JP2004339499A - Fluorene-based composition and molded product of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a fluorene-based composition having excellent diepersibility of an additive and capable of making the additive exhibit its function, by mixing a small amount of a fluorene compound into the composition, and to obtain a molded product of the same. <P>SOLUTION: This fluorene-based composition contains the compound expressed by formula (I) [X<SP>1</SP>and X<SP>2</SP>are identical to or different from each other and are each a hydroxy, -O(AO)<SB>p</SB>H (A is a 2-3C alkylene; and p is an integer of 1 or more), amino or an N-monosubstituted amino; R<SP>1</SP>to R<SP>4</SP>are identical to or different from each other and are each a nonreactive group; m1 and m2 are identical to or different from each other and are each 0 or an integer of 1 to 3, and (m1+m2) is an integer of 1 to 6; and n1 to n4 are identical to or different from each other and are each an integer of 0 to 4; provided that (m1+n1) and (m2+n2) are each an integer of 0 to 5] or its derivative and the additive. The molded product is formed by using the composition. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a composition containing a compound having a fluorene skeleton and an additive, and a molded article thereof.

  In some cases, additives such as colorants (such as pigments) and fillers are added to the resin material in order to improve the function. Additives include, for example, conductive particles mixed with resin for antistatic and conductive applications, coloring agents such as pigments mixed with transparent resin for colored filter applications, and resin mixed for high strength structural applications (For example, carbon materials such as carbon fiber and carbon powder) are used.

  When an additive such as a coloring agent or a filler is added to the resin, its function is improved, but the resin becomes brittle or the dispersion stability is reduced. In particular, when a compound containing an aromatic ring is used as an additive, the tendency is remarkable. For example, when a coloring agent having an aromatic ring is blended, the moldability of the resin (resin composition) may be reduced. In addition, the amount of the carbon material such as carbon fiber and carbon powder is increased with respect to the resin in order to exhibit a sufficient function, and the mechanical properties of the resin are reduced.

As a resin having a fluorene skeleton, for example, JP-A-2-73816 (Patent Document 1) discloses a heat-resistant resin obtained from 9,9-bis (4-hydroxyphenyl) fluorene, maleic acid and terephthalic acid. Water soluble or solvent insoluble unsaturated polyesters are disclosed.
JP-A-2-73816 (claims, page 2, lower left column, lines 3-7)

  Therefore, an object of the present invention is to provide a fluorene-based composition which is excellent in dispersibility of an additive and can exhibit the function of the additive with a small amount of compounding, and a molded article thereof.

  Another object of the present invention is to provide a fluorene-based composition which can be highly dispersed even if the additive is a compound having an aromatic ring, and which can effectively exhibit the properties of a resin, and a molded article thereof.

  Still another object of the present invention is to provide a fluorene-based composition capable of improving the dispersibility and coloring (coloring degree) of a coloring agent and a filler, and a molded article thereof.

  The present inventors have conducted intensive studies to achieve the above object, and as a result, when a compound having a fluorene skeleton or a derivative thereof is combined with an additive, the dispersibility of the additive can be improved, and even when the amount is small, the additive The present inventors have found that the function can be effectively exhibited, and completed the present invention.

  That is, the composition of the present invention contains a compound represented by the following formula (I) or a derivative thereof, and an additive.

[In the formula, X ¹ and X ² are the same or different and each is a hydroxyl group, -O (AO) _pH group (where A represents a C _2-3 alkylene group, and p represents an integer of 1 or more. ), An amino group or an N-monosubstituted amino group, R ^{1 to} R ⁴ are the same or different and represent a non-reactive group, m1 and m2 are the same or different and are integers of 0 or 1 to 3, m1 + m2 = It is an integer of 1 to 6, and n1 to n4 are the same or different and are integers of 0 to 4. However, m1 + n1 and m2 + n2 are integers of 0-5. ]
The derivative of the compound represented by the formula (I) may be a resinous substance (oligomer or resin), for example, a polyester resin, a polycarbonate resin, a urethane resin, an acrylic resin, a polyamide resin, Resins such as a polyimide resin, an epoxy resin, a vinyl ester resin, a phenol resin, and an aniline resin may be used. The additive may be composed of a filler, a coloring agent, a flame retardant, and the like. The additive may be a compound having an aromatic ring. The additive may be a carbon material. The ratio of the additive is about 0.1 to 300 parts by weight based on 100 parts by weight of the compound (I) or a derivative thereof. When the derivative of the compound (I) is a resin, the ratio of the additive may be about 0.3 to 50 parts by weight based on 100 parts by weight of the resin. The composition of the present invention can also be used as a coating composition (or coating solution).

  The present invention also includes a molded article formed from the composition. The present invention also includes a method for improving the dispersibility of an additive by using the compound (I) or a derivative thereof. As described above, in the present invention, the dispersibility of the additive can be improved, so that the characteristics of the additive can be improved. For example, by using the compound (I) or a derivative thereof, the coloring property or coloring degree of the coloring agent can be improved.

  In the present invention, since the compound having the fluorene skeleton and the additive are combined, the dispersibility of the additive is improved, and the function of the additive can be exhibited even with a small amount of compounding. Further, even when the additive is a compound having an aromatic ring, the dispersibility is excellent, and the properties of the resin can be prevented from deteriorating. For example, the dispersibility and coloring (coloring degree) of the coloring agent and the filler can be greatly improved.

  The fluorene-based composition of the present invention contains the compound represented by the formula (I) or a derivative thereof and an additive.

[Compound (I) having fluorene skeleton or derivative thereof]
In the formula (I), p represents the number of repeating oxyalkylene groups, preferably an integer of 1 to 50, preferably an integer of 1 to 30, and more preferably an integer of 1 to 10 (for example, 1 to 5). It is.

The N-monosubstituted amino group represented by X ¹ and X ² was substituted with a hydrocarbon group (C _1-6 alkyl group, C _5-6 cycloalkyl group, C _6-10 aryl group, etc.). And N-monosubstituted amino groups.

The substitution position of X ¹ and X ² is not particularly limited, and may be any of the o-, m- and p-positions with respect to fluorene, but the m- and / or p-positions are preferred.

In the formula (I), the term "non-reactive group" means a group that is non-reactive with a reaction such as an ester bond forming reaction, a urethane bond forming reaction, an amide bond forming reaction, and an imide bond forming reaction. The non-reactive groups represented by R ^{1 to} R ⁴ include a hydrocarbon group, an alkoxy group, an N, N-disubstituted amino group, a halogen atom, and the like. Examples of the hydrocarbon include a linear or branched C _1-6 alkyl group (such as a methyl group), a linear or branched C _2-6 alkenyl group (such as a vinyl group), and a C _5-6 cycloalkyl group (such as a cyclohexyl group). , A _C5-6 cycloalkenyl group (such as a cyclohexenyl group), a _C6-10 aryl group (such as a phenyl group), a _C6-10 aryl-linear or branched _C1-4 alkyl group (such as a benzyl group). No. The alkoxy group includes a linear or branched C _1-6 alkoxy group such as a methoxy group, and the N, N-disubstituted amino group corresponds to the N-monosubstituted amino group and the hydrocarbon group And a disubstituted amino group (such as a dimethylamino group). Halogen atoms include fluorine, chlorine, bromine and iodine atoms.

  n1 and n2 are preferably an integer of 0 to 2, and more preferably 0 or 1. n3 and n4 are preferably an integer of 0 to 3, more preferably an integer of 0 to 2, especially 0 or 1. m1 and m2 are each often an integer of 1 to 3, preferably an integer of 1 to 2 (particularly 1), and are usually 1 (m1 = m2 = 1), 2 (m1 = m2 = 2) or 3 (m1 = m2 = 3).

The substitution position of the group X ¹ (or X ² ) is not particularly limited, and can be selected from the 2 to 6 positions of the phenyl group substituted at the 9 position of fluorene. For example, when m1 (or m2) is 1, the substitution position of the group X ¹ (or X ² ) may be, for example, 2 to 6 (preferably 2 or 4 and particularly 4), and m1 When (or m2) is 2, it may be, for example, 3,4-position, 3,5-position, etc., and when m1 (or m2) is 3, for example, 3,4,5-position, 2 , 3,4-position, 2,3,5-position, 2,3,6-position and the like.

Among the compounds of the above formula (I), compounds in which m1 = m2 = 1, 2 or 3, ie, bisphenolfluorene [9,9-bis (monohydroxyphenyl) fluorenes], 9,9-bis (dihydroxyphenyl) ) Fluorenes, bisphenolfluorenes such as 9,9-bis (trihydroxyphenyl) fluorenes and their C _2-4 alkylene oxide adducts (9,9-bis (hydroxyphenyl) fluorenes); and bisanilinefluorene and Bisanilinefluorenes (9,9-bis (aminophenyl) fluorenes) such as bis (N-monosubstituted aniline) fluorene are preferred.

Among the above bisphenolfluorenes, bisphenolfluorene includes 9,9-bis (4-hydroxyphenyl) fluorene (bisphenolfluorene, BPF); biscresolfluorene (BCF, for example, 9,9-bis (4-hydroxy-3). 9,9-bis (C _1-4 alkylhydroxyphenyl) fluorene such as -methylphenyl) fluorene, 9,9-bis (3-hydroxy-2-methylphenyl) fluorene; 9,9-bis (4-hydroxy- 3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-2,6-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-di-t-butylphenyl) fluorene 9,9-bis (such as di-C _1-4 alkyl-hydroxyphenyl) fluorene; This Corresponds to the compound, bisphenol fluorenes are exemplified substituents R ¹ and R ² are C _3-10 cycloalkyl or C _6-12 aryl group.

As the 9,9-bis (dihydroxyphenyl) fluorenes, fluorenes corresponding to the above-mentioned bisphenolfluorenes (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 (alkyl-dihydroxyphenyl) fluorene [eg, 9,9-bis (3,4-dihydroxy-5-methylphenyl) fluorene, 9,9-bis (3,4-dihydroxy) 9,9-bis (C _1-4 alkyl) such as -6-methylphenyl) fluorene 9,9-bis (diC _1-4 alkyl-dihydroxyphenyl) fluorene, such as -dihydroxyphenyl) fluorene, 9,9-bis (2,4-dihydroxy-3,6-dimethylphenyl) fluorene, etc .; 9,9-bis (dihydroxyphenyl) fluorenes corresponding to the compound and in which the substituents R ¹ and R ² are C _3-10 cycloalkyl or C _6-12 aryl group.

  As the 9,9-bis (trihydroxyphenyl) fluorenes, fluorenes corresponding to the above 9,9-bis (mono or dihydroxyphenyl) fluorenes, for example, 9,9-bis (3,4,5-triene) (Hydroxyphenyl) fluorene, 9,9-bis (2,4,6-trihydroxyphenyl) fluorene, 9,9-bis (2,4,5-trihydroxyphenyl) fluorene, 9,9-bis (2,3 , 4-trihydroxyphenyl) fluorene, 9,9-bis (2,3,5-trihydroxyphenyl) fluorene, 9,9-bis (2,3,6-trihydroxyphenyl) fluorene Bis (trihydroxyphenyl) fluorene and the like are included.

Among the bisphenol fluorenes, the alkylene oxide adduct is 1 to 10 moles (preferably 1 to 5 moles, particularly 1 to 3 moles) of _C2-4 alkylene oxide per mole of the hydroxyl group of the bisphenol fluorenes. And the like). Examples of the compound to which 1 mol of alkylene oxide has been added include, for example, 9,9-bis (hydroxyalkoxyphenyl) fluorenes [eg, 9,9-bis (4-hydroxyethoxyphenyl) fluorene (bisphenoxyethanolfluorene, BPEF) 9,9-bis [4- (hydroxyC _2-3 alkoxy) phenyl] fluorene; 9,9-bis (4-hydroxyethoxy-3-methylphenyl) fluorene (biscresolethanolfluorene, BCEF), 9,9- 9,9-bis (alkylhydroxy C _2-3 alkoxyphenyl) fluorene such as bis (4-hydroxyisopropoxy-3-methylphenyl) fluorene; 9,9-bis (4-hydroxyethoxy-3,5-dimethylphenyl) ) Fluorene, 9,9-bis (4- Mud carboxymethyl isopropoxyphenyl-2,6-dimethylphenyl) 9,9-bis (di-hydroxy C _2-3 alkoxyphenyl, such as fluorene) fluorene; 9,9-bis (4-hydroxyethoxy-3-phenyl) fluorene 9,9-bis (cycloalkylhydroxy C _2-3 alkoxyphenyl) fluorene; 9,9-bis (arylhydroxy C _2-3 ) such as 9,9-bis (4-hydroxyethoxy-3-phenylphenyl) fluorene 9,9-bis [di (hydroxyalkoxy) phenyl] fluorenes corresponding to these compounds {eg, 9,9-bis [3,4-di (2-hydroxyethoxy) phenyl]) 9,9-bis fluorene [di (2-hydroxy-C _2-3 alkoxy) 9,9-bis [tri (hydroxyalkoxy) phenyl] fluorenes corresponding to these compounds, for example, 9,9-bis [3,4,5-tri (2-hydroxyethoxy) phenyl 9,9-bis [3,4,5-tri (2-hydroxyC _2-3 alkoxy) phenyl] fluorene such as fluorene and the like.

