JP5367991B2 - Fluorene polyester oligomer and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorene-based polyester oligomer excellent in the reactivity and flowability and a manufacturing method thereof. <P>SOLUTION: The fluorene-based polyester oligomer is such a fluorene-based polyester oligomer that a polyester-based resin containing a fluorene with a skeleton of 9, 9-bis(hydroxyaryl)fluorene is depolymerized with a depolymerizing agent. The above fluorene-based polyester oligomer may have a weight-average molecular weight of the order of 5,000-30,000. The above fluorene-based polyester oligomer may have an acid value of the order of 0-100 mgKOH/g or may have an hydroxy value of the order of 5-400 mgKOH/g. The above fluorene-based polyester oligomer is excellent in the affinity to resins and is useful as various kinds of optical materials. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a fluorene-based polyester oligomer excellent in reactivity and fluidity, a production method thereof, and an application thereof.

  Polyester resins are useful for various uses such as beverage bottles, films and fibers. From the viewpoint of heat resistance, weather resistance, and the like, polyester resins are also used as paints, adhesives, and the like by being modified by various methods to impart various functions.

  For example, JP-A-9-302054 (Patent Document 1) discloses a branched diol (b-1) having a polybasic acid (A) as an acid component and an alkyl group having 2 or more carbon atoms in the side chain and hydrogenation. A polyester resin (I) obtained by polycondensation of polybutadiene polyol (b-2) as a glycol component (B) has a functional group that reacts with a carboxyl group after depolymerization in the presence of a polybasic acid (C). A polyester resin composition comprising a polyester (meth) acrylate resin (II) obtained by reacting (meth) acrylate (D) with a sensitizer (III) is disclosed (claim 1). ). This document describes that by reacting a polyester resin with (meth) acrylate, the adhesion with an olefin resin can be increased, and it is useful as a paint or an adhesive. However, since the resin composition is inferior in optical properties such as transparency and mechanical strength, its use may be limited.

  Japanese Patent Application Laid-Open No. 8-73579 (Patent Document 2) discloses a compound having a number average molecular weight of 6000 or more synthesized using aromatic dicarboxylic acids and / or aliphatic dicarboxylic acids as acid components and dialcohols as alcohol components. A branched polyester resin is produced by depolymerizing 100 parts by weight of a chain polyester resin with 0.2 to 10 parts by weight of a trivalent or higher valent hydroxycarboxylic acid, and then a high molecular weight to a weight average molecular weight of 20,000 or more by reduced pressure polycondensation reaction A process for producing a polyester resin characterized in that is disclosed. In the branched polyester resin obtained by this production method, a reactive group (or functional group) is introduced by the reaction of a linear polyester resin and a trivalent or higher-valent hydroxycarboxylic acid, and adhesion, mechanical strength, It describes that it has improved water resistance and is useful as a paint and an adhesive. However, since the polyester resin has a branched chain structure and a high molecular weight, the polyester resin is inferior in fluidity (or moldability) and cannot be said to have sufficient adhesiveness. Moreover, it is inferior in transparency, and mechanical strength is still inadequate.

  With the recent rapid advancement of information technology, the demand for adhesives (optical adhesives) that can be used for optical members is expanding. A polyester resin having a fluorene skeleton (fluorene skeleton-containing polyester resin) has been proposed as a transparent resin having a high refractive index and low birefringence and useful for optical applications. For example, Japanese Patent Application Laid-Open Nos. 7-149981 (Patent Document 3) and Japanese Patent Application Laid-Open No. 8-109249 (Patent Document 4) disclose dihydroxy compounds or ester-forming derivatives thereof and dihydroxy compounds having a fluorene skeleton (for example, 9 , 9-bis [4- (2-hydroxyethoxy) phenyl] fluorenes) and aliphatic glycols having 2 to 4 carbon atoms are disclosed. The polyester polymer is excellent in moldability (or fluidity), but is still insufficient for use in applications such as adhesives and paints. Moreover, the said polyester polymer is also low in reactivity and affinity with resin, and is inferior to adhesiveness (or sclerosis | hardenability).

The fluorene skeleton-containing polyester polymer is miscible with components such as resins (eg, polyester resins such as polyethylene terephthalate and polyethylene naphthalate) and fine particles (eg, organic fine particles such as carbon nanotubes, inorganic fine particles, etc.). (Or compatibility and dispersibility) are also inferior, and the use of the polyester polymer is currently limited.
JP-A-9-302054 (Claim 1, paragraph [0046]) JP-A-8-73579 (Claim 1, paragraphs [0015] and [0028]) Japanese Patent Laid-Open No. 7-158881 JP-A-8-109249

  Accordingly, an object of the present invention is to provide a fluorene-based polyester oligomer excellent in reactivity and fluidity and a method for producing the same.

