl ether, etc.), glycol ether esters (ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate etc.), amides (N, N-dimethylformamide, N, N-dimethylacetamide etc.), Sulfoxides (dimethyl sulfoxide, etc.), nitriles (acetonitrile, benzonitrile, etc.), N-methylpyrrolidone Which organic solvents. The solvent can be used alone or as a mixed solvent.

  The ratio of the total amount of fluorene compound and dithiol compound in the solvent (the ratio of the total amount of fluorene compound and dithiol compound in the composition containing the solvent) is, for example, 1 to 90% by weight, preferably 3 to 80% by weight, more preferably May be about 5 to 50% by weight.

  The enethiol reaction proceeds by bringing a fluorene compound and a dithiol compound into contact with each other. Usually, the reaction (enthiol reaction) may be performed by applying active energy to a reaction system including a fluorene compound and a dithiol compound. By applying active energy, the enethiol reaction can be easily advanced.

  As the active energy, thermal energy and / or light energy (particularly, at least light energy) can be used depending on the type of the polymerization initiator.

  In the case of applying thermal energy, the heating temperature may be, for example, 50 to 250 ° C, preferably 60 to 200 ° C, and more preferably about 80 to 180 ° C. The application (heating) of thermal energy may be performed not only when a thermal polymerization initiator is used as an initiator but also when a photopolymerization initiator is used.

  In addition, when applying (or irradiating) light energy (for example, when using a photopolymerization initiator), as the light, radiation (gamma rays, X-rays, etc.), ultraviolet rays, visible rays, etc. can be used. Usually, it is often ultraviolet rays. In addition, when using a thermal polymerization initiator as an initiator, irradiation of light energy is not necessarily required.

  As the light source, for example, in the case of ultraviolet rays, a deep UV lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a halogen lamp, a laser light source (light source such as helium-cadmium laser or excimer laser), etc. Can be used. The wavelength of light may be, for example, about 150 to 800 nm, preferably 150 to 600 nm, more preferably about 200 to 400 nm (particularly 300 to 400 nm). The amount of irradiation light (irradiation energy) is not particularly limited, and can be selected from a range of about 1 mW to 10000 W (for example, 0.05 to 7000 W), for example, 0.1 to 5000 W, preferably 1 to 3000 W, and more preferably 10 About 2000W (for example, 30-1000W) may be sufficient. The irradiation time is not particularly limited, and may be, for example, 5 seconds to 5 hours, preferably 10 seconds to 2 hours, more preferably about 30 seconds to 1 hour, and usually about 1 to 30 minutes. May be.

  Note that heat energy (heating) and light energy (light irradiation) may be combined.

  As described above, the thermoplastic resin of the present invention is obtained. Separation and purification of the thermoplastic resin from the reaction mixture can be performed using a conventional method.

  In addition, the thermoplastic resin of this invention is obtained by reaction (enthiol reaction) of a fluorene compound and a dithiol compound as mentioned above. Therefore, the present invention includes a composition (composition for enthiol reaction) containing at least a fluorene compound and a dithiol compound. That is, such a composition is useful as a composition for obtaining the thermoplastic resin. In addition, the said composition may contain the polymerization initiator and the solvent, and the ratio of each component is the same as the said ratio (use ratio).

  Moreover, the diallyl ether compound represented by the formula (1) is also included in the present invention. Such a compound can be used for various uses (for example, optical materials) as a heat or photopolymerizable resin, including the raw material of the thermoplastic resin.

  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.

(1) Refractive index The refractive index of the compound obtained in Example 1 is maintained at a temperature of 25 ° C. using a multi-wavelength Abbe refractometer [manufactured by Atago, DR-M2 (using a circulating water bath 60-C3)]. The refractive index at 589 nm was measured by extrapolation.

  Moreover, the refractive index of the thermoplastic resin obtained in Examples 2 and 3 was measured as follows.