Examples of the bisanilinefluorenes (9,9-bis (aminophenyl) fluorenes) include 9,9-bis (monoaminophenyl) fluorenes [eg, 9,9-bis (4-aminophenyl) fluorene ( 9,9-bis (amino-C ₁ ) such as 9,9-bis (4-amino-3-methylphenyl) fluorene and 9,9-bis (3-amino-2-methylphenyl) fluorene; _-4 alkylphenyl) fluorene; 9,9-bis (4-amino-3,5-dimethylphenyl) fluorene, 9,9-bis (4-amino-2,6-dimethylphenyl) fluorene, 9,9-bis (4-amino-3,5-di -t- butyl phenyl) fluorene such as 9,9-bis (amino - di C _1-4 alkylphenyl) fluorene; these reduction 9,9-bis (di- or triaminophenyl) fluorenes corresponding to the compounds; alkylene oxide adducts of these compounds; bisanilinefluorenes corresponding to these compounds, wherein the amino group is an N-monosubstituted amino group Corresponding to these compounds, bisanilinefluorenes in which the substituents R ¹ and R ² are C _3-10 cycloalkyl or C _6-12 aryl groups.

  Bisphenol fluorenes with n = 0 are described in, for example, literatures [J. Appl. Polym. Sci., 27 (9), 3289, 1982], JP-A-6-145087, and JP-A-8-217713. It can be produced by condensing fluorenone with phenols using hydrogen chloride gas and mercaptopropionic acid as catalysts according to the method described. Further, a hydrochloric acid solution or sulfuric acid may be used instead of the hydrogen chloride gas.

  Bis (monohydroxyphenyl) fluorenes can be synthesized by various synthetic methods, for example, (a) a method of reacting a fluorenone with a phenol in the presence of hydrogen chloride gas and mercaptocarboxylic acid (J. Appl. Polym. Sci., 27 (9), 3289, 1982], JP-A-6-145087 and JP-A-8-217713), and (b) 9-fluorenone in the presence of an acid catalyst (and an alkyl mercaptan). A method of reacting alkylphenols (JP-A-2000-26349), a method of reacting fluorenones and phenols in the presence of (c) hydrochloric acid and thiols (such as mercaptocarboxylic acid) (JP-A-2002-47227). Publication), (d) reacting fluorenones with phenols in the presence of sulfuric acid and thiols (such as mercaptocarboxylic acid) to obtain hydrocarbons Of bisphenol fluorene by crystallization with a crystallization solvent composed of a compound and a polar solvent (JP-A-2003-221352).

  In the method for producing 9,9-bis (monohydroxyphenyl) fluorenes, instead of phenols, 9,9-bis (di or trihydroxyphenyl) fluorenes are used instead of phenols. (Phenols, trihydroxyphenols). Of 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 higher purity may be obtained. Many.

Further, the method for producing an alkylene oxide adduct of 9,9-bis (monohydroxyphenyl) fluorenes is not particularly limited. For example, 9,9-bis (hydroxyphenyl) fluorenes and the corresponding alkylene oxide (C _2-4 alkylene oxide) or an alkylene carbonate (C _2-4 alkylene carbonate) in the presence of a catalyst (such as a base catalyst) if necessary, or fluorenone and a corresponding phenoxy C _2-4 alcohol. (For example, JP-A-11-349657). The alkylene oxide adduct of 9,9-bis (di or trihydroxyphenyl) fluorene is used in the above-mentioned production method instead of 9,9-bis (hydroxyphenyl) fluorene or phenoxy C _2-4 alcohol. And the corresponding alcohols [9,9-bis (di or trihydroxyphenyl) fluorenes, di or tri (hydroxy _C2-4 alkoxy) benzenes, etc.].

The bisaniline fluorene in which X ¹ and X ² are amino groups can be prepared by using the corresponding aniline in place of the phenol in the method for producing bisphenol fluorene.

Examples of the derivative of the compound represented by the formula (I) include resinous substances (oligomers and resins), for example, a reaction product of the above bisphenolfluorenes and a monofunctional compound [monocarboxylic acid (saturated or unsaturated C ₂ Esters with _-10 aliphatic monocarboxylic acids, saturated or unsaturated _C5-10 alicyclic monocarboxylic acids, and aromatic _C6-14 monocarboxylic acids; urethane compounds with monoisocyanate compounds]; Reaction products of bisaniline fluorenes and monofunctional compounds (such as amides with the monocarboxylic acids); oligomers and polymers (resins) containing the bisphenol fluorenes or bisphenol anilines as constituent monomers (hereinafter referred to as oligomers and polymers) Simply referred to as “polymer” or “resin”). Among these derivatives, resins (thermoplastic resins, thermosetting resins) are preferred.

  The molecular weight (weight average molecular weight) of the derivative of the compound represented by the formula (I) can be selected, for example, from about 300 to 1,000,000, preferably from 400 to 500,000, more preferably from about 500 to 100,000. Good. In particular, when the derivative of the compound represented by the formula (I) is a resin, the weight average molecular weight may be about 1,000 to 1,000,000, preferably about 3,000 to 300,000, and more preferably about 5,000 to 100,000. When the derivative of the compound represented by the formula (I) is an oligomer (or a monomer), the weight average molecular weight is 400 to 50,000, preferably 450 to 30,000, more preferably about 500 to 10,000. Is also good.

  Examples of bisphenol fluorene resins include thermoplastic resins (polyester resins; polycarbonate resins; polyurethane resins, etc.) and thermosetting resins [unsaturated polyester resins; polyurethane resins (urethane resins); epoxy resins; Vinyl ester resin; (meth) acrylic resin obtained by an esterification reaction between the bisphenolfluorenes and a polymerizable monomer having a carboxyl group; phenolic resin, etc.]. In these resins, the bisphenol fluorenes can be used alone or in combination of two or more.

  Examples of the bisaniline fluorene resin include a thermoplastic resin (a polyamide resin; a thermoplastic polyimide resin, etc.) and a thermosetting resin (a polyimide resin; an aniline resin, etc.). These resins can be used alone or in combination of two or more. In these resins, the bisaniline fluorenes can be used alone or in combination of two or more.

(1) Polyester resin (including unsaturated polyester resin)
The polyester resin can be obtained by reacting a diol component composed of at least the bisphenolfluorenes (9,9-bis (monohydroxyphenyl) fluorenes) with a dicarboxylic acid component. In addition to a saturated or unsaturated polyester resin, a polyarylate resin using an aromatic dicarboxylic acid as a polymerization component is also included.

The diol component of the polyester resin may be configured by combining the bisphenolfluorenes with other diols. Examples of such diols include linear alkylene glycols (eg, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, tetramethylene glycol, hexanediol, neopentyl glycol, octanediol, decanediol, and the like). Or branched C _2-12 alkylene glycols, etc.), (poly) oxyalkylene glycols (eg, di to tetra C _2-4 alkylene glycols such as diethylene glycol, triethylene glycol and dipropylene glycol), alicyclic diols (For example, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2,2-bis (4-hydroxycyclohexyl) propane and its alkylene oxide adduct (2,2-bis (4- 2-hydroxyethoxy) cyclohexyl) propane), etc.), aromatic diol (e.g., biphenol, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), bisphenol AD, bisphenol F and their alkylene oxide (C _2-3 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, especially C _2-6 alkylene glycols (for example, linear or branched chains such as ethylene glycol, propylene glycol, 1,4-butanediol and the like). _C2-4 alkylene glycol). As diols, at least ethylene glycol is often used. Use of such a diol (for example, ethylene glycol) can increase polymerization reactivity and also impart flexibility to the resin.

  The ratio (molar ratio) of the bisphenolfluorenes and the diols is, for example, the former / latter = 100/0 to 50/50, preferably 100/0 to 75/25 (for example, 100/0 to 70/30). And more preferably about 100/0 to 90/10 (for example, about 100/0 to 80/20).

  If necessary, a polyol such as glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, or the aforementioned 9,9-bis (di or trihydroxyphenyl) fluorene may be used in combination with the diol component.

Examples of the dicarboxylic acid component constituting the polyester resin include an aliphatic dicarboxylic acid, an alicyclic dicarboxylic acid, an aromatic dicarboxylic acid, and a derivative thereof capable of forming an ester [for example, an acid anhydride; an acid halide (such as an acid chloride); Lower alkyl esters (eg, C _1-2 alkyl esters)]. These dicarboxylic acids can be used alone or in combination of two or more.

Examples of the aliphatic dicarboxylic acids include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, and saturated _C3-20 aliphatic dicarboxylic acids such as hexadecanedicarboxylic acid. Acids (preferably saturated C _3-14 aliphatic dicarboxylic acids and the like); unsaturated C _4-20 aliphatic dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid and mesaconic acid (preferably unsaturated C _4-14 aliphatic) Dicarboxylic acids, etc.); and derivatives thereof capable of forming an ester. In the unsaturated polyester resin, the proportion of the aliphatic unsaturated dicarboxylic acid (such as 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 (such as cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and cycloheptanedicarboxylic acid). C _3-10 cycloalkane-dicarboxylic acid, etc.), unsaturated alicyclic dicarboxylic acid (C _3-10 cycloalkene-dicarboxylic acid such as 1,2-cyclohexene dicarboxylic acid, 1,3-cyclohexene dicarboxylic acid, etc.); Cyclic alkanedicarboxylic acids (di or tricyclo C _7-10 alkane-dicarboxylic acids such as bornandicarboxylic acid, norbornanedicarboxylic acid and adamantanedicarboxylic acid), and polycyclic alkenedicarboxylic acids (bornendicarboxylic acid, norbornenedicarboxylic acid, etc.) di- or tricyclic C _7-10 A Ken - dicarboxylic acid), etc. These esters can form derivatives can be exemplified.

Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid (such as 2,6-naphthalenedicarboxylic acid), 4,4′-diphenyldicarboxylic acid, diphenylether-4,4′-dicarboxylic acid, Aromatic C _8-16 dicarboxylic acids such as 4,4′-diphenylmethane dicarboxylic acid and 4,4′-diphenyl ketone dicarboxylic acid; and their ester-formable derivatives.

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

As the dicarboxylic acid component, usually at least one selected from aliphatic dicarboxylic acids and alicyclic dicarboxylic acids, in particular, aliphatic dicarboxylic acids (saturated aliphatic dicarboxylic acids or their ester-forming derivatives, particularly adipic acid, Saturated C _3-14 aliphatic dicarboxylic acids such as suberic acid and sebacic acid) and alicyclic dicarboxylic acids (C _5-10 cycloalkanedicarboxylic acids such as cyclohexanedicarboxylic acid) are preferred.

  In the polyarylate 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. / 50 or so.

  In the polyester resin, the ratio (molar ratio) of the dicarboxylic acid component to the diol component (such as bisphenolfluorenes and diols) is usually the former / the latter = 1.5 / 1 to 0.7 / 1, preferably 1 .2 / 1 to 0.8 / 1 (especially 1.1 / 1 to 0.9 / 1).

The weight average molecular weight Mw (in terms of polystyrene) of the polyester resin is not particularly limited, and is, for example, 400 to 50 × 10 ⁴ , preferably 500 to 30 × 10 ⁴ (for example, 1000 to 20 × 10 ⁴ ), and more preferably 3000. It is about 30 × 10 ⁴ . In the case of an unsaturated polyester resin, the molecular weight per double bond may be about 300 to 1,000, preferably about 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 if necessary.

  The polyester resin can be produced by a conventional method, for example, a direct polymerization method (direct esterification method) or a transesterification method, for example, by subjecting a diol component composed of bisphenolfluorenes to a condensation reaction with the dicarboxylic acid component. .

(2) Polycarbonate Resin As the polycarbonate resin, for example, a reaction between a diol component composed of at least the bisphenolfluorenes (9,9-bis (monohydroxyphenyl) fluorenes) and phosgene according to a conventional method ( Phosgene method) or a polycarbonate-based resin obtained by a reaction (ester exchange method) between the bisphenolfluorenes (9,9-bis (monohydroxyphenyl) fluorenes) and a carbonate ester.

  The diol component may be composed of bisphenolfluorenes alone, or composed of bisphenolfluorenes and other diols (diols exemplified in the section of the polyester resin, particularly aromatic diols and alicyclic diols). May be. 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 bisphenolfluorenes and the diols 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, and is, for example, 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 ), and more preferably about 1 × 10 ^{4 to} 25 × 10 ⁴ (for example, 1 × 10 ⁴ to 10 × 10 ⁴ ).

(3) Polyurethane resin (urethane resin)
The diol component constituting the polyurethane resin may be composed solely of the above-mentioned bisphenolfluorenes (9,9-bis (monohydroxyphenyl) fluorenes). You may use together with diols. Furthermore, a diol component containing bisphenol fluorenes as a constituent unit, for example, a polyester diol formed by the reaction of a diol component composed of bisphenol fluorenes with a dicarboxylic acid component, a diol component composed of bisphenol fluorenes and an alkylene oxide, Can be used as the diol component of the polyurethane resin. The diol component may be used alone or in combination of two or more. If necessary, the diol component may be used in combination with a polyol component such as a triol.

  In the diol component, the content of bisphenolfluorenes (or units) is, for example, about 10 to 100 mol%, preferably about 20 to 80 mol%, and more preferably about 30 to 70 mol%, based on the whole diol component. May be.

Examples of the diisocyanate compound constituting the polyurethane resin include aromatic diisocyanates [paraphenylene diisocyanate, tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), tetramethyl xylylene 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.], fats 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; monoisocyanate compounds (C _1-6 alkyl isocyanates such as methyl isocyanate; C _5-6 cycloalkyl isocyanates such as cycloalkyl isocyanates; C _{6- 10} aryl isocyanate). The isocyanate compound also includes a derivative such as a polymer or a modified form of the polyisocyanate compound.