  Another object of the present invention is to provide a fluorene-based polyester oligomer having excellent affinity for a resin and a method for producing the same.

  Still another object of the present invention is to provide a fluorene-based polyester oligomer useful as an optical material and a method for producing the same.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have depolymerized a fluorene-containing polyester oligomer containing a 9,9-bisarylfluorene skeleton, which contains the fluorene skeleton. The oligomer depolymerized with the agent was found to have high reactivity and excellent fluidity, and the present invention was completed.

  That is, the fluorene-based polyester oligomer of the present invention is a fluorene-based polyester oligomer obtained by depolymerizing a fluorene-containing polyester-based resin containing a 9,9-bis (hydroxyaryl) fluorene skeleton with a depolymerizer. The fluorene polyester oligomer may have a weight average molecular weight of about 5000 to 30000. The fluorene-based polyester oligomer may have an acid value of about 0 to 100 mgKOH / g or a hydroxyl value of about 5 to 400 mgKOH / g.

  The fluorene-containing polyester resin has at least the following formula (1)

(In the formula, Z ¹ and Z ² are the same or different and each represents an aromatic hydrocarbon group. R ^1a and R ^1b represent the same or different alkylene group, and R ^2a and R ^2b represent the same or different hydrocarbon. Group, alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group or substituted amino group, R ^3a and R ^3b are the same or different and carbonized A hydrogen group, an alkoxy group, a halogen atom, a nitro group, a cyano group or a substituted amino group, wherein m and n are the same or different and are 0 or an integer of 1 or more, and h1 and h2 are the same or different and represent 0-4. An integer, j1 and j2 are the same or different and are integers of 0 to 4)
The resin which uses the diol component represented by these, and the dicarboxylic acid component as a polymerization component may be sufficient.

  In the fluorene-based polyester oligomer, the depolymerizer may contain two or more hydroxyl groups in one molecule, and the hydroxyl value may be about 30 to 400 mgKOH / g. Further, in the fluorene-based polyester oligomer, the depolymerizer may contain 3 or more hydroxyl groups in one molecule, and the hydroxyl value may be about 50 to 400 mgKOH / g. The fluorene polyester oligomer is useful as an optical material.

  The present invention also includes a method for producing the fluorene polyester oligomer by melting and kneading a fluorene-containing polyester resin containing a 9,9-bisarylfluorene skeleton in the presence of a depolymerizer.

  In the above method, the depolymerizing agent may be a compound having two or more functional groups selected from a hydroxyl group and a carboxyl group in one molecule. The depolymerizing agent may be at least one selected from trifunctional or higher functional polyols and trifunctional or higher functional polycarboxylic acids. Furthermore, you may use the said depolymerizing agent in the ratio of about 1-30 weight part with respect to 100 weight part of the said fluorene containing polyester-type resin.

  The present invention also includes a conductive composition containing the fluorene polyester oligomer and a conductive agent.

  Since the specific fluorene-containing polyester resin is depolymerized with a depolymerizing agent, the fluorene polyester oligomer of the present invention has high reactivity and excellent fluidity. The fluorene-based polyester oligomer satisfies a specific molecular weight and a specific acid value or hydroxyl value, has high reactivity, and is excellent in fluidity. In addition, the fluorene-based polyester oligomer has a low degree of polymerization, excellent fluidity, a high content of reactive groups (or functional groups) in the oligomer, and excellent reactivity. Excellent compatibility. Therefore, the fluorene-based polyester oligomer of the present invention is useful as an optical material (for example, an optical additive).

[Fluorene polyester oligomer]
The fluorene-based polyester oligomer of the present invention (hereinafter sometimes simply referred to as “oligomer” or “polyester oligomer”) comprises a dicarboxylic acid component containing a 9,9-bis (carboxyaryl) fluorene skeleton and a diol component. Although an oligomer as a polymerization component may be used, a fluorene-based polyester oligomer is generally an oligomer having a diol component containing a 9,9-bis (hydroxyaryl) fluorene skeleton and a dicarboxylic acid component as polymerization components. . Such an oligomer includes, for example, an oligomer having at least a diol component represented by the formula (1) and a dicarboxylic acid component as polymerization components.

  The fluorene-based polyester oligomer may be an oligomer obtained by polymerizing at least a diol component represented by the formula (1) and a dicarboxylic acid component at a low degree of polymerization and without depolymerization, but terminal reaction. Since the kind of the functional group can be easily controlled (or adjusted), the fluorene-based polyester oligomer is usually a fluorene-containing polyester having at least a diol component represented by the formula (1) and a dicarboxylic acid component as polymerization components. It is an oligomer (depolymerized) obtained by depolymerizing a base resin with a depolymerizing agent.