  0.3 parts by weight of the sample was added to a beaker containing 10 parts by weight of cyclohexanone, and stirred and dissolved at room temperature. 1 ml of the obtained solution is dropped on a glass substrate or a silicon substrate, spin-coated with a spin coater (1H-DX, manufactured by Mikasa), and dried at 80 ° C. for 3 minutes on a hot plate to obtain a transparent film. It was. The refractive index of the obtained cured film was measured at a wavelength of 589 nm using an optical interference film thickness meter (reflected spectral film thickness meter FE-3000 manufactured by Otsuka Electronics Co., Ltd.).

(2) Weight average molecular weight Mw
Using a GPC apparatus (Shodex GPC-101 manufactured by Showa Denko KK), three LF-804s manufactured by Shodex were used for the column, the solvent was THF, and the molecular weight in terms of styrene was measured at 40 ° C.

(3) ¹ H-NMR spectrum Using AL-300 manufactured by JEOL Ltd., 0.02 g of sample was dissolved in 0.4 ml of deuterated chloroform, and 1H-NMR spectrum of the sample was measured. (4) IR spectrum Thermo Fisher Scientific The IR spectrum of the sample was measured using NICOLET 4700 manufactured by Tific.

(5) Melting point (glass transition temperature)
Glass transition temperature was measured under a nitrogen atmosphere using a differential scanning calorimeter (DSC) EXSTAR DSC6000 manufactured by SII Nano Technology.

(6) Thermal decomposition temperature The differential thermal thermogravimetric simultaneous measurement apparatus (TG / DTA) made by SII Nanotechnology Co., Ltd. The thermal decomposition temperature was measured under an atmosphere of nitrogen using EXSTAR TG / DTA6000.

(7) LC / MS
Shimadzu High Performance Liquid Chromatograph Mass Spectrometer (LC / MS) Mass spectrum was measured using LCMS-2010A.

(8) HPLC
The LC purity was measured using a high-performance liquid chromatograph LaChrom Elite manufactured by Hitachi High-Technologies.

Example 1
To a 500 ml four-necked separable flask equipped with a stirrer, 20.3 parts by weight (0.045 mol) of 9,9-bis (6-hydroxy-2-naphthyl) fluorene (BNF, Osaka Gas Chemical Co., Ltd.) 16.4 parts by weight (0.135 mol) of allyl bromide (manufactured by Kanto Chemical Co., Ltd.) and 27.4 parts by weight (0.2 mol) of potassium carbonate (manufactured by Kanto Chemical Co., Ltd.) at 50 ° C. with 40 ml of methyl ethyl ketone. The reaction was stirred at reflux for an hour. After confirming disappearance of the raw material BNF by HPLC, the formed salt was filtered, concentrated under reduced pressure at 50 ° C. and 10 torr, 100 parts by weight of ethanol was added, and the mixture was heated to 50 ° C. and dissolved. When cooled to 10 ° C. or lower, white crystals were formed. The obtained crystals were filtered and dried at 85 ° C. for 24 hours to obtain 19.1 parts by weight (yield 80%). When the obtained crystal was analyzed by HPLC, the purity was 94%. Moreover, NMR and IR of the obtained crystal were measured, and it was confirmed that it was the target product [9,9-bis (6-allyloxy-2-naphthyl) fluorene] represented by the following formula.

¹ H-NMR (CDCl ₃ -300 MHz): δ (ppm) = 7.81 (d, 2H, J = 7.5 Hz), 7.25-7.62 (m, 14H), 7.10 (d, 4H, J = 7.2 Hz), 6.03-6.16 (m, 2H), 5.23-5.47 (m, 4H), 4.62 (d, 4H, J = 5.4 Hz)
Melting point 140.0 ° C., refractive index 1.697