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

(4) epoxy resin The diol component or the polyol component constituting the epoxy resin may be composed of the bisphenolfluorenes alone, and the bisphenolfluorenes and other diols exemplified in the section of the polyester resin. (Especially aromatic diols and alicyclic diols). Other diols can be used alone or in combination of two or more. Among the diols, aromatic diols such as bisphenols such as bisphenol A, AD, and F are particularly preferable. The ratio between the bisphenolfluorenes and the diols can be selected from the same range as in the case of the polyester resin. Further, the above-mentioned bisphenolfluorenes and other diols may be used in combination with polyols (for example, phenol novolak) if necessary.

  The epoxy resin can be obtained by reacting at least the above-mentioned bisphenolfluorenes and epichlorohydrin. Examples of the epoxy resin include 9,9-bis (glycidyloxyphenyl) fluorene [eg, 9,9-bis (4-glycidyloxyphenyl) fluorene (BPFG), 9,9-bis (4-glycidyloxy-). 9,9-bis (monoglycidyloxyphenyl) fluorenes such as 3-methylphenyl) fluorene (BCFG); 9,9-bis [3,4-di (glycidyloxy) phenyl] fluorene (biscatecholfluorenetetraglycidyl ether) ) And the like; 9,9-bis (diglycidyloxyphenyl) fluorenes; 9,9-bis (triglycidyloxyphenyl) such as 9,9-bis [3,4,5-tri (glycidyloxy) phenyl] fluorene Fluorenes], 9,9-bis (glycidyloxyalkoxyphenyl) ) Fluorenes [eg, 9,9-bis (4-glycidyloxyethoxyphenyl) fluorene (bisphenoxyethanol fluorenediglycidyl ether) (BPEFG), 9,9-bis (4-glycidyloxyethoxy-3-methylphenyl) fluorene 9,9-bis (monoglycidyloxyalkoxyphenyl) fluorenes such as (BCEFG); and 9,9-bis (di or tri (glycidyloxyalkoxy) phenyl) fluorenes corresponding thereto. The weight average molecular weight Mw of the epoxy resin may be, for example, about 300 to 30,000, preferably about 400 to 10,000, and more preferably about 500 to 5,000.

(5) Vinyl ester resin The vinyl ester resin is prepared by a conventional method, for example, by reacting the epoxy resin having the bisphenolfluorene unit with a polymerizable monomer having at least a carboxyl group (unsaturated monocarboxylic acid). Obtainable. If necessary, the polymerizable monomer having a carboxyl group may be a dicarboxylic acid (for example, an aliphatic dicarboxylic acid, an alicyclic dicarboxylic acid, or an aromatic dicarboxylic acid (such as isophthalic acid or terephthalic acid)) described in the section of the polyester resin. May be used in combination.

  As the polymerizable monomer having a carboxyl group, an unsaturated monocarboxylic acid can be used. As the unsaturated monocarboxylic acid, (meth) acrylic acid can be usually used, and cinnamic acid, crotonic acid, sorbic acid, monoalkyl maleate (such as monomethyl malate) and the like may be used. These monomers may be used alone or in combination of two or more.

  The amount of the unsaturated monocarboxylic acid to be used is 0.5 to 1.2 mol, preferably 0.7 to 1.1 mol, more preferably 0.8 to 1 mol, per 1 mol of the epoxy group of the epoxy resin. Degree.

  The vinyl ester resin can also be obtained by a reaction between bisphenolfluorenes and glycidyl (meth) acrylate. The amount of glycidyl (meth) acrylate used may be, for example, 1 to 3 mol, and preferably about 1 to 2 mol, per 1 mol of bisphenolfluorenes.

  Note that typical vinyl ester-based resins also include vinyl ester-based resins described in JP-A-2004-2635 and JP-A-2004-2636.

(6) Acrylic resin The acrylic resin can be obtained by reacting the bisphenolfluorenes with a polymerizable monomer having a carboxyl group. As the polymerizable monomer having a carboxyl group, generally, an unsaturated monocarboxylic acid, particularly (meth) acrylic acid, can be used, and cinnamic acid, crotonic acid, sorbic acid, monoalkyl esters of maleic acid (such as monomethyl malate) Or the like may be used. Further, the unsaturated carboxylic acid may be a reactive derivative such as an acid chloride or a C _1-2 alkyl ester. These monomers may be used alone or in combination of two or more.

  The amount of the unsaturated monocarboxylic acid to be used is 0.5 to 1.2 mol, preferably 0.7 to 1.1 mol, more preferably 0.8 to 1 mol per mol of the hydroxyl group of the bisphenol fluorene. It may be on the order of moles. Such an acrylic resin is often an oligomer (resin precursor).

The acrylic resin in the form of an oligomer may be polymerized with a copolymerizable monomer, if necessary, to form an acrylic copolymer. Examples of the copolymerizable monomer include carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; and C _1-6 alkyl (meth) acrylates such as methyl (meth) acrylate. Esters; vinyl cyanides such as (meth) acrylonitrile; aromatic vinyl monomers such as styrene; carboxylic acid vinyl esters such as vinyl acetate; α-olefins such as ethylene and propylene. These copolymerizable monomers can be used alone or in combination of two or more.

(7) In the production of the phenolic resin phenolic resin, a bisphenol fluorenes, in the formula (I), a compound n1 and n2 is 0 or 1, X ¹ and X ² is a hydroxyl group can be used. Also, if n1 and n2 is 1, the substitution position of R ¹ and R ^2, is a position which does not interfere with the addition reaction of an aldehyde.

As the aldehyde, an aliphatic C _1-4 aldehyde, usually, formaldehyde or paraformaldehyde can be used.

Further, co-condensation components such as phenols (eg, C _1-4 alkyl-phenols such as phenol and cresol, dihydroxybenzenes such as resorcinol), urea, guanamines, and melamines are used together with the bisphenol fluorenes. Is also good. The ratio of the bisphenolfluorenes to the co-condensation component is the former / the latter (molar ratio) = 100/0 to 5/95, preferably 100/0 to 10/90, and more preferably about 100/0 to 20/80. There may be.

  The phenolic resin can be produced according to a conventional method for producing a phenolic resin. In the presence of an acid catalyst, a novolak-type phenolic resin is obtained, and in the presence of a base catalyst, a resol-type phenolic resin is obtained.

(8) Polyamide resin The diamine component may be composed of bisaniline fluorenes (9,9-bis (monoaminophenyl) fluorenes) alone, or a combination of bisaniline fluorenes and diamines. Is also good. Examples of the diamines include linear C _2-14 aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, hexamethylenediamine, and dodecanediamine; Cyclic _C6-14 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 can be exemplified. These diamines can be used alone or in combination of two or more.

  The ratio of bisaniline fluorenes to diamines is the former / the latter (molar ratio) = 100/0 to 5/95, preferably 90/10 to 10/90, and more preferably about 80/20 to 20/80. is there.

  As the dicarboxylic acids of the polyamide resin, the dicarboxylic acids (aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids) exemplified in the section of the polyester resin can be used. The dicarboxylic acids can be used alone or in combination of two or more.

In the preparation of the polyamide resin, at least one component selected from aminocarboxylic acids (such as ω-aminoundecanoic acid) and lactams (such as C _3-12 lactam such as ε-caprolactam) is used as a copolymerization component. Is also good.

(9) Polyimide Resin Bisanilinefluorenes (9,9-bis (monoaminophenyl) fluorenes) may be used alone or in combination with a diamine component. Examples of the diamine component include, in addition to the diamines exemplified in the section of the polyamide resin, bis (diaminophenyl) alkane such as diaminophenyl ether and 2,2-bis (3,4-diaminophenyl) propane. Diamines can be used alone or in combination of two or more.

  Examples of the raw material polycarboxylic acids include tetracarboxylic acids, for example, pyromellitic acid or its anhydride, biphenyltetracarboxylic acid or its anhydride, benzophenonetetracarboxylic acid or its anhydride, 2,2-bis (3,4- Examples include bis (dicarboxyphenyl) alkanes such as dicarboxyphenyl) propane or anhydrides thereof, bis (carboxyphenyl) fluoroalkanes such as 2,2-bis (3,4-carboxyphenyl) hexafluoropropane, and bismaleimide. it can. These polycarboxylic acids can be used alone or in combination of two or more.

  The polyimide resin may be thermoplastic or thermosetting.

(10) The bis-anilines fluorenes used as starting material aniline resin aniline resin, said formula (I), n1 and n2 are 0 or 1, X ¹ is an amino group or a hydroxyl group (X ¹ is at least amino Group) can be used. Also, if n1 and n2 is 1, the substitution position of R ¹ and R ^2, is a position which does not interfere with the addition reaction of an aldehyde.

The bisaniline fluorenes may be used alone or in combination with anilines (C _1-4 alkyl-aniline such as aniline and methyl aniline, diaminobenzene and the like). The ratio of bisanilinefluorenes to anilines is the former / the latter (molar ratio) = 100/0 to 5/95, preferably 100/0 to 10/90, and more preferably about 100/0 to 20/80. is there.

  As the aldehydes, the aldehydes (formaldehyde, paraformaldehyde, etc.) described in the section of the phenol resin can be used.

  The aniline-based resin can be produced according to a conventional method for producing an aniline resin. In the presence of an acid catalyst, a novolak-type aniline-based resin is obtained, and in the presence of a base catalyst, a resole-type aniline-based resin is obtained.

  When the derivative of compound (I) is a thermosetting resin, the composition of the present invention may contain a suitable curing agent and the like. For example, the resin composition containing the epoxy-based resin or the urethane-based resin may include an amine-based curing agent or the like, and the resin composition containing the unsaturated polyester-based resin or the vinyl ester-based resin includes an initiator ( Peroxides), polymerization accelerators (organic metal compounds such as metal octenoate), and copolymerizable monomers (reactive diluents such as (meth) acrylic acid esters and styrene). When a curing agent is used, the curing agent may be composed of the compound (I) or a derivative thereof in order to further improve the dispersibility of the additive. For example, the curing agent for the epoxy resin may be composed of the bisphenolfluorenes or the bisanilinefluorenes.

  The compound (I) or a derivative thereof may be combined with another resin (a thermoplastic resin or a thermosetting resin). For example, compound (I) or its derivative in low molecular or oligomer form may be combined with other resins.

  Examples of the thermoplastic resin include olefin resins (polyethylene, polypropylene, polymethylpentene, amorphous polyolefin and the like), vinyl resins (acrylic resins such as polyvinyl chloride and polymethyl methacrylate), polystyrene and acrylonitrile-styrene. Styrene resin such as resin), polycarbonate resin (bisphenol A type polycarbonate etc.), polyester resin (polyalkylene arylate such as polyethylene terephthalate, polybutylene terephthalate, polycyclohexane dimethylene terephthalate, and polyethylene naphthalate, polyarylate, liquid crystal) Polyester, etc., polyacetal resin, polyamide resin (nylon 6, nylon 66, nylon 46, nylon 6T, nylon MXD, etc.) , Polyphenylene ether-based resin (modified polyphenylene ether, etc.), polysulfone-based resin (polysulfone, polyethersulfone, etc.), polyphenylene sulfide, polyetherketone, polyetheretherketone, polyetherimide, polyamideimide, polyaminobismaleimide, bismaleimidetriazine Resins, thermoplastic elastomers, fluorinated resins and the like can be mentioned. Examples of the thermosetting resin include a phenol resin, a furan resin, a urea resin, a melamine resin, an unsaturated polyester, an epoxy resin, a urethane resin, a silicone resin, a polyimide, a diallyl phthalate resin, and a vinyl ester resin. These resins can be used alone or in combination of two or more.

  The ratio (weight ratio) between the other resin and the compound (I) or a derivative thereof can be selected from a range of about 99/1 to 1/99 (for example, 90/10 to 10/90), Usually, it is about 99/1 to 50/50, preferably about 98/2 to 70/30, and more preferably about 97/3 to 80/20.

[Additive]
In the present invention, the additive may be a liquid at room temperature (for example, a temperature of about 15 to 25 ° C.) or a solid (for example, a powdery solid). Additives include fillers or reinforcing agents, colorants (dyes), conductive agents, flame retardants, plasticizers, lubricants, stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers, etc.), release agents Molding agents (natural waxes, synthetic waxes, linear fatty acids and their metal salts, acid amides, esters, paraffins, etc.), antistatic agents, dispersants, flow regulators, leveling agents, defoamers, surfaces Modifiers (silane coupling agents, titanium coupling agents, etc.), low stress agents (silicone oil, silicone rubber, various plastic powders, various engineering plastic powders, etc.), heat resistance improvers (sulfur compounds, polysilanes, etc.) , Carbon materials and the like. These additives can be used alone or in combination of two or more. Among these additives, a filler, a colorant (for example, a dye pigment such as a black pigment, a red pigment, a green pigment, and a blue pigment), a flame retardant, and a carbon material are preferable. Further, a carbon material that functions as a filler or a reinforcing agent (reinforcing material), a coloring agent, a conductive agent, or the like is also preferable.

  Examples of the filler or filler include oxide-based inorganic fillers (silica, alumina, zirconia, mica, etc.) and non-oxide-based inorganic fillers (silicon carbide, silicon nitride, graphite, etc.). In some applications, metal powders such as aluminum, zinc, and copper can also be used. More specifically, silica-based fillers (silica sand, quartz, novaculite, diatomaceous earth, etc.), synthetic amorphous silica, silicate-based fillers (kaolinite, mica, talc, wollastonite, asbestos, silicic acid) Calcium, aluminum silicate, etc.), glass filler (glass powder, glass sphere, hollow glass sphere, glass flake, foam glass sphere, etc.), non-oxide inorganic filler (graphite, carbon black, boron nitride, boron carbide) , Aluminum nitride, aluminum carbide, silicon nitride, silicon carbide, titanium boride, titanium nitride, titanium carbide, etc.), carbonate fillers (such as calcium carbonate), metal oxide fillers (zinc oxide, alumina, zirconia, Magnesia, titanium oxide, beryllium oxide, etc.). As these fillers, fillers of various shapes such as fibrous, needle-like (including whisker), powdery and granular, and scale-like can be used. Fibrous fillers include carbon fibers, activated carbon fibers, glass fibers, aluminosilicate fibers, aluminum oxide fibers, silicon carbide fibers, metal fibers, inorganic fibers such as boron fibers and potassium titanate fibers, and organic fibers such as aramid fibers. Also included. These fillers can be used alone or in combination of two or more.