(Fluorene-containing polyester resin)
In Z ¹ and Z ² of the formula (1), examples of the aromatic hydrocarbon group include groups corresponding to C _6-14 aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, biphenyl, and indene. Z ¹ and Z ² are preferably a group corresponding to benzene (for example, a phenylene group).

In the formula (1), the alkylene group represented by R ^1a and R ^1b is a linear or branched C _2-4 alkylene group such as an ethylene group, a propylene group, a trimethylene group, or a tetramethylene group. Can be illustrated. In R ^1a and R ^1b , the types of alkylene groups may be different from each other. Further, the types of the alkylene groups R ^1a and R ^1b may be different depending on the numbers of the coefficients m and n. A preferable alkylene group is a _C2-3 alkylene group (ethylene group, propylene group), and is usually an ethylene group in many cases.

R ^2a and R ^2b are alkyl groups (eg, linear or branched C _1-8 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and t-butyl groups). (In particular, a C _1-6 alkyl group)), a cycloalkyl group (C _5-10 cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, preferably a C _5-8 cycloalkyl group, more preferably a C _{5- 6} cycloalkyl group), aryl group [eg, phenyl group, alkylphenyl group (methylphenyl group (or tolyl group, 2-methylphenyl group, 3-methylphenyl group, etc.), dimethylphenyl group (xylyl group), etc.) and _{C 6-10} aryl group such as a naphthyl group, an aralkyl group (benzyl group, _{C 6-10} aryl, such as phenethyl group - _1-4 such as an alkyl group) carbon atoms and the like; alkoxy group (e.g., methoxy group, an ethoxy group, a propoxy group, n- butoxy group, isobutoxy group, _{C 1-8} alkoxy (especially C, such as t- butoxy _1-6 alkoxy group)); cycloalkoxy group (C _5-10 cycloalkyloxy group such as cyclohexyloxy group); aryloxy group (C _6-10 aryloxy group such as phenoxy group); aralkyloxy group (For example, C _6-10 aryl-C _1-4 alkyloxy group such as benzyloxy group); acyl group (such as C _1-6 acyl group such as acetyl group); alkoxycarbonyl group (C such as methoxycarbonyl group) _1-4, such as an alkoxycarbonyl group), a halogen atom (fluorine atom, such as chlorine atom); nitro group; shea Group; and the like substituted amino group (such as dialkylamino group).

The substitution numbers h1 and h2 of the substituents R ^2a and R ^2b may generally be an integer of about 0 to 4 (for example, 0 to 2). The substitution positions of the substituents R ^2a and R ^2b are not particularly limited. Preferred substituents R ^2a and R ^2b are C _1-6 alkyl groups (particularly methyl groups), and preferred substitution numbers h1 and h2 are integers of about 0 to 2 (for example, 0 or 1).

Examples of R ^3a and R ^3b include the hydrocarbon groups, alkoxy groups, halogen atoms, nitro groups, cyano groups, and substituted amino groups described above.

The substitution numbers j1 and j2 of the substituents R ^3a and R ^3b may be an integer of generally 0 to 4, preferably 0 to 2 (for example, 0 or 1). The substitution positions of the substituents R ^3a and R ^3b are not particularly limited. Preferred substituents R ^3a and R ^3b are C _1-6 alkyl groups (particularly methyl groups), and preferred substitution numbers j1 and j2 are 0 or 1 (eg, 0).

  The number of repetitions m and n of the oxyalkylene unit is 0 or an integer of 1 or more, and is usually an integer of about 1 to 10, preferably 1 to 7, and more preferably about 1 to 5 (for example, 1 to 3). May be.

Further, the fluorene-containing polyester-based resin includes a diol component represented by the above formula (1), and the following formula (2).
HO—R ^1c —OH (2)
(In the formula, R ^1c represents an alkylene group.)
The polyester resin which uses the diol component represented by these and the below-mentioned dicarboxylic acid component as a polymerization component may be sufficient. In the formula (2), examples of the alkylene group represented by R ^1c include linear or branched C _2-10 alkylene groups such as ethylene group, propylene group, trimethylene group and tetramethylene group. A chain or branched C _2-4 alkylene group (for example, ethylene group, tetramethylene group, etc.) is preferred.

  In the diol component, the ratio (molar ratio) between the diol represented by the formula (1) and the diol represented by the formula (2) is the former / the latter = 100/0 to 10/90 (for example, 100/0 30/70), usually 99/1 to 50/50, preferably 99/1 to 55/45, more preferably 98/2 to 60/40, especially 97/3 to 65/35. (For example, about 95/5 to 70/30) may be sufficient.