(Example 2)
In a 20 ml sample container, 1.06 parts by weight (2 mmol) of the compound synthesized in Example 1, 0.19 parts by weight (2 mmol) of 1,2-ethanedithiol (manufactured by Kanto Chemical Co., Ltd.), photopolymerization initiator ( IRGACURE 184 (manufactured by Ciba Japan) 0.02 parts by weight and 10 parts by weight of tetrahydrofuran (THF) were stirred and dissolved, and then stirred with an ultraviolet irradiation device (SP-9 manufactured by Ushio Electric Co., Ltd.) Ultraviolet irradiation was performed at 250 W for 600 seconds. When the obtained reaction solution was dropped into a 300 ml beaker containing 150 parts by weight of hexane, white crystals were formed. The obtained slurry was filtered and dried under reduced pressure at 40 ° C. for 1 hour to obtain 1.1 parts by weight (yield 88%) of white crystals. When NMR of the obtained crystal was measured, it was confirmed to be a thermoplastic resin having a repeating unit represented by the following formula.

¹ H-NMR (CDCl ₃ -300 MHz): δ (ppm) = 7.77 (d, 2H, J = 5.7 Hz), 7.23-7.59 (m, 14H), 7.01-7. 04 (m, 4H), 4.09 (m, 4H), 2.73 (m, 4H), 2.32-2.36 (m, 4H) 2.05 (m, 4H)
The obtained crystal had a molecular weight Mw of 8000, a melting point of 116.5 ° C., a 5% thermogravimetric reduction temperature of 331 ° C., and a refractive index of 1.687.

In addition, by measuring the IR spectrum of the obtained crystal, it was confirmed that the peak of the allyl group derived from the compound synthesized in Example 1 (near 940 cm ⁻¹ ) disappeared.

  Moreover, when the odor (thiol odor) of the obtained crystal was confirmed, there was almost no thiol odor.

(Example 3)
In a 20 ml sample container, 1.06 parts by weight (2 mmol) of the compound synthesized in Example 1, 0.22 parts by weight (2 mmol) of 1,3-propanedithiol (manufactured by Kanto Chemical Co., Ltd.), photopolymerization initiator ( IRGACURE 184 (manufactured by Ciba Japan) 0.02 parts by weight and 10 parts by weight of THF were stirred and dissolved, and then stirred for 250 seconds at 250 W using an ultraviolet irradiation device (SP-9 manufactured by Ushio Electric Co., Ltd.). UV irradiation was performed. When the obtained reaction solution was dropped into a 300 ml beaker containing 150 parts by weight of hexane, white crystals were formed. The obtained slurry was filtered and dried under reduced pressure at 40 ° C. for 1 hour to obtain 1.2 parts by weight (yield 94%) of white crystals. When NMR of the obtained crystal was measured, it was confirmed to be a thermoplastic resin having a repeating unit represented by the following formula.

¹ H-NMR (CDCl ₃ -300 MHz): δ (ppm) = 7.79 (d, 2H, J = 7.2 Hz), 7.21-7.64 (m, 14H), 7.01-7. 09 (m, 4H), 4.10 (s, 4H), 2.58-2.71 (m, 8H), 1.82-2.05 (m, 6H)
The obtained crystal had a molecular weight Mw of 4000, a melting point of 73.1 ° C., a 5% thermogravimetric reduction temperature of 304 ° C., and a refractive index of 1.688.

In addition, by measuring the IR spectrum of the obtained crystal, it was confirmed that the peak of the allyl group derived from the compound synthesized in Example 1 (near 940 cm ⁻¹ ) disappeared.

  Moreover, when the odor (thiol odor) of the obtained crystal was confirmed, there was almost no thiol odor.