  Colorants (or dyes) include inorganic pigments and organic dyes and pigments. The colorant (pigment, dye, dye, etc.) may be water-soluble or oil-soluble. Examples of inorganic pigments include black pigments [carbon black (eg, acetylene black, lamp black, thermal black, furnace black, channel black, Ketjen black, etc.)], white pigments [titanium-based white pigments (titanium oxide, etc.), zinc] White pigments (zinc oxide, zinc sulfide, etc.), composite white pigments (lithopone, etc.), extender pigments (magnesium silicate, calcium carbonate, barium sulfate, aluminum hydroxide, bentonite, etc.), yellow pigments such as chrome yellow, oxidation Red pigments such as iron red, orange pigments such as molybdate orange, green pigments such as chrome green, blue pigments such as dark blue, purple pigments such as manganese violet, cadmium pigments, lead pigments, and cobalt pigments. . Organic dyes and 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 (lake red, Watchang Red), cyanine dyes, carbazole dyes, pyromethene dyes, anthraquinone dyes, naphthoquinone dyes, quinacridone dyes, perylene dyes, perinone dyes, isoindoline dyes Dyes and pigments, dioxazine dyes and pigments, sullen dyes and the like can be mentioned. Coloring agents include functional dyes, for example, near-ultraviolet absorbing dyes, fluorescent dyes, photochromic dyes, organic photoconductive materials (carrier generation materials, carrier transfer materials, etc.), liquid crystal display dyes, solar energy storage materials, laser dyes, It may be a photographic dye, a diazo photosensitive paper dye, a thermochromic dye (thermochromic dye), a pressure-sensitive / thermosensitive dye (color former), a sublimation transfer dye, a toner charge transfer agent, and the like.

  These colorants (or dyes) can be used alone or in combination of two or more.

Flame retardants include inorganic flame retardants (boric acid flame retardants, phosphorus flame retardants, other inorganic flame retardants), organic flame retardants (nitrogen flame retardants, halogen flame retardants, etc.), colloid flame retardants (Eg, Sb ₂ O ₃ ).

  Examples of the boric acid-based flame retardant include zinc borate and barium metaborate. Examples of the phosphorus-based flame retardant include ammonium phosphate, melamine phosphate, red phosphorus, phosphate [tricresyl phosphate, tri (β-chloroethyl) phosphate, tri (dichloropropyl) phosphate, tri (dibromopropyl) phosphate. , 2,3-dibromopropyl-2,3-dichloropropyl phosphate, etc.]. Other inorganic flame retardants include, for example, inorganic hydroxides such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, calcium hydroxide, barium hydroxide, basic magnesium carbonate, dolomite, tin oxide hydrate, borax, etc. Metal hydrate, zinc carbonate, magnesium-calcium carbonate, barium carbonate, magnesium oxide, molybdenum oxide, zirconium oxide, tin oxide, expanded graphite and the like can be mentioned. Examples of the nitrogen-based flame retardant include phosphonitrile, guanidine phosphate, guanidine sulfamate, guanylurea phosphate, guanidine carbonate, and the like. Examples of the halogen-based flame retardant include tetrabromobisphenol A derivative (TBA), tetrabromobisphenol S derivative, hexabromobenzene, decabromodiphenyl ether, tetrabromoethane (TBE), tetrabromobutane (TBB), and hexabromocyclodecane. (HBCD) and the like, and chlorinated paraffin, chlorinated polyphenyl, chlorinated diphenyl, perchloropentacyclodecane, chlorinated naphthalene and the like. These halogen-based flame retardants exhibit higher flame retardancy when used in combination with antimony trioxide and the like. These flame retardants can be used alone or in combination of two or more.

  Examples of the carbon material include graphite, carbon black (such as the above-described carbon black and conductive carbon black), carbon fiber (such as the above-described carbon fiber), fullerene, and carbon nanotube.

  The carbon nanotube (nanoscale carbon tube) may be a carbon tube having a nano-sized diameter, and a metal (iron or the like) may be included in a space inside the tube of the carbon tube. Representative nanoscale carbon tubes include (i) single-wall or multiwall carbon nanotubes, (ii) amorphous nanoscale carbon tubes, (iii) nanoflake carbon tubes, (iv) nanoflake carbon tubes and nested structures. At least one kind of carbon nanotubes (a) selected from multi-walled carbon nanotubes, and iron carbide or iron, and iron carbide or iron (b) filled in the space inside the tube of the carbon nanotubes (a). And the like. The carbon nanotubes may be used alone or as a mixture of two or more.

  Among these carbon nanotubes, in particular, from the viewpoint of dispersibility in a solvent or a compound (resin) having a fluorene skeleton, an amorphous nanoscale carbon tube (ii), a nanoflake carbon tube (iii), an iron-carbon composite (Iv) and the like are preferable. The reason why the dispersibility of these tubes is good is not clear, but since the carbon network surface of the outermost layer of these tubes is discontinuous, a solvent or a compound (resin) having a fluorene skeleton for these tubes is used. It is considered that the affinity is high.

  Hereinafter, the carbon nanotube will be described in detail.

(carbon nanotube)
A carbon nanotube is a hollow carbon material in which a graphite sheet (that is, a carbon atom surface of a graphite structure or a graphene sheet) is closed in a tubular shape, the diameter is on a nanometer scale, and the wall structure has a graphite structure. . Among carbon nanotubes, those with a wall structure closed in a tubular shape with a single graphite sheet are called single-walled carbon nanotubes, and those with multiple graphite sheets closed in a tubular shape and nested are It is called a multi-walled carbon nanotube (nested multi-walled carbon nanotube). In the present invention, any of these single-walled carbon nanotubes and multi-walled carbon nanotubes can be used.

  The size of the single-walled carbon nanotube is about 0.4 to 10 nm in diameter and about 1 to 500 μm in length, preferably about 0.7 to 5 nm in diameter and about 1 to 100 μm, and more preferably 0 to 100 μm. The thickness may be about 0.7 to 2 nm and the length may be about 1 to 20 μm.

  The size of the multi-walled carbon nanotube is about 1 to 100 nm in diameter and about 1 to 500 μm in length, preferably about 1 to 50 nm in diameter and about 1 to 100 μm, and more preferably about 1 to 40 nm in diameter. And the length may be about 1 to 20 μm.

(Amorphous nanoscale carbon tube)
The amorphous nanoscale carbon tube is not particularly limited. For example, the nanotube described in WO00 / 40509 (Japanese Patent No. 3355442), that is, has a main skeleton composed of carbon, and has a diameter of 0.1 to 1000 nm. A nanoscale carbon tube having an amorphous structure, having a linear shape, and a plane of a carbon network plane (002) measured by a diffractometer method in an X-ray diffraction method (incident X-ray: CuKα). The interval (d002) is 3.54 ° or more (especially 3.7 ° or more), the diffraction angle (2θ) is 25.1 degrees or less (especially 24.1 degrees or less), and the half width of the 2θ band is 3.2. Carbon tube (in particular, 7.0 degree or higher) (an amorphous nanoscale carbon tube).

  An amorphous nanoscale carbon tube is made of a thermally decomposable resin having a decomposition temperature of 200 to 900 ° C. in the presence of a catalyst composed of at least one kind of chloride of a metal such as magnesium, iron, cobalt and nickel. It can be obtained by exciting fluoroethylene, polyvinylidene chloride, polyvinylidene fluoride, polyvinyl alcohol, and the like.

  The shape of the thermally decomposable resin as a starting material is not particularly limited, and may be any shape such as a film, a sheet, a powder, and a lump. For example, when obtaining a carbon material in which a thin-film amorphous nanoscale carbon tube is formed on a substrate, excitation treatment may be performed under appropriate conditions with a thermally decomposable resin applied or placed on the substrate. .

  Examples of the excitation treatment include a method of performing heat treatment in an inert atmosphere, preferably in a temperature range of about 450 to 1800 ° C. and at a temperature equal to or higher than the thermal decomposition temperature of the raw material, or in a temperature range of room temperature to about 3000 ° C. and A method (or treatment) such as a method of performing plasma treatment at a decomposition temperature or higher can be exemplified.

  An amorphous nano-scale carbon tube is a nano-scale carbon nanotube having an amorphous structure (amorphous structure), which has a hollow linear shape and whose pores are highly controlled. The shape is mainly a cylinder, a square pillar, or the like, and at least one of the ends often has no cap (opens). When the tip is closed, the shape is often flat.

  The outer diameter of the amorphous nanoscale carbon tube is usually in the range of usually about 1 to 1000 nm, preferably about 1 to 200 nm, and more preferably about 1 to 100 nm. The aspect ratio (length / diameter of the tube) of the amorphous nanoscale carbon tube is, for example, 2 times or more (for example, about 2 to 500 times), and preferably 5 times or more (for example, about 5 to 200 times). ).

  Here, the term “amorphous structure” means not a graphitic structure composed of a continuous carbon layer of regularly arranged carbon atoms, but a carbonaceous structure composed of irregular carbon network planes. It means that the graphene sheets are irregularly arranged. According to transmission electron microscopy images, a typical analysis technique, the nanoscale carbon tube with an amorphous structure shows that the plane of the carbon network plane is smaller than one time the diameter of the amorphous nanoscale carbon tube. I understand. As described above, since the amorphous surface of the amorphous nanoscale carbon tube has an amorphous structure in which the network surface is irregularly distributed, the carbon network surface constituting the outermost layer is not continuous over the entire length in the longitudinal direction of the tube. It has become. In particular, the length of the carbon netting surface constituting the outermost layer is often less than 20 nm (for example, about 0.1 to 15 nm), particularly less than 5 nm (about 1 to 3 nm) in many cases.

Amorphous carbon generally does not show X-ray diffraction, but does show broad reflections. In the graphitic structure, the carbon network planes are regularly stacked, so that the carbon network plane interval (d ₀₀₂ ) becomes narrow, and the broad reflection shifts to the high angle side (2θ) and becomes gradually sharper (2θ band). half-value width becomes narrow), it becomes possible to observe as d ₀₀₂ diffraction line (if you are stacked regularly graphite positional relation is d ₀₀₂ = 3.354Å).

In contrast, an amorphous structure generally does not exhibit X-ray diffraction as described above, but partially exhibits very weak coherent scattering. In the X-ray diffraction method (incident X-ray = CuKα), the theoretical crystallographic properties of an amorphous nanoscale carbon tube measured by the diffractometer method are defined as follows: carbon network plane spacing (d ₀₀₂ ) is 3.54 ° or more (for example, about 3.6 to 4.1 °), preferably 3.7 ° or more (for example, about 3.75 to 3.95 °); the diffraction angle (2θ) is 25 0.1 degrees or less (for example, about 20 to 25 degrees), preferably 24.1 degrees or less (for example, about 21 to 24 degrees); the half bandwidth of the 2θ band is 3.2 degrees or more (for example, 4 to 25 degrees). About 1.0 to 11.0 degrees), preferably 7.0 degrees or more (for example, about 7.5 to 10.0 degrees).

A typical amorphous nanoscale carbon tube has a diffraction angle (2θ) by X-ray diffraction in the range of 18.9 to 22.6 degrees and a carbon network plane interval (d ₀₀₂ ) of 3.9 to 4.7 °. , And the half width of the 2θ band is often in the range of 7.6 to 8.2 degrees.

The term “linear”, which is one term that describes the shape of an amorphous nanoscale carbon tube, is defined as follows. That is, the length of the amorphous nanoscale carbon tubes image by a transmission electron microscope is L, the length of time that extended the amorphous nanoscale carbon tubes in the case of the L _0, L / L ₀ is 0.9 or more (For example, 1 to 100).

  The tube wall portion of such an amorphous nanoscale carbon tube has an amorphous structure composed of a plurality of fine carbon network planes (graphene sheets) oriented in all directions. It has the advantage that it has an excellent affinity with the resin, probably because it has active sites depending on the interval.

(Iron-carbon composite)
The iron-carbon composite is not particularly limited, and is, for example, an iron-carbon composite described in JP-A-2002-338220, that is, (a) a group consisting of a nanoflake carbon tube and a nested multi-walled carbon nanotube. Iron comprising a selected carbon tube and (b) iron carbide or iron, wherein iron carbide or iron (b) is filled in a range of 10 to 90% of the space in the tube of the carbon tube (a). Examples thereof include a carbon composite. That is, in the iron-carbon composite, iron carbide or iron is not completely filled in the range of 100% of the space in the tube, but is filled in the range of 10 to 90% of the space in the tube. (Ie, partially filled). Note that, in such a nanoflake carbon tube, the wall portion has a patchwork shape or a papier shape (a so-called paper make shape).

  In addition, the “nanoflake carbon tube” refers to an aggregate of graphite sheets in which a plurality (usually many) of flake graphite sheets are assembled in a patchwork or papier-mache (paper matche) shape. Means a carbon tube.