  On the other hand, the dicarboxylic acid component may be an aliphatic dicarboxylic acid component, but is an alicyclic dicarboxylic acid component or an aromatic dicarboxylic acid component from the viewpoint of optical properties (for example, refractive index, birefringence, etc.). Is preferred.

Examples of the alicyclic dicarboxylic acid component include cycloalkane dicarboxylic acids (cyclopentane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, cycloheptane dicarboxylic acid, etc. _5-10 cycloalkane-dicarboxylic acid), polycyclic alkane dicarboxylic acids (di or tricyclo C _7-10 alkane-dicarboxylic acid such as bornane dicarboxylic acid and norbornane dicarboxylic acid) and the like. Usually, the alicyclic dicarboxylic acid component is C _5-10 cycloalkane-dicarboxylic acid (particularly 1,4-cyclohexanedicarboxylic acid).

Examples of the aromatic dicarboxylic acid component include C _6-14 arene-dicarboxylic acid such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, and C _12-14 biphenyl-dicarboxylic acid such as biphenyl-4,4′-dicarboxylic acid. Etc. can be exemplified. Usually, the aromatic dicarboxylic acid component is a C _6-12 arene-dicarboxylic acid (particularly terephthalic acid).

The dicarboxylic acid component may be an acid anhydride, a lower C _1-4 alkyl ester such as dimethyl ester, or a derivative capable of forming an ester such as an acid halide corresponding to the dicarboxylic acid. The dicarboxylic acid component may include one or more substituents such as a hydrocarbon group [for example, an alkyl group (for example, a C _1-4 alkyl group such as a methyl group), a cycloalkyl group (for example, a cyclohexyl group, etc.). C _5-10 cycloalkyl group), aryl group (for example, C _6-10 aryl group such as phenyl group)], haloalkyl group, hydroxyl group, alkoxy group (for example, C _1-10 alkoxy group such as methoxy group) ), A haloalkoxy group, a carboxyl group, an alkoxycarbonyl group (eg, a C _1-10 alkoxy-carbonyl group such as a methoxycarbonyl group), an acyl group (eg, a C _2-5 acyl group such as an acetyl group), an amino group , Substituted amino group, halogen atom, nitro group, cyano group, etc. It can be appropriately selected depending on the.

  The ratio (use ratio) of the dicarboxylic acid component and the diol component can be selected from the former / the latter (molar ratio) = about 5/1 to 0.1 / 1, and usually the former / the latter = 1.5 / 1. It may be about 0.5 / 1, preferably 1.2 / 1 to 0.7 / 1 (particularly 1.1 / 1 to 0.8 / 1). By adjusting the ratio (use ratio) between the dicarboxylic acid component and the diol component, the type of terminal group of the fluorene-containing polyester resin to be generated can be adjusted.

Preferred fluorene-containing polyester resins include, for example, (i) in the formula (1), R ^1a and R ^1b are ethylene groups, m and n are 1, and R ^2a and R ^2b are alkyl groups (for example, , A C _1-6 alkyl group such as a methyl group) or an aryl group (for example, a C _6-10 aryl group such as a phenyl group), h1 and h2 are 0 to 2, and j1 and j2 are 0 A copolymer comprising a component and a diol component in which R ^1c is an ethylene group and a dicarboxylic acid component that is terephthalic acid in the formula (2) as a polymerization component, and represented by the following formula (3a) A copolymer having a unit and a unit represented by the following formula (4a), (ii) In the formula (1), R ^1a and R ^1b are ethylene groups, m and n are 1, and R ^2a And R ^2b is a An alkyl group (eg, a C _1-6 alkyl group such as a methyl group) or an aryl group (eg, a C _6-10 aryl group such as a phenyl group), h1 and h2 are 0 to 2, and j1 and j2 are A diol component that is 0, a diol component in which R ^1c is an ethylene group in the above formula (2), and a dicarboxylic acid component that is 1,4-cyclohexanedicarboxylic acid, and the like. . For example, as an example of the copolymer contained in (i), a copolymer having a unit represented by the following formula (3a) and a unit represented by the following formula (4a) As an example of the copolymer contained, a copolymer having a unit represented by the following formula (3b) and a unit represented by the following formula (4b) can be given.

  The ratio of the unit represented by the following formula (3a) and the unit represented by the following formula (4a) is the former / the latter (unit number ratio) = 50/50 to 100/0, preferably 60/40 to 95. / 5, more preferably about 65/35 to 90/10. The ratio of the unit represented by the following formula (3b) to the unit represented by the following formula (4b) is also the former / the latter (unit number ratio) = 50/50 to 100/0, preferably 60/40. It may be about ~ 95/5, more preferably about 65/35 to 90/10.