  The thermoplastic resin (and diallyl ether compound) of the present invention is derived from the sulfur atom introduced into the resin skeleton and the 9,9-bis-fused polycyclic aryl fluorene skeleton, and thus has excellent heat resistance and high refractive index. Characteristics (particularly optical characteristics). Moreover, since it is a thermoplastic resin, various molding methods, such as extrusion molding and injection molding, can be applied, it is highly practical, and various forms of molded products can be obtained efficiently. Therefore, the thermoplastic resin (and diallyl ether compound) of the present invention can be suitably used for optical lenses, optical films or optical sheets, pickup lenses, holograms, liquid crystal films, organic EL films, and the like. Further, the thermoplastic resin (and diallyl ether compound) of the present invention can be used for paints, antistatic agents, inks, adhesives, adhesives, resin fillers, charging trays, conductive sheets, protective films (electronic devices, liquid crystal members, etc.). Protective film, etc.), electrical / electronic materials (carrier transport agent, light emitter, organic photoreceptor, thermal recording material, hologram recording material), electrical / electronic components or equipment (optical disc, inkjet printer, digital paper, organic semiconductor laser, dye) Suitable for resins for sensitized solar cells, EMI shield films, photochromic materials, organic EL elements, color filters, etc.), resins for machine parts or equipment (automobiles, aerospace materials, sensors, sliding members, etc.), etc. Available. In particular, since the thermoplastic resin (and diallyl ether compound) of the present invention is excellent in optical properties, it is useful for constituting (or forming) a molded product (optical molded product) for optical applications such as an optical film. It is.

Claims (9)

A thermoplastic resin obtained by an enethiol reaction between a 9,9-bis-fused polycyclic arylfluorene skeleton and a fluorene compound having two ethylenically unsaturated bonds and a dithiol compound , wherein the fluorene compound is represented by the following formula (1) include diallyl ether compound represented by), dithiol compound comprises a C _2-6 alkane thiol, thermoplastic resin.

Wherein ring Z is a condensed polycyclic arene ring, R ¹ and R ² are the same or different substituents, k is an integer of 0-4, m is an integer of 0-4, R ³ is an alkylene group, n Represents an integer of 0 to 4.) In the formula (1), a thermoplastic resin according to claim 1, wherein ring Z is a naphthalene ring. R ¹ Is a cyano group or C _1-4 An alkyl group, R ² But C _1-4 Alkyl group, C _6-10 Aryl group, C _1-4 An alkoxy group, R ³ Is C _2-4 The thermoplastic resin according to claim 1 or 2, which is an alkylene group, wherein k is 0 or 1, m is 0 to 2, and n is 0 to 2. In formula (1), n is 0, The thermoplastic resin in any one of Claims 1-3 . A fluorene compound having a 9,9-bis-fused polycyclic arylfluorene skeleton and two ethylenically unsaturated bonds is reacted with a dithiol compound to produce a thermoplastic resin according to any one of claims 1 to 4. A manufacturing method in which the fluorene compound contains a diallyl ether compound represented by the following formula (1), and the dithiol compound contains C _2-6 alkanedithiol .

Wherein ring Z is a condensed polycyclic arene ring, R ¹ and R ² are the same or different substituents, k is an integer of 0-4, m is an integer of 0-4, R ³ is an alkylene group, n Represents an integer of 0 to 4.) The production method according to claim 5 , wherein the composition containing the fluorene compound, the dithiol compound and the photopolymerization initiator is irradiated with light to cause an enethiol reaction. The diallyl ether compound represented by formula (1) according to claim 1 as a fluorene compound having a 9,9-bis-fused polycyclic arylfluorene skeleton and two ethylenically unsaturated bonds, and C ₂ as a dithiol compound _-6 a composition comprising an alkane thiol, comprises the fluorene compound diallyl ether compound represented by the following formula (1), dithiol compound comprises a C _2-6 alkane thiol, composition.

Wherein ring Z is a condensed polycyclic arene ring, R ¹ and R ² are the same or different substituents, k is an integer of 0-4, m is an integer of 0-4, R ³ is an alkylene group, n Represents an integer of 0 to 4.) Furthermore, the composition of Claim 7 containing a photoinitiator. Diallyl ether compound represented by the following formula (1).

Wherein ring Z is a condensed polycyclic arene ring, R ¹ and R ² are the same or different substituents, k is an integer of 0-4, m is an integer of 0-4, R ³ is an alkylene group, n Represents an integer of 0 to 4.)