The iron-carbon composite can be manufactured according to the method described in JP-A-2002-338220. For example, (1) the pressure is adjusted to about 10 ⁻⁵ Pa to 200 kPa in an inert gas atmosphere, and The reaction furnace was adjusted so that the ratio B / A when the reaction furnace volume was A (liter) and the oxygen amount was B (Ncc) was about 1 × 10 ^-10 to 1 × 10 ^-1. (2) introducing an inert gas into the reaction furnace, introducing a pyrolytic carbon source at a pressure of about 10 ^-5 Pa to 200 kPa, and heating the iron halide to about 600 to 900 ° C. It is manufactured by a manufacturing method including a step of performing a heat treatment at about 600 to 900 ° C. Here, “Ncc” which is a unit of the oxygen amount B means a volume (cc) when the gas is converted into a standard state at 25 ° C.

  The iron-carbon composite is composed of (a) a carbon tube selected from the group consisting of a nanoflake carbon tube and a nested multi-walled carbon nanotube, and (b) iron carbide or iron. Instead of filling substantially all of the space (that is, the space surrounded by the tube wall), a part of the space, more specifically about 10 to 90%, preferably about 30 to 80% More preferably, about 40 to 70% is filled with iron carbide or iron.

  In the iron-carbon composite, as described in JP-A-2002-338220, the carbon part is cooled at a specific rate after the production steps (1) and (2), and then the nanoflake carbon is cooled. After performing the manufacturing steps (1) and (2), the tube is subjected to a heat treatment in an inert gas and cooled at a specific cooling rate, thereby obtaining a nested multi-walled carbon nanotube.

(1) Nano-flake carbon tube and iron-carbon composite comprising iron carbide or iron The nano-flake carbon tube and iron-carbon composite comprising iron carbide or iron are typically columnar. FIGS. 1 and 2 show transmission electron microscope (TEM) photographs showing an example of such a columnar iron-carbon composite. FIG. 1 is a transmission electron microscope (TEM) photograph of the side surface of the columnar iron-carbon composite obtained in Example 1 of JP-A-2002-338220, and FIG. 1 is a TEM photograph of a cross section of a columnar iron-carbon composite obtained in Example 1 of Japanese Patent Application Laid-Open Publication No. H10-209, which crosses the longitudinal direction. FIG. 4A-1 is a schematic TEM image of a columnar iron-carbon composite (nanoflake carbon tube). In (a-1) of FIG. 4, 100 schematically shows a TEM image in the longitudinal direction of the nanoflake carbon tube, and 200 shows a TEM image of a cross section almost perpendicular to the longitudinal direction of the nanoflake carbon tube. It is shown schematically.

  The nano-flake carbon tube constituting the iron-carbon composite typically has a hollow cylindrical shape, and when a cross section thereof is observed with a TEM, arc-shaped graphene sheet images are gathered concentrically. Has a discontinuous ring. When the longitudinal direction is observed by a TEM, the substantially linear graphene sheet images are arranged in a multilayer shape almost in parallel with the longitudinal direction. Is characterized by being discontinuous and not continuous over the entire length in the longitudinal direction.

  FIG. 4A-1 is a schematic TEM image of a columnar iron-carbon composite (nanoflake carbon tube). In (a-1) of FIG. 4, 100 schematically shows a TEM image in the longitudinal direction of the nanoflake carbon tube, and 200 shows a TEM image of a cross section almost perpendicular to the longitudinal direction of the nanoflake carbon tube. It is shown schematically.

  More specifically, as seen from 200 of FIG. 2 and FIG. 4 (a-1), a cross section perpendicular to the longitudinal direction of the nanoflake carbon tube constituting the iron-carbon composite was observed by TEM. In this case, a large number of arc-shaped graphene sheet images are gathered concentrically (multi-layered tube shape), but individual graphene sheet images are, for example, as shown at 210 and 214 in (a-1) of FIG. Does not form a completely closed continuous ring, but forms a discontinuous ring that is interrupted on the way. Some graphene sheet images may be branched as shown at 211 in FIG. 4A-1. At the discontinuous point, a plurality of arc-shaped TEM images constituting one discontinuous ring may be partially disturbed as shown at 222 in (a-1) of FIG. Although there may be an interval between adjacent graphene sheet images as shown at 223 in FIG. 4 (a-1), a large number of arc-shaped graphene sheet images observed by TEM may be A multilayer tube structure is formed.

  Further, as is apparent from 100 of FIGS. 1 and 4A-1, when the longitudinal direction of the nanoflake carbon tube is observed by TEM, a large number of substantially linear graphene sheet images show the iron-carbon composite. Are arranged in a multilayer shape substantially in parallel with the longitudinal direction, but the individual graphene sheet images 110 are not continuous over the entire length of the iron-carbon composite in the longitudinal direction, and are discontinuous on the way. Some graphene sheet images may be branched, as indicated by 111 in (a-1) of FIG. At the discontinuous point, among the TEM images arranged in layers, the TEM image of one discontinuous layer is at least partially separated from the adjacent graphene sheet image as shown at 112 in (a-1) of FIG. In some cases, there are cases in which the graphene sheet images are overlapped with each other, and in some cases, as shown at 113, there is a slight distance from an adjacent graphene sheet image. However, a large number of substantially linear TEM images form a multilayer structure as a whole.

  The structure of such a nanoflake carbon tube is significantly different from a multi-walled carbon nanotube. FIG. 4A-2 is a schematic TEM image of the nested multi-walled carbon nanotube. In FIG. 4A-2, reference numeral 300 schematically shows a TEM image in the longitudinal direction of the nested multi-walled carbon nanotube, and 400 indicates a cross section substantially perpendicular to the longitudinal direction of the nested multi-walled carbon nanotube. Are schematically shown. That is, as shown at 400 in FIG. 4A-2, the multi-walled carbon nanotube having a nested structure has a TEM image of a cross section perpendicular to the longitudinal direction thereof, as shown at 410, a perfect circular TEM image. 4 (a-2) of FIG. 4 and a structure in which linear graphene sheet images 310 continuous over the entire length in the longitudinal direction are arranged in parallel. Concentric cylindrical or nested structure).

  From the above, although the details have not been completely elucidated yet, the nano-flake carbon tube that constitutes the iron-carbon composite forms a tube as a whole by a large number of flake-like graphene sheets overlapping in a patchwork or papier shape. Seems to be doing.

  Such a nano-flake carbon tube and an iron-carbon composite made of iron carbide or iron contained in a space inside the tube are made of a nested multi-walled carbon nanotube tube as described in Japanese Patent No. 2546114. The structure of the carbon tube is significantly different from that of the composite in which the metal is included in the space.

  When the nano-flake carbon tube constituting the iron-carbon composite is observed by TEM, with respect to a number of substantially linear graphene sheet images oriented in the longitudinal direction, the length of each graphene sheet image is: Usually, it is about 2 to 500 nm, especially about 10 to 100 nm. That is, as shown by 100 in FIG. 4A-1, a large number of TEM images of the substantially linear graphene sheet indicated by 110 are collected to form a TEM image of the wall of the nanoflake carbon tube. The length of each substantially linear graphene sheet image is usually about 2 to 500 nm, particularly about 10 to 100 nm. As described above, in the iron-carbon composite, the outermost layer of the nanoflake carbon tube constituting the wall portion is formed of a discontinuous graphene sheet that is not continuous over the entire length in the longitudinal direction of the tube. The length of the outer carbon net surface is usually about 2 to 500 nm, especially about 10 to 100 nm.

As described above, the carbon portion of the wall of the nanoflake carbon tube constituting the iron-carbon composite has a tubular shape with many flake-like graphene sheets oriented in the longitudinal direction as described above. It has a graphitic structure in which the average distance (d ₀₀₂ ) between carbon net surfaces is 0.34 nm or less (for example, about 0.335 to 0.339 nm) as measured by the method.

  The wall of the iron-carbon composite nanoflake carbon tube used in the present invention has a thickness of 49 nm or less (for example, about 0.1 to 40 nm), particularly about 0.1 to 20 nm, and preferably about 1 to 20 nm. About 10 nm, and is substantially uniform over the entire length.

(2) Iron-carbon composite comprising nested multi-walled carbon nanotubes and iron carbide or iron As described above, it is obtained by performing a specific heating step after performing steps (1) and (2). The carbon tube constituting the iron-carbon composite becomes a multi-walled carbon nanotube having a nested structure.

  The nested multi-walled carbon nanotube thus obtained is a concentric tube whose TEM image of a cross section perpendicular to the longitudinal direction forms a substantially perfect circle, as shown at 400 in FIG. And a structure (concentric cylindrical or nested structure) in which continuous graphene sheet images are arranged in parallel over the entire length in the longitudinal direction.

  An average distance (d002) between carbon mesh planes of a carbon portion of a wall portion of a nested multi-walled carbon nanotube constituting an iron-carbon composite is 0.34 nm or less (for example, as measured by an X-ray diffraction method). (About 0.335 to 0.339 nm).

  The thickness of the wall portion composed of the nested multi-walled carbon nanotube of the iron-carbon composite is 49 nm or less (for example, about 0.1 to 40 nm), particularly about 0.1 to 20 nm, and preferably about 1 to 10 nm. And is substantially uniform over its entire length.

(B) Included iron carbide or iron The filling rate (10 to 90%) of iron carbide or iron in the space inside the carbon tube selected from the group consisting of the nanoflake carbon tube and the nested multi-walled carbon nanotube is iron. Observing the carbon composite with a transmission electron microscope, and comparing the area of the image of the space of each carbon tube (that is, the space surrounded by the tube wall of the carbon tube) with the area of iron carbide or iron-filled It is the ratio of the area of the image.

  The filling form of iron carbide or iron includes a form in which the space in the carbon tube is continuously filled, a form in which the space in the carbon tube is intermittently filled, and the like. Is filled. Therefore, the iron-carbon composite used in the present invention may be referred to as a metal-containing carbon composite, an iron compound-containing carbon composite, iron carbide, or an iron-containing carbon composite.

  In addition, iron carbide or iron included in the iron-carbon composite is oriented in the longitudinal direction of the carbon tube, has high crystallinity, and corresponds to the area of the TEM image in the range in which the iron carbide or iron is filled. The ratio of the area of the TEM image of crystalline iron carbide or iron (hereinafter referred to as “crystallization ratio”) is generally about 90 to 100%, particularly about 95 to 100%.

  The high crystallinity of the encapsulated iron carbide or iron is evident from the fact that, when observed by TEM from the side of the iron-carbon composite, the TEM images of the inclusions are arranged in a lattice, and the electron beam It is clear from the fact that a clear diffraction pattern is obtained in the diffraction.

  The inclusion of iron carbide or iron in the iron-carbon composite used in the present invention can be easily confirmed by an electron microscope and an EDX (energy dispersive X-ray detector).

(Overall shape of iron-carbon composite)
Since the iron-carbon composite has a small curvature, is straight, and has a substantially uniform thickness throughout its entire length, it has a uniform shape over its entire length. I have. Its shape is columnar, mainly cylindrical.

  The outer diameter of the iron-carbon composite is usually in the range of about 1 to 100 nm, particularly about 1 to 50 nm, preferably in the range of about 1 to 30 nm, and more preferably in the range of about 10 to 30 nm. The aspect ratio (L / D) of the length (L) of the tube to the outer diameter (D) is about 5 to 10,000, particularly about 10 to 1,000.

  The phrase “straight”, which is one term that describes the shape of the iron-carbon composite, is defined as follows. That is, the carbonaceous material containing the iron-carbon composite was observed in a range of 200 to 2000 nm square by a transmission electron microscope, the length of the image was W, and the length when the image was linearly extended was Wo. In this case, it means shape characteristics in which the ratio W / Wo is 0.8 or more, particularly 0.9 or more.

  The iron-carbon composite has the following properties when viewed as a bulk material. That is, in the present invention, iron or iron carbide is filled in a range of 10 to 90% of the space in the tube of the carbon tube selected from the above-mentioned nanoflake carbon tube and nested multi-walled carbon nanotube. The carbon composite is not a trace amount that can be barely observed by microscopic observation, but is a bulk material containing a large number of the iron-carbon composites, a carbonaceous material including the iron-carbon composite, or iron carbide or iron carbide. It can be obtained in large quantities in the form of a material that can be called an encapsulated carbonaceous material.

  FIG. 3 shows an electron micrograph (transmission electron micrograph) of the nanoflake carbon tube manufactured in Reference Example 2 to be described later and a carbonaceous material made of iron carbide filled in the inner space of the tube. As can be seen from FIG. 3, in the carbonaceous material containing the iron-carbon composite, basically, almost all (particularly, 99% or more) of the carbon tube has the space (that is, the carbon tube). Usually, iron carbide or iron is filled in a range of 10 to 90% of the space surrounded by the tube wall, and there is usually no carbon tube in which the space is not substantially filled. However, in some cases, a trace amount of iron carbide or a carbon tube not filled with iron may be mixed.

  Further, in the carbonaceous material, an iron-carbon composite in which iron or iron carbide is filled in 10 to 90% of the space inside the carbon tube as described above is a main component. Other than the body, soot may be included. In such a case, the components other than the iron-carbonaceous composite are removed to improve the purity of the iron-carbonaceous composite in the carbonaceous material, and the carbonaceous material substantially consisting only of the iron-carbon composite is removed. You can also get

  Further, unlike a material which can be confirmed only in a small amount by conventional microscopic observation, a large amount of a carbonaceous material containing an iron-carbon composite can be synthesized, so that the weight can be easily increased to 1 mg or more.