  The fluorene-containing polyester-based resin may be a commercially available product or a synthesized product synthesized using (or applying) a conventional method. The fluorene-containing polyester resin can be obtained by reacting a corresponding diol component with a dicarboxylic acid component. For a method for producing such a polyester resin, for example, JP-A-2004-315676 can be referred to.

  The weight average molecular weight of the fluorene-containing polyester resin is, for example, 7000-60000, preferably 10000-58000 when measured using gel permeation chromatography (solvent: tetrahydrofuran, reference resin: polystyrene) at 40 ° C. More preferably, it may be about 15000 to 55000, particularly about 20000 to 52000 (for example, 25000 to 45000).

(Depolymerization agent)
The fluorene polyester oligomer of the present invention may be a depolymer obtained by depolymerizing the fluorene-containing polyester resin with the depolymerizer. The depolymerizing agent (depolymerizing agent for polyester resin) may be a compound containing a plurality of functional groups (or reactive groups) capable of reacting (transesterification reaction) with the polyester resin in one molecule. For example, the depolymerizing agent may be a compound containing at least two (or a plurality) of at least one functional group selected from a hydroxyl group and a carboxyl group. Specifically, examples of the depolymerizer include (i) a depolymerizer having a hydroxyl group (or polyols), (ii) a depolymerizer having a carboxyl group (or polycarboxylic acids) listed below: iii) Depolymerizers (or hydroxycarboxylic acids) having a hydroxyl group and a carboxyl group.

(I) Examples of the depolymerizing agent (or polyols) having a hydroxyl group include diols (for example, C _2-10 aliphatic diols such as ethylene glycol and propylene glycol, diethylene glycol, dipropylene glycol, and triethylene glycol). Such as polyalkylene glycols having a number average molecular weight of about 150 to 1,000, alicyclic diols, aromatic diols, etc., and trifunctional or higher polyols (for example, aliphatics such as glycerin, trimethylolethane, trimethylolpropane). C _3-10 triols; tetraols such as pentaerythritol and erythritol). The depolymerizing agent having a hydroxyl group can be used alone or in combination of two or more. Among these depolymerizers having a hydroxyl group, trifunctional or higher functional polyols (for example, aliphatic C _3-10 triols (for example, trimethylolpropane)) and the like are preferable. If necessary, the diol may be a monool (for example, a C _1-10 aliphatic monool such as methanol or ethanol; an alicyclic monool such as cyclohexanol; an aromatic monool such as phenol. Or the like). Trifunctional or higher functional polyols may be used in combination with the diols and / or the monools.

(ii) Examples of the depolymerizing agent (or carboxylic acids) having a carboxyl group include dicarboxylic acids (for example, C _2-20 aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid; C _6-20 alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; C _8-20 aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid (such as 2,6-naphthalenedicarboxylic acid) Carboxylic acids such as tricarboxylic acid (eg trimellitic acid, pyromellitic acid) or derivatives thereof (eg acid anhydride, acid halide (eg acid chloride), lower alkyl) Esters (for example, C _1-6 alkyl esters and the like) and the like are preferably used. The depolymerizing agent having a carboxyl group can be used alone or in combination of two or more. Among these depolymerizers having a carboxyl group, dicarboxylic acids (for example, cyclohexanedicarboxylic acid), trifunctional or higher polycarboxylic acids (or their acid anhydrides, lower alkyl esters (for example, C _1-6 alkyl esters) Etc.), etc.) are preferred, and in particular, trifunctional or higher functional polycarboxylic acids (eg, pyromellitic acid (or its lower alkyl ester (eg, C _1-6 alkyl ester))) are preferred. If necessary, the dicarboxylic acid may be a monocarboxylic acid (for example, a saturated C _1-18 aliphatic monocarboxylic acid such as acetic acid or propionic acid; an alicyclic monocarboxylic acid such as cyclohexanecarboxylic acid; an aromatic such as benzoic acid, etc. Monocarboxylic acids and the like) may be used in combination. Trifunctional or higher polycarboxylic acids may be used in combination with the dicarboxylic acids and / or the monocarboxylic acids.

  (iii) As the depolymerizing agent having a hydroxyl group and a carboxyl group, for example, hydroxycarboxylic acids such as tartaric acid, citric acid, lactic acid and gluconic acid are preferably used. The depolymerizing agent may be appropriately selected according to the type of terminal group required in the fluorene-based polyester oligomer. The said depolymerizing agent can be used individually or in combination of 2 or more types.

  The depolymerizing agent may be a compound containing at least two functional groups selected from a hydroxyl group and a carboxyl group, but a compound having three or more functional groups (for example, polyols, When a depolymerizing agent containing polycarboxylic acids) is used, a free functional group is introduced into the oligomer to be produced, so that the acid value or hydroxyl value of the oligomer can be increased, which is advantageous for improving the reactivity. It is.

  The fluorene-based polyester oligomer of the present invention is easily reduced in molecular weight and has improved fluidity. The weight average molecular weight of the fluorene polyester oligomer is 10 to 90%, preferably 20 to 80% (for example, 22 to 75%), more preferably 25 to 70, as compared with the weight average molecular weight of the fluorene-containing polyester resin. % (For example, 27 to 65%), especially 30 to 70% (for example, 30 to 60%) may be reduced (or low molecular weight). Specifically, the weight average molecular weight of the fluorene-containing polyester oligomer is, for example, 5000 to 30000, preferably when measured using gel permeation chromatography (solvent: tetrahydrofuran, reference resin: polystyrene) at 40 ° C. May be about 5500 to 29000, more preferably about 6000 to 28000 (for example, 7000 to 26000), particularly about 8000 to 25000 (for example, 8500 to 20000). The weight average molecular weight of the fluorene-containing polyester oligomer may be about 1000 to 10,000, preferably about 1500 to 7000, and more preferably about 2000 to 5000.

  In addition, the fluorene-based polyester oligomer is highly reactive because it has a low molecular weight and a high acid value or hydroxyl value. The acid value of the fluorene polyester oligomer may be, for example, 0 to 100 mgKOH / g, preferably 0.5 to 70 mgKOH / g, more preferably 1 to 50 mgKOH / g. The hydroxyl value of the fluorene-based polyester oligomer may be about 5 to 400 mgKOH / g, preferably about 10 to 350 mgKOH / g, and more preferably about 30 to 300 mgKOH / g.

  In addition, according to the kind of depolymerizer to be used, the acid value and / or hydroxyl value of the fluorene-type polyester oligomer to produce | generate can be adjusted. For example, when the polyester-based resin is depolymerized using a depolymerizing agent having a hydroxyl group, a polyester oligomer whose terminal group is substantially a hydroxyl group is obtained. Specifically, when the depolymerizing agent contains at least two hydroxyl groups in one molecule, the hydroxyl value of the resulting fluorene-based polyester oligomer is 5 to 400 mgKOH / g, preferably 10 to 380 mgKOH / g, Preferably, it may be about 15-350 mgKOH / g, and may be about 30-400 mgKOH / g. In particular, when the depolymerizer is a trifunctional or higher functional polyol, the hydroxyl value of the fluorene-based polyester oligomer to be generated is 10 to 400 mgKOH / g, preferably 15 to 380 mgKOH / g, more preferably 20 to 350 mgKOH / g. g (for example, about 30 to 200 mgKOH / g) or about 50 to 400 mgKOH / g may be used. Thus, when the depolymerizer is a trifunctional or higher functional polyol, the hydroxyl value of the resulting fluorene-based polyester oligomer can be effectively improved.

  On the other hand, when the polyester-based resin is depolymerized using a depolymerizing agent having a carboxyl group, a polyester oligomer whose terminal group is substantially a carboxyl group is obtained. Specifically, when the depolymerizer contains at least two carboxyl groups in one molecule, the acid value of the fluorene-based polyester oligomer produced is 0 to 100 mgKOH / g, preferably 0.5 to 70 mgKOH / g. More preferably, it may be about 1 to 50 mgKOH / g. In particular, when the depolymerizing agent is a tri- or higher functional polycarboxylic acid, the acid value of the fluorene-based polyester oligomer produced is 0 to 100 mgKOH / g, preferably 10 to 95 mgKOH / g, more preferably 30 to 90 mgKOH. / G may be sufficient. Thus, when the depolymerizing agent is a tri- or higher functional polycarboxylic acid, the acid value of the resulting fluorene-based polyester oligomer can be effectively improved.

  Based on such knowledge, the type of the depolymerizing agent to be used may be selected depending on the purpose. In addition, when (i) the depolymerizer which has a hydroxyl group is used among the said depolymerizers, it can suppress effectively that the produced | generated depolymer is colored.

  The fluorene-based polyester oligomer of the present invention may contain the depolymerizing agent as its structural unit. In the fluorene-based polyester oligomer, the unit corresponding to the depolymerization agent may include, for example, 0 to 2 units, preferably about 1 to 2 units, in one molecule of the fluorene-based polyester oligomer.