The carbonaceous material has an irradiation area of 25 mm ² or more with respect to 1 mg of the carbonaceous material, and in powder X-ray diffraction measurement in which CuKα X-rays are irradiated, 40 ° <2θ belonging to iron or iron carbide contained therein. The integrated intensity of the peak exhibiting the strongest integrated intensity among the peaks at <50 ° is defined as Ia, and the peak at 26 ° <2θ <27 ° attributed to the average distance (d ₀₀₂ ) between the carbon netting planes of the carbon tube. When the integrated intensity is Ib, the ratio R (= Ia / Ib) of Ia to Ib is preferably about 0.35 to 5, particularly about 0.5 to 4, and more preferably about 1 to 3. is there.

In the present specification, the ratio of Ia / Ib is called an R value. This R value is such that when a carbonaceous material containing an iron-carbon composite is observed in an X-ray diffraction method with an X-ray irradiation area of 25 mm ² or more, peak intensity is observed as an average value of the entire carbonaceous material. Therefore, instead of the encapsulation rate or filling rate in one iron-carbon composite that can be measured by TEM analysis, the filling rate or encapsulation of iron carbide or iron as a whole carbonaceous material that is an aggregate of iron-carbon composites It shows the average value of the ratio.

  The average filling rate of the carbonaceous material as a whole including a large number of iron-carbon composites is determined by observing a plurality of visual fields with a TEM and observing iron carbide or iron in a plurality of iron-carbon composites observed in each visual field. It can also be determined by measuring the average filling rate and calculating the average value of the average filling rates of a plurality of visual fields. When measured by such a method, the average filling rate of iron carbide or iron as the whole carbonaceous material comprising the iron-carbon composite is about 10 to 90%, particularly about 40 to 70%.

(Nanoflake carbon tube)
By subjecting the iron-carbon composite to acid treatment, the contained iron or iron carbide is dissolved and removed, and a hollow nanoflake carbon tube having no iron or iron carbide in the tube space can be obtained.

  Examples of the acid used in the acid treatment include hydrochloric acid, sulfuric acid, nitric acid, and hydrofluoric acid, and the concentration thereof is preferably about 0.1 to 2N. As the acid treatment method, various methods can be used. For example, about 1 g of an iron-containing nanoflake carbon tube is dispersed in 100 ml of 1N hydrochloric acid, and stirred at room temperature for about 6 hours. After filtration and separation, the same treatment is further performed twice with 100 ml of 1N hydrochloric acid, whereby a hollow nanoflake carbon tube can be obtained.

  The basic configuration of the nanoflake carbon tube is not particularly changed by such an acid treatment. Therefore, even in a hollow nanoflake carbon tube in which iron or iron carbide does not exist in the space in the tube, the length of the carbon netting surface constituting the outermost surface is 500 nm or less, particularly 2 to 500 nm, particularly 10 to 10 nm. 100 nm.

  Furthermore, in the present invention, even if the additive is a compound having an aromatic ring, the dispersibility can be improved. Among the additives, examples of the compound having an aromatic ring include, for example, carbon black (acid carbon black, neutral carbon black, Ketjen black, etc.), graphite, carbon fiber (carbon fiber), activated carbon, fullerene, carbon nanotube, and the like. Such as carbon materials (carbon materials), colored dyes for color resists (red (R), blue (B), green (G), etc.), near-infrared absorbing dyes, carrier transport agents and charge transfer agents for solar cells And functional pigments (phthalocyanine dyes, carbazole dyes, cyanine dyes, azo dyes, pyromethene dyes, etc.). Among them, it is effective to combine the compound (I) or a derivative thereof with a coloring agent, carbon black (particularly neutral carbon black), a carbon material such as carbon nanotube or graphite, and the like.

  The proportion of the additive can be appropriately selected depending on the kind of the compound (I) or a derivative thereof. For example, the additive can be selected from a range of about 0.1 to 300 parts by weight based on 100 parts by weight of the compound (I) or the derivative thereof. When the compound (I) or its derivative is a resin, for example, 0.1 to 100 parts by weight, preferably 0.3 to 50 parts by weight, more preferably 0.5 to 30 parts by weight (particularly 1 to 20 parts by weight) Part) degree.

  When the compound (I) or a derivative thereof is a low molecular weight compound or an oligomer, the proportion of the additive is, for example, 10 to 300 parts by weight, preferably 30 to 200 parts by weight, based on 100 parts by weight of the compound (I) or a derivative thereof. It may be about parts by weight.

  In particular, in the present invention, 1 to 500 parts by weight of an additive [for example, 3 to 450 parts by weight (for example, 3 to 200 parts by weight), preferably 5 to 500 parts by weight, based on 100 parts by weight of compound (I) or a derivative thereof. Even at a high additive concentration of about 400 parts by weight (for example, 10 to 350 parts by weight), more preferably about 20 to 300 parts by weight (for example, 30 to 250 parts by weight), physical properties and moldability are not reduced. The dispersibility can be efficiently improved. Therefore, the composition of the present invention can be suitably used as a masterbatch containing the compound (I) or a derivative thereof and an additive.

  The ratio of the additive is, for example, about 0.1 to 100 parts by weight, preferably about 0.3 to 50 parts by weight, based on 100 parts by weight of the resin component containing the compound (I) or a derivative thereof. Good.

  The form of the composition of the present invention can be appropriately selected depending on the form of the compound having a fluorene skeleton (eg, resin), and is, for example, in the form of powder or granules, pellets (eg, resin pellets, master batch pellets), and the like. And may be in the form of a coating composition (coating liquid) as described below.

  Further, the composition of the present invention can also be used as a coating composition (coating solution). The coating composition may be composed of the compound (I) or a derivative thereof and an additive, and may be a solventless coating composition (coating agent) or a solvent-containing coating composition (coating agent). Is also good. The coating composition containing a solvent may be a solution or a dispersion. In the coating composition (coating solution), the solvent is not particularly limited. Depending on the type of the compound having a fluorene skeleton and the additive, a common solvent such as a hydrocarbon (for example, an aliphatic hydrocarbon such as pentane or hexane) may be used. Hydrogens, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene, halogen-based solvents (haloalkanes such as dichloromethane, haloarenes such as monochlorobenzene), alcohols (methanol, ethanol, Alkyl alcohols such as isopropanol, etc.), diols (alkane diols such as ethylene glycol and propylene glycol, (poly) oxyalkylene glycols such as diethylene glycol and polyoxyethylene glycol), ethers (diethyl ether) Any chain ethers, cyclic ethers such as tetrahydrofuran, etc., esters (acetates such as ethyl acetate), ketones (dialkyl ketones such as acetone and ethyl methyl ketone, cyclic ketones such as cyclohexanone). And glycol ether esters (eg, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, cellosolve acetate), cellosolves (eg, methyl cellosolve, ethyl cellosolve), and carbitols (eg, carbitol). These solvents may be used alone or in combination of two or more.

  The proportion of the solvent may be within a range that does not impair the applicability, and 0.5 to 100 parts by weight of the solvent relative to 1 part by weight of the solid content of the composition (for example, the compound having the fluorene skeleton and the additive). , Preferably about 1 to 50 parts by weight, more preferably about 2 to 30 parts by weight.

  The composition of the present invention can be produced or prepared by mixing a compound having a fluorene skeleton, an additive, and if necessary, other components (such as a solvent). The mixing method can be appropriately selected according to the form of the composition, for example, mixing of a ribbon blender, a tumble mixer, a Hensiel mixer, a sand mill, a dyno mill, a homogenizer, an attritor, a ball mill, a paint shaker, a sand grinder, a fluidizer, and the like. A method using a mixing machine or a dispersing machine, a method using melt kneading using a mixing means with a kneading machine such as an open roller, a kneader, a Banbury mixer, an extruder, and the like can be used. In the coating composition, a dispersion medium, for example, beads (glass beads, zirconia beads, etc.) may be used depending on the type of the mixer or the disperser (such as a paint shaker). These mixing methods may be used alone or in combination of two or more.

  In addition, the fluorene-based composition of the present invention can be formed by a known molding method, for example, an injection molding method, an injection compression molding method, an extrusion molding method, a transfer molding method, depending on the form of the composition (resin pellets, coating composition, etc.). A molded product can be obtained by a method such as a blow molding method, a pressure molding method, and a coating method (spin coating method, roll coating method, curtain coating method, dip coating method, casting molding method, and the like). The shape of the molded product may be a two-dimensional structure (film, sheet, coating (or thin film), plate, etc.), a three-dimensional structure (eg, pipe, rod, tube, leather, hollow article, etc.). No.

  The fluorene-based composition of the present invention and the molded article thereof have improved dispersibility of additives and exhibit their functions with a small amount, so that the inherent properties of the resin are not impaired. Therefore, in the composition of the present invention and the molded article thereof, the properties of the additive, for example, coloring, coloring, conductivity, mechanical strength, and the like can be efficiently improved depending on the type of the additive. Specifically, for example, a coloring agent (colorant) can improve coloring property or degree of coloring by the coloring agent, and a conductive agent can improve conductivity by the conductive agent. Further, the composition of the present invention is coatable, so that it can be applied in a wide range of applications. Furthermore, the composition of the present invention can be effectively used as a masterbatch or the like because the dispersibility can be efficiently improved even when the concentration of the additive is high. In such a masterbatch, the content of additives (filler, conductive agent, colorant, etc.) is 30 to 500 parts by weight based on 100 parts by weight of the compound represented by the formula (I) or a derivative thereof. Preferably, it may be about 50 to 400 parts by weight, more preferably about 75 to 300 parts by weight (for example, 100 to 250 parts by weight).

  Therefore, the composition of the present invention and a molded article thereof include a paint, an antistatic material, a charging tray, a conductive sheet, a protective film for electronic devices and liquid crystal members, an optical disk, an inkjet printer, a digital paper, an organic semiconductor laser, a thermosensitive recording material, Holographic recording materials, dye-sensitized solar cells, electromagnetic interference (EMI) shielding films, photochromic materials, organic electroluminescent (EL) elements, organic photoreceptors, color filters or color materials for color filters (eg, black matrix (BM)) , Color filter layer on which R, G, B pixels are arranged, etc.), sliding members, automotive parts materials, aerospace materials, dye-type solar cells, carrier transport agents, inks, adhesives, adhesives, building materials, interiors Suitable for materials, resin fillers, colored glass, luminous bodies, sensors and the like.

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

Synthesis Example 1
Normal melt polymerization using 1 mol of cyclohexanedicarboxylic acid (CHDA), 0.1 mol of ethylene glycol (EG), 0.9 mol of 9,9-bis {4- (2-hydroxyethoxy) phenyl} fluorene (BPEF) as raw materials Thus, a copolymerized polyester was obtained. The weight average molecular weight Mw of this copolymerized polyester was 51,000, and the glass transition point Tg was 120 ° C.

Example 1
100 parts by weight of the copolymerized polyester obtained in Synthesis Example 1 was dry blended with 3 parts by weight of carbon black (MA100, manufactured by Mitsubishi Chemical Corporation) and melt-kneaded at 210 ° C. using an extruder to obtain resin pellets. Got. Next, a plate (0.1 mm thick) was formed from the obtained pellets using a desktop hot press machine (resin temperature 220 ° C.). The coloring degree of the molded plate was measured using a spectrophotometer (Macbeth Color Eye CE-3000). As a result of using a D65 light source (10-degree visual field) and evaluating with CIE 1976 (Lab-color system), the L value was 5.51.

Comparative Example 1
The same procedure as in Example 1 was carried out except that polystyrene was used instead of the copolymerized polyester obtained in Synthesis Example 1, and as a result of measuring the L value as an evaluation of the degree of coloring, the value was 9.38. In comparison, the degree of coloring was low.

Example 2
As an epoxy resin, 100 parts by weight of bisphenoxyethanol full orange glycidyl ether (manufactured by Osaka Gas Chemical Co., Ltd., Mw 550.6) is dissolved in 100 parts by weight of toluene, and 6.5 parts by weight of carbon black (MA100, manufactured by Mitsubishi Chemical Corporation) is used. , 27 parts by weight of a modified aliphatic polyamine-based curing agent (ADEKA HARDNER EH-458) as a curing agent, and after stirring and dispersing, form a 0.3 mm thick coating film on a polypropylene plate and heat at 60 ° C. for 3 hours. To prepare a sample. The coloring degree of the prepared coating film was measured using a spectrophotometer (Macbeth Color Eye CE-3000). As a result of using a D65 light source (10-degree visual field) and evaluating with CIE 1976 (Lab-color system), the L value was 6.69.

Comparative Example 2
An epoxy resin was prepared in the same manner as in Example 2 except that 100 parts by weight of a bisphenol A-based epoxy resin (ADEKARESIN EP-4520) was dissolved in 100 parts by weight of 2-butanone. As a result, it was 15.32, and the coloring degree was lower than that of Example 2.

Example 3
As a vinyl ester resin, 2 parts by weight of t-butyl peroxybenzoate was added to 100 parts by weight of an acrylic monomer having a fluorene skeleton (bisphenoxyethanol fluorene acrylate, manufactured by Osaka Gas Chemical Co., Ltd., Mw 546.6), and then toluene was further added. 100 parts by weight and 6.5 parts by weight of carbon black (manufactured by Mitsubishi Chemical Corporation, MA100) were added, and after stirring and dispersion, a 0.2 mm-thick coating film was formed on a polypropylene plate. A sample was prepared through three steps of heat treatment at 1 ° C. for 1 hour and 180 ° C. for 1 hour. The coloring degree of the prepared coating film was measured using a spectrophotometer (Macbeth Color Eye CE-3000). As a result of using a D65 light source (10-degree visual field) and evaluating by CIE 1976 (Lab-color system), the L value was 6.38 and the degree of coloring was high.