  The fluorene polyester oligomer is also excellent in various optical properties. For example, the fluorene polyester oligomer has a high refractive index, for example, 1.56 to 1.70, preferably 1.57 to 1.68, and more preferably about 1.58 to 1.65. The fluorene polyester oligomer has low birefringence. Specifically, the retardation value of the fluorene-based polyester oligomer is 0 to 1000 nm, preferably 0 to 500 nm, and more preferably about 0 to 300 nm. Furthermore, the fluorene polyester oligomer is also excellent in transparency, and the light transmittance at 550 nm is 80 to 97%, preferably 82 to 96%, more preferably about 85 to 95%.

  In addition, when using the said fluorene-type polyester oligomer for various uses (For example, the uses mentioned later, such as optical materials), you may use the said fluorene-type polyester oligomer together with an additive as needed. Examples of the additive include plasticizers, softeners, colorants, dispersants, mold release agents, stabilizers (oxidants such as hindered phenol antioxidants, phosphorus antioxidants, sulfur antioxidants). An inhibitor, an ultraviolet absorber, a heat stabilizer, etc.), an antistatic agent, a flame retardant, an antiblocking agent, a crystal nucleus growth agent, and the like. These additives can be used alone or in combination of two or more. The proportion of the additive may be selected according to the type and is not particularly limited, but can be selected from a range of about 0.01 to 100 parts by weight with respect to 100 parts by weight of the fluorene polyester oligomer. It may be about 50 parts by weight, preferably about 0.5 to 20 parts by weight.

[Method for producing fluorene polyester oligomer]
The fluorene-based polyester oligomer may be produced by polycondensing the diol component and the dicarboxylic acid component to a desired degree of polymerization, but it is easy to adjust (or control) the types of terminal groups of the oligomer, etc. From the above, the fluorene-containing polyester resin may be produced by reacting with the depolymerizing agent. For example, the fluorene-based polyester oligomer may be produced by melt-kneading the fluorene-containing polyester resin together with the depolymerizing agent and depolymerizing (or depolymerizing) the fluorene-containing polyester resin.

  The depolymerization reaction is a sequential reaction, and an oligomer having a desired molecular weight and end group can be formed according to the reaction conditions and the type and ratio of the depolymerizer. The proportion of the depolymerizer can be appropriately selected according to the type of the depolymerizer to be used. For example, 1 to 30 parts by weight, preferably 1.2 to 28 parts by weight with respect to 100 parts by weight of the fluorene-containing polyester resin. Part, more preferably 1.5 to 25 parts by weight, particularly 1.8 to 20 parts by weight (for example, 2 to 20 parts by weight).

  The depolymerization reaction may be performed in the presence of a solvent. For example, the fluorene-containing polyester-based resin, a depolymerizing agent, and a solvent (a solvent capable of dissolving (or mixing) the fluorene-containing polyester-based resin and the depolymerizing agent) may be mixed (or kneaded) and reacted. For example, the fluorene-containing polyester resin may be dissolved in a solvent to prepare a resin solution, and a depolymerizing agent may be added to the resin solution and mixed (or kneaded or stirred) for reaction. However, the depolymerization reaction is preferably performed in the absence of a solvent from the viewpoints of operability, cost and environment.

  The depolymerization reaction may be performed in the air, but is usually performed in an inert gas (nitrogen, helium, argon, etc.) atmosphere or a degassed atmosphere in many cases. In addition, the depolymerization reaction may be performed under normal pressure, or may be performed under reduced pressure or under pressure. Furthermore, the depolymerization reaction can be performed at a temperature of about 200 to 300 ° C, preferably 220 to 290 ° C, and more preferably about 230 to 280 ° C.

  The reaction time can be appropriately selected according to the desired degree of polymerization of the oligomer, reaction conditions, and the like, and can be selected, for example, from about 1 to 90 minutes, 1 to 80 minutes, preferably 3 to 75 minutes, more preferably 5 to 5 minutes. It may be about 70 minutes.

  The fluorene-based polyester oligomer of the present invention is useful as various optical materials because it is excellent in optical properties and fluidity and affinity (or compatibility) with various resins. For example, the fluorene-based polyester oligomer is useful as an optical additive (or optical modifier) that can impart (or improve) various optical properties. When the fluorene-based polyester oligomer is added to various resins, the operability of the resin can be improved, and excellent optical properties (low birefringence, high refractive index, etc.) can be imparted to the resin. For example, the fluorene-based polyester oligomer may be used as a birefringence improving agent for suppressing an increase in birefringence of various resins. The fluorene-based polyester oligomer can be applied (or added) to various resins and used as a crystal nucleating agent for the resin.