Synthesis Example 2
Synthesis Example 1 was the same as Synthesis Example 1 except that ethylene glycol (EG) was changed to 0.2 mol and 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (BPEF) was changed to 0.8 mol. Similarly, a copolymer polyester was obtained by ordinary melt polymerization. The weight average molecular weight Mw of this copolymerized polyester was 42,000, and the glass transition point Tg was 118 ° C.

Example 4
35 parts by weight of the copolymerized polyester obtained in Synthesis Example 2, 35 parts by weight of polycarbonate (manufactured by Teijin Chemicals Ltd., Panlite (L-1225L)), 30 parts by weight of carbon fiber (UAL1 manufactured by Toho Tenax Co., Ltd.) Was kneaded at 270 ° C. using a twin screw extruder, and the obtained strand was cut with a pelletizer to obtain pellets. The obtained pellet was dried with hot air at 110 ° C. for 12 hours, and then injection molded at a molding temperature of 270 ° C. to obtain a test piece. As a result of measuring five samples for each of the obtained test pieces, the average value was 4.3 Ω · cm in horizontal direction, 136 MPa in tensile strength, 136 MPa in maximum strain, 8.1% in bending strength, and It was 192 MPa.

Comparative Example 4
A test piece was obtained in the same manner as in Example 4, except that 35 parts by weight of the copolymerized polyester in Example 4 was replaced with 35 parts by weight of polycarbonate (manufactured by Teijin Chemicals Ltd., Panlite (L-1225L)). A similar test was performed on the obtained test piece, and as a result, the conductivity was 50.5 Ω · cm, the tensile strength was 137 MPa, the maximum strain was 7.1%, and the bending strength was 177 MPa.

Example 5
40 parts by weight of the copolymerized polyester of Example 4, 40 parts by weight of polycarbonate (manufactured by Teijin Chemicals Ltd., Panlite (L-1225L)), and 30 parts by weight of carbon fiber (UAL1 manufactured by Toho Tenax Co., Ltd.) A test piece was obtained in the same manner as in Example 4, except that nickel-plated carbon fiber (MC manufactured by Toho Tenax Co., Ltd., MC) was replaced by 20 parts by weight. A similar test was performed on the obtained test piece, and as a result, the conductivity was 9.06 Ω · cm, the tensile strength was 120 MPa, the maximum strain was 6.8%, and the bending strength was 150 MPa.

Comparative Example 5
A test piece was obtained in the same manner as in Example 5, except that 35 parts by weight of the copolyester of Example 5 was replaced with 35 parts by weight of polycarbonate (manufactured by Teijin Chemicals Ltd., Panlite (L-1225L)). A similar test was performed on the obtained test piece. As a result, the conductivity was 715 Ω · cm, the tensile strength was 95 MPa, the maximum strain was 4.5%, and the bending strength was 144 MPa.

Synthesis Example 3
A copolymerized polyester was obtained in the same manner as in Synthesis Example 1, except that 1 mol of terephthalic acid was used instead of 1 mol of CHDA in Synthesis Example 1, and 0.3 mol of EG and 0.7 mol of BPEF were used. The weight average molecular weight Mw of this copolymerized polyester was 45,000, and the glass transition point Tg was 142 ° C.

Example 6
5 g of the copolymerized polyester obtained in Synthesis Example 3 was dissolved in 45 g of chloroform to prepare a chloroform solution having a resin concentration of 10% by weight. 0.05 g of a phthalocyanine dye (Lionol Blue FG-7315 manufactured by Toyo Ink Co., Ltd.) was mixed with 5 g of the obtained 10% by weight chloroform solution (copolymerized polyester: dye (weight ratio) = 10: 1). The mixture was dispersed with a paint shaker for 2 hours to obtain a filler dispersion.

Example 7
A filler dispersion was prepared in the same manner as in Example 6, except that the phthalocyanine dye was changed to 0.15 g.

Example 8
A filler dispersion was prepared in the same manner as in Example 6, except that the phthalocyanine dye was changed to 0.25 g.

Comparative Example 6
A filler dispersion was prepared in the same manner as in Example 6, except that the copolymerized polyester was replaced with polycarbonate (manufactured by GE Plastics Co., Ltd., Lexan 121R-111).

Comparative Example 7
A filler dispersion was prepared in the same manner as in Example 7, except that the copolymerized polyester was changed to polycarbonate (manufactured by GE Plastics Co., Ltd., Lexan 121R-111).

Comparative Example 8
A filler dispersion was prepared in the same manner as in Example 8, except that the copolymerized polyester was changed to polycarbonate (manufactured by GE Plastics Co., Ltd., Lexan 121R-111).

Example 9 and Comparative Example 9
The dispersions obtained in Examples 6 to 8 and Comparative Examples 6 to 8 were coated on a black-and-white concealing paper and a glass plate, and the obtained coating film was measured with a gloss meter (IAS-, manufactured by Quality Engineering Associates, Inc.). 1000), the gloss values of the white background portion, the black background portion, and the glass plate of the black-and-white concealment paper were measured at an angle of 60 ° C. in accordance with JIS-K7105. Table 1 shows the obtained results. Under the same conditions of the content of the dye, in each case, the coating film obtained from the dispersion of the example having a fluorene skeleton shows a higher gloss value than the coating film obtained from the dispersion of the comparative example. Was.

Synthesis Example 4
A copolymerized polyester was obtained in the same manner as in Synthesis Example 3 except that EG was changed to 0.6 mol and BPEF was changed to 0.4 mol. The weight average molecular weight Mw of this copolymerized polyester was 44,000, and the glass transition point Tg was 128 ° C.

Example 10
A filler dispersion was prepared in the same manner as in Example 6, except that the copolymerized polyester was replaced with the copolymerized polyester obtained in Synthesis Example 4 and the phthalocyanine dye was replaced with carbon black (Printex 75R, manufactured by Degussa Co., Ltd.). Got.

Example 11
A dispersion was prepared in the same manner as in Example 10, except that 0.15 g of carbon black was used.

Example 12
A dispersion was prepared in the same manner as in Example 10 except that carbon black was changed to 0.25 g.

Example 13
A dispersion was prepared in the same manner as in Example 10, except that the carbon black was changed to carbon black (MA100 (pH = 3.5), manufactured by Mitsubishi Chemical Corporation).

Example 14
A dispersion was prepared in the same manner as in Example 10, except that the carbon black was changed to carbon black (MA40 (pH = 7.5), manufactured by Mitsubishi Chemical Corporation).

Example 15
A dispersion was prepared in the same manner as in Example 10, except that the carbon black was changed to carbon black (manufactured by Mitsubishi Chemical Corporation, MA600 (pH = 7)).

Example 16
A dispersion was prepared in the same manner as in Example 10, except that carbon black was changed to quinacridone (PV19, manufactured by Ciba).

Example 17
A dispersion was prepared in the same manner as in Example 10, except that the carbon black was replaced with a yellow oil die (Py147, manufactured by Ciba).

Comparative Example 10
A dispersion was prepared in the same manner as in Example 10 except that the copolymerized polyester was replaced with polycarbonate (manufactured by GE Plastics Co., Ltd., Lexan 121R-111).

Comparative Example 11
A dispersion was prepared in the same manner as in Example 11 except that the copolymerized polyester was changed to polycarbonate (manufactured by GE Plastics Co., Ltd., Lexan 121R-111).

Comparative Example 12
A dispersion was prepared in the same manner as in Example 12, except that the copolymerized polyester was changed to polycarbonate (manufactured by GE Plastics Co., Ltd., Lexan 121R-111).

Comparative Example 13
A dispersion was prepared in the same manner as in Example 13 except that the copolymerized polyester was changed to polycarbonate (manufactured by GE Plastics Co., Ltd., Lexan 121R-111).

Comparative Example 14
A dispersion was prepared in the same manner as in Example 14 except that the copolymerized polyester was replaced with polycarbonate (GE Plastic Co., Ltd., Lexan 121R-111).

Comparative Example 15
A dispersion was prepared in the same manner as in Example 15 except that the copolymerized polyester was replaced with polycarbonate (manufactured by GE Plastics Co., Ltd., Lexan 121R-111).

Comparative Example 16
A dispersion was prepared in the same manner as in Example 16, except that the copolymerized polyester was replaced with polycarbonate (manufactured by GE Plastics Co., Ltd., Lexan 121R-111).

Comparative Example 17
A dispersion was prepared in the same manner as in Example 17 except that the copolymerized polyester was replaced with polycarbonate (manufactured by GE Plastics Co., Ltd., Lexan 121R-111).

Example 18 and Comparative Example 18
The solutions obtained in Examples 10 to 17 and Comparative Examples 10 to 17 were respectively coated on black-and-white concealing paper and a glass plate, and the obtained coating film was measured with a gloss meter (Quality Engineering Associates, Inc., IAS). -1000), the gloss values of the white background portion, the black background portion, and the glass plate of the black-and-white concealment paper were measured. Table 2 shows the obtained results. Under the same conditions of the content of additives such as carbon black, in each case, the coating film obtained from the dispersion of the example having a fluorene skeleton has a higher gloss value than the dispersion of the comparative example. Was.

Example 19
100 parts by weight of the copolymerized polyester obtained in Synthesis Example 4 and 1 part by weight of an organic bentonite (Esven-E, manufactured by Hojun Co., Ltd.) were kneaded at 210 ° C. using a twin-screw extruder, and the obtained strand was mixed. The pellet was cut with a pelletizer. After the obtained pellets were dried with hot air at 110 ° C. for 12 hours, they were injection molded to obtain test pieces.

Example 20
A test piece was prepared in the same manner as in Example 19 except that the amount of the organic bentonite was changed to 3 parts by weight.

Example 21
A test piece was prepared in the same manner as in Example 19 except that the organic bentonite was changed to 5 parts by weight.

Comparative Example 19
Only the copolymerized polyester obtained in Synthesis Example 4 was injection molded to obtain a test piece.

Example 22
The elastic modulus, tensile strength, elongation at break, and energy at break of the test pieces obtained in Examples 19 to 21 and Comparative Example 19 were measured. Table 3 shows the obtained results. High physical properties were obtained by mixing the organic bentonite.

Example 23
2.31 g of bisphenol fluor orange glycidyl ether (manufactured by Osaka Gas Chemical Co., Ltd.) as an epoxy component, 1.75 g of bisphenol fluorene (manufactured by Osaka Gas Chemical Co., Ltd.) as a curing component, 5.94 g of methyl ethyl ketone (MEK), carbon black ( 1.2 g of MA100 (manufactured by Mitsubishi Chemical Corporation) was dispersed in a paint shaker for 1 hour. The obtained filler dispersion liquid was formed into a film on a glass plate using a spin coater (rotation speed: 500 rpm, 10 seconds), and the conductivity in the horizontal direction was measured. The resistivity was 6.79E + 03 (6.79 × 10 ³ ) It was Ω · cm.

Comparative Example 23
The epoxy component was changed to 2 g of a bisphenol A type epoxy resin (EP4520, manufactured by Asahi Denka Co., Ltd.), the curing component was changed to 0.8 g of an amine curing agent (“EH458” manufactured by Asahi Denka Co., Ltd.), and MEK was changed to MEK. A film was formed in the same manner as in Example 23 except that the amount was changed to 4.7 g, and the conductivity was measured. As a result, the resistivity was 2.44E + 05 (2.44 × 10 ⁵ ) Ω · cm.

Reference Example 1
Production of Amorphous Nanoscale Carbon Nanotubes Amorphous nanoscale carbon nanotubes were produced by the following method.

10 mg of anhydrous iron chloride powder (particle size: 500 μm or less) was uniformly sprinkled on a 60 μm × 10 mm × 10 mm polytetrafluoroethylene (PTFE) film, and then plasma-excited. The conditions for plasma excitation were as follows:
Atmosphere: Argon (Ar)
Internal pressure: 0.01 torr
Input power: 300W
RF frequency: 13.56 MHz
After completion of the reaction (after plasma excitation), it was confirmed by a scanning electron microscope (SEM) and X-ray diffraction that an amorphous nanoscale carbon tube (outer diameter; 10 to 60 nm, length: 5 to 6 μm) was formed. The X-ray diffraction angle (2θ) of the obtained amorphous nanoscale carbon tube is 19.1 °, and the carbon network plane interval (d002) calculated from the angle is 4.6 °, and the half value width of the band at 2θ is 8.8. It was once.

Reference Example 2
Using toluene as a raw material and ferric chloride as a catalyst and performing a reaction according to the method described in JP-A-2002-338220, iron carbide is partially included in the space inside the tube of the nanoflake carbon tube. Thus, a carbonaceous material containing the iron-carbon composite was obtained.

  From the result of SEM observation, the obtained iron-carbon composite had an outer diameter of 20 to 100 nm and a length of 1 to 10 μm and was highly linear. The thickness of the carbon wall was 5 to 40 nm, and was substantially uniform over the entire length. In the transmission electron microscope (TEM) observation, the wall has a carbon wall surface that looks neither patch-shaped nor scroll-shaped, but patch-shaped (so-called paper-mache or papier-shaped). X-ray diffraction confirmed that the nanoflake carbon tube had a graphitic structure with an average distance (d002) between carbon mesh planes of 0.34 nm or less. In addition, X-ray diffraction and energy dispersive X-ray analysis (EDX) confirmed that iron carbide was included in the iron-carbon composite.

  When the obtained carbonaceous material containing a large number of iron-carbon composites was observed with an electron microscope (TEM), it was found that the carbonaceous material entered the space of the nanoflake carbon tube (that is, the space surrounded by the tube wall of the nanoflake carbon tube). And iron-carbon composites having various filling rates in the range of 20 to 60%. Further, the average filling rate calculated by observing a plurality of visual fields of the TEM observation image of iron carbide in the space inside the nanoflake carbon tube of the obtained many iron-carbon composites was 30%. Further, the R value calculated from the X-ray diffraction was 0.57.

Example 24
0.03 g of the amorphous nanoscale carbon tube obtained in Reference Example 1 was placed in a resin solution obtained by dissolving 1 g of the copolymerized polyester obtained in Synthesis Example 2 in 4 g of THF, and dispersed with a paint shaker. The obtained dispersion was coated on a polyethylene terephthalate (PET) film so as to have a thickness of 5 μm, and the surface resistance of the obtained coating film was measured. As a result, 2.43E + 06 (2.43 × 10 ⁶⁾ ) Ω / □.

Example 25
A solution in which 0.03 g of the iron-carbon composite obtained in Reference Example 2 was dissolved in 2 g of THF was added dropwise to a resin solution in which 1 g of the copolymerized polyester obtained in Synthesis Example 2 was dissolved in 4 g of THF, and a paint shaker was used. And dispersed. The obtained dispersion was coated on a PET film so as to have a film thickness of 5 μm, and the surface resistance of the obtained coating film was measured. As a result, it was 4.79E + 08 (4.79 × 10 ⁸ ) Ω / □. there were.

Example 26
A solution prepared by dissolving 0.03 g of commercially available carbon nanotubes (manufactured by Shenzhen Nanotech Port Co., Ltd., diameter: 10 nm to 20 nm) in 2 g of THF in a resin solution obtained by dissolving 1 g of the copolymerized polyester obtained in Synthesis Example 2 in 4 g of THF. Was dropped and dispersed with a paint shaker. This dispersion was coated on a PET film so as to have a thickness of 5 μm, and the surface resistance of the obtained coating film was measured to be 8.94E + 08 (8.94 × 10 ⁸ ) Ω / □. .

Synthesis Example 5
100 parts by weight of polytetramethylene glycol ether (PTMG) having hydroxyl groups at both ends and having a number average molecular weight of 2,000, and 52.84 parts by weight of diphenylmethane diisocyanate (MDI) were added, and the mixture was stirred at 130 ° C. for 60 minutes under a nitrogen atmosphere to obtain a prepolymer. Was synthesized. To this prepolymer, 66.34 parts by weight of bisphenoxyethanol fluorene (BPEF) and 3.32 parts by weight of glycerin were added and stirred to obtain a polyurethane resin having a fluorene skeleton.

Example 27
A plate was formed in the same manner as in Example 1, except that the copolymerized polyester of Example 1 was replaced with the polyurethane obtained in Synthesis Example 5. When the degree of coloring of the molded plate was measured in the same manner as in Example 1, the L value was 6.89.

Comparative Example 27
A plate was formed in the same manner as in Example 27 except that BPEF of Synthesis Example 5 was replaced with PTMG. When the degree of coloring of the molded plate was measured in the same manner as in Example 27, the L value was 9.75, which was lower than that of Example 27.

Synthesis Example 6
1 mol of isophthalic acid and 2 mol of propylene glycol were added to a four-necked flask (2 L) equipped with a stirrer, a thermometer, a cooling condenser, a dropping funnel, and an inert gas introduction tube while introducing nitrogen gas. For 3 hours. After reacting until the solid acid value (solid content acid value) became 15 mgKOH / g or less, the mixture was cooled to 150 ° C., 1 mol of maleic anhydride was added, and the reaction was continued. When the solid acid value became 100 to 150 mgKOH / g, the mixture was cooled to 110 ° C., 2 mol of 9,9-bis (4-glycidyloxyethoxyphenyl) fluorene (BPEFG) was added, and the solid acid value became 3 mgKOH / g or less. After the reaction was completed, 2 mol of methacrylic acid, 0.1% by weight of triethylammonium iodide with respect to the reaction mixture, and 500 ppm of hydroquinone monomethyl ether as a polymerization inhibitor were added, and the mixture was further reacted for 3 hours. Thereafter, 40% by weight of diethylene glycol dimethacrylate was added to the solid (solid content) to obtain a vinyl ester resin.

Synthesis Example 7
A vinyl ester resin was obtained in the same manner as in Synthesis Example 6 except that diglycidyl ether of bisphenol A was used instead of BPEFG.

Example 28
100 parts by weight of the vinyl ester resin having a fluorene skeleton obtained in Synthesis Example 6 was mixed with 3 parts by weight of carbon black (MA100, manufactured by Mitsubishi Chemical Corporation), and 6% by weight of cobalt octenoate was added to the solid at 25 ° C. Add 0.5% by weight and sufficiently agitate, add 1.0% by weight of a curing agent (328E, manufactured by Kayaku Akzo Co., Ltd.) to the solid and further stir for about 1 minute to obtain a cured product Was. When the degree of coloring was measured in the same manner as in Example 1, the L value of the obtained cured product was 5.12.

Comparative Example 28
A cured product was obtained in the same manner as in Example 28 except that the vinyl ester resin was changed to the vinyl ester resin obtained in Synthesis Example 7. When the degree of coloring was measured in the same manner as in Example 1, the L value of the obtained cured product was 8.97, which was lower than that in Example 28.

Example 29
The copolymerized polyester and carbon black (MA100, manufactured by Mitsubishi Chemical Corporation) obtained in Synthesis Example 4 were each dried at 120 ° C. for one day. Magnesium stearate (manufactured by Kanto Chemical Co., Ltd.) and the carbon black were mixed in a ratio of the former / the latter (weight ratio) = 20/80 using a paint shaker. The copolymerized polyester and the carbon black are co-extruded at a ratio of the former / the latter (weight ratio) = 99/1 using a twin screw extruder (KZW15-30MG manufactured by Technovel Corp.) to obtain a composite. Obtained. In the co-extrusion, the barrel temperature, the second barrel temperature, and the third barrel temperature in the feed region were set to 220 ° C., and the temperature of the die portion was set to 210 ° C. for co-extrusion. The composite was hot-pressed at 150 ° C. to produce a plate having a mirror-polished surface. The degree of coloring (luminance) of the molded plate was measured using a spectrophotometer (Macbeth Color Eye CE-3000). As a result of using a D65 light source (10-degree visual field) and evaluating with CIE 1976 (Lab-color system), the L value was 5.45.

Comparative Example 29
A plate was obtained in the same manner as in Example 29 except that the copolymerized polyester obtained in Synthesis Example 4 was replaced with a polyethylene terephthalate resin (manufactured by Negoro Sangyo Co., Ltd., weight average molecular weight Mw = 44000). When the degree of coloring of the molded plate was measured in the same manner as in Example 29, the L value was 11.59.

Comparative Example 30
A plate was obtained in the same manner as in Example 29 except that the copolymerized polyester obtained in Synthesis Example 4 was changed to polystyrene (US310, manufactured by Idemitsu Petrochemical Co., Ltd.). When the coloring degree of the molded plate was measured in the same manner as in Example 29, the L value was 11.38.

Example 30
A plate was obtained in the same manner as in Example 29, except that the ratio of the copolymerized polyester obtained in Synthesis Example 4 to carbon black was changed to the ratio of the former / the latter (weight ratio) = 97/3. When the degree of coloring of the molded plate was measured in the same manner as in Example 29, the L value was 5.51.

Comparative Example 31
A plate was obtained in the same manner as in Example 30, except that the copolymerized polyester obtained in Synthesis Example 4 was replaced with a polyethylene terephthalate resin (Negoro Sangyo Co., Ltd., weight average molecular weight Mw = 44000). When the coloring degree of the molded plate was measured in the same manner as in Example 30, the L value was 9.41.

Comparative Example 32
A plate was obtained in the same manner as in Example 30, except that the copolymerized polyester obtained in Synthesis Example 4 was replaced with polystyrene (US310, manufactured by Idemitsu Petrochemical Co., Ltd.). When the degree of coloring of the molded plate was measured in the same manner as in Example 30, the L value was 9.38.

Example 31
A plate was obtained in the same manner as in Example 29, except that the ratio between the copolymerized polyester obtained in Synthesis Example 4 and carbon black was changed to the ratio of the former / the latter (weight ratio) = 95/5. When the coloring degree of the molded plate was measured in the same manner as in Example 29, the L value was 6.08.

Comparative Example 33
A plate was obtained in the same manner as in Example 31, except that the copolymerized polyester obtained in Synthesis Example 4 was replaced with a polyethylene terephthalate resin (Negoro Sangyo Co., Ltd., weight average molecular weight Mw = 44000). When the coloring degree of the formed plate was measured in the same manner as in Example 31, the L value was 8.58.

Comparative Example 34
A plate was obtained in the same manner as in Example 31 except that the copolymerized polyester obtained in Synthesis Example 4 was replaced with a polystyrene resin (US310, manufactured by Idemitsu Petrochemical Co., Ltd.). When the degree of coloring of the molded plate was measured in the same manner as in Example 31, the L value was 8.40.

Examples 32-34 and Comparative Examples 35-37
In Example 29, the production of a plate was attempted in the same manner as in Example 29, except that the proportion of the copolyester and / or the type of the resin was changed to the proportion and / or the resin shown in Table 4, and evaluated based on the following criteria. did.

AA: Similar to the case without additives, plate forming is possible without problems and easy to handle. A: Plate forming is possible, but plate is somewhat brittle. B: Plate forming is possible, but plate is brittle. C: Plate cannot be formed and brittle. Very fragile carbon black aggregates.

  Table 4 shows the results. In Table 4, the resin “PET” used in place of the copolymerized polyester was the polyethylene terephthalate resin used in Comparative Example 33, “PC” was a polycarbonate resin (manufactured by Mitsubishi Chemical Corporation, Iupilon), and “PS” was Each of the polystyrene resins used in Comparative Example 34 is shown.

  As is clear from Table 4, in Examples 32 to 34, molding was possible without lowering moldability even when the additive (carbon black) was used at a high concentration.

  5 and 6 show electron micrographs (magnification: 50,000 times) of the plate cross sections obtained in Example 32 and Comparative Example 37, respectively. As is clear from FIGS. 5 and 6, in the molded article of Example 32, the additive (carbon black) was uniformly dispersed without agglomeration as compared with the molded article of Comparative Example 37.

Example 35
1 mol of bisphenol fluorene was reacted with 1 mol of phosgene to obtain a polycarbonate resin having a fluorene skeleton (weight average molecular weight: about 20,000). A plate was molded in the same manner as in Example 1 except that the copolymerized polyester was replaced with the obtained polycarbonate resin having a fluorene skeleton. When the degree of coloring of the obtained plate was measured in the same manner as in Example 1, a high degree of coloring as in Example 1 was shown.

FIG. 1 is a transmission electron microscope (TEM) photograph of the side surface of the columnar iron-carbon composite obtained in Example 1 of JP-A-2002-338220. FIG. 2 is a transmission electron microscope (TEM) photograph of a cross section of the columnar iron-carbon composite obtained in Example 1 of JP-A-2002-338220, which crosses the longitudinal direction. FIG. 3 is a transmission electron microscope (TEM) photograph of the nanoflake carbon tube manufactured in Reference Example 2 and a carbonaceous material made of iron carbide filled in the inner space of the tube. FIG. 4 is a schematic diagram (a-1) of a TEM image of a columnar iron-carbon composite (nanoflake carbon tube) and a schematic diagram (a-2) of a nested multi-walled carbon nanotube. . FIG. 5 is an electron micrograph of a cross section of the plate obtained in Example 32. FIG. 6 is an electron micrograph of a cross section of the plate obtained in Comparative Example 37.

Explanation of reference numerals

100: TEM image in the longitudinal direction of the nanoflake carbon tube 200: TEM image of a cross section substantially perpendicular to the longitudinal direction of the nanoflake carbon tube 300: TEM image in the longitudinal direction of the nested multilayer carbon nanotube 400: nested multilayer carbon TEM image of a cross section almost perpendicular to the longitudinal direction of the nanotube

Claims (12)

A composition comprising a compound represented by the following formula (I) or a derivative thereof, and an additive.
[In the formula, X ¹ and X ² are the same or different and each is a hydroxyl group, -O (AO) _pH group (where A represents a C _2-3 alkylene group, and p represents an integer of 1 or more. ), An amino group or an N-monosubstituted amino group, R ^{1 to} R ⁴ are the same or different and represent a non-reactive group, m1 and m2 are the same or different and are integers of 0 or 1 to 3, m1 + m2 = It is an integer of 1 to 6, and n1 to n4 are the same or different and are integers of 0 to 4. However, m1 + n1 and m2 + n2 are integers of 0-5. ]   The composition according to claim 1, wherein the derivative of compound (I) is a resin.   The resin is at least one selected from polyester resins, polycarbonate resins, urethane resins, acrylic resins, polyamide resins, polyimide resins, epoxy resins, vinyl ester resins, phenol resins, and aniline resins. A composition according to claim 2.   The composition according to claim 1, wherein the additive comprises at least one selected from a filler, a colorant, and a flame retardant.   The composition according to claim 1, wherein the additive is a compound having an aromatic ring.   The composition according to claim 1, wherein the additive is a carbon material.   The composition according to claim 1, comprising 0.1 to 300 parts by weight of the additive based on 100 parts by weight of the compound (I) or a derivative thereof.   The composition according to claim 1, wherein the derivative of the compound (I) is a resin, and the additive contains 0.3 to 50 parts by weight based on 100 parts by weight of the resin.   The composition according to claim 1, which is a coating composition.   A molded article formed from the composition according to claim 1.   A method for improving the dispersibility of an additive by using the compound (I) according to claim 1 or a derivative thereof.   A method for improving the coloring property or coloring degree of a coloring agent using the compound (I) according to claim 1 or a derivative thereof.