  Examples of resins that can be used in combination with the fluorene polyester oligomer include heat such as phenol resin, furan resin, urea resin, melamine resin, epoxy resin, unsaturated polyester resin, urethane resin, silicone resin, and polyimide resin. Curable resin (or photo-curable resin); olefin resin, styrene resin, vinyl chloride resin, vinyl acetate resin, polyvinyl alcohol resin, polyester resin (including aromatic polyester resin), thermoplastic acrylic Resin, polyacetal resin, polycarbonate resin, fluorine resin, polyamide resin, polysulfone resin (polysulfone resin, polyethersulfone resin, etc.), thermoplastic resin such as polyphenylene ether resin, polyphenylene sulfide resin, etc. It is below. The proportion of the resin can be appropriately selected depending on the type, and is, for example, 1 to 1000 parts by weight, preferably 3 to 700 parts by weight, and more preferably about 5 to 500 parts by weight with respect to 100 parts by weight of the fluorene polyester oligomer. There may be.

  Furthermore, the fluorene-based polyester oligomer is useful as an adhesive (or adhesive raw material) because it has a high acid value or hydroxyl value, the type of terminal group is controlled (or adjusted), and it has excellent reactivity. It is. Since the fluorene-based polyester oligomer is excellent in fluidity and affinity with various resins as described above, it can be applied to an adherend composed of various resins and has excellent adhesiveness. The adhesive may be, for example, a chemically reactive adhesive, a solvent volatilizing adhesive, a hot melt adhesive, a pressure sensitive adhesive, etc., but from the viewpoint of reactivity and adhesiveness (or curability). In particular, it is useful as a chemical reaction type adhesive, a solvent volatilization type adhesive, or the like. When the fluorene-based polyester oligomer is used as a chemically reactive adhesive, it may be a one-component adhesive that is cured by heat, light, moisture, etc., and is cured by adding (or mixing) a curing agent. It may be a liquid adhesive (or its main agent). When the fluorene-based polyester oligomer is used as a two-component adhesive, the oligomer itself may be used as a main agent, the oligomer is used as a main agent raw material, and a compound capable of reacting with a reactive group of the oligomer is reacted with the main agent. May be formed.

  Specifically, for example, a fluorene-based polyester oligomer having a high hydroxyl value (for example, about 50 to 400 mgKOH / g) is used as the main material, and a carboxyl group (or the derivative-forming group), an isocyanate group, a glycidyl group, and the like. To form a main agent or an adhesive (for example, a polyester-based adhesive, a urethane-based adhesive, an epoxy-based adhesive, a reactive acrylic adhesive having a (meth) acryloyl end), etc. Also good. Further, as the main ingredient raw material, a fluorene-based polyester oligomer having a high acid value (for example, about 30 to 100 mgKOH / g) is used and reacted with a compound having a hydroxyl group, an amino group, an isocyanate group, etc. For example, a polyester-based adhesive, a polyamide-based adhesive, a urethane-based adhesive, or the like may be formed. Note that the fluorene-based polyester oligomer has a fluorene skeleton and is excellent in various optical properties, and therefore, an adhesive (or optical adhesive) used for adhesion in optical applications (for example, adhesion of optical members (or parts)). ) Is also useful.

  Moreover, since the said fluorene-type polyester oligomer can disperse | distribute a particulate and / or fibrous filler (or reinforcing agent) efficiently, you may use it with the form of the composition containing the said filler. The filler may be a conventional filler. For example, the filler (or conductive agent) having conductivity [for example, a simple metal such as gold, silver, platinum, aluminum, or an alloy thereof, a metal Metal particles such as carbides and metal oxides; Carbon particles such as graphite and conductive carbon black; Conductive particles such as magnetic materials (for example, ferrite); Conductive fibers such as carbon fibers (for example, carbon nanotubes) ]. For example, a molded body (for example, a conductor such as a conductive film) is formed by molding a composition (or a conductive composition) formed using a conductive agent (for example, a conductive fiber such as carbon nanotube). You may get For example, the proportion of the conductive agent may be 1 to 200 parts by weight, preferably 3 to 150 parts by weight, and more preferably about 5 to 120 parts by weight with respect to 100 parts by weight of the fluorene polyester oligomer.

  The fluorene polyester oligomer may be used as a carrier, and the filler may be dispersed to form a master batch, which may be used in combination with the various resins exemplified above.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, the symbol of each evaluation method and component in an Example and a comparative example is as follows.

[Evaluation method]
(Average molecular weight)
The number average molecular weight and the weight average molecular weight were measured using gel permeation chromatography (GPC) [manufactured by JASCO, “Intelligent HPLC”]. The measurement was performed using tetrahydrofuran as an eluent under conditions of a column temperature of 40 ° C. and a flow rate of 1.0 ml / min, and a measured value in terms of polystyrene was obtained. As for the column, two “KF-804L” manufactured by Shodex were connected in series.

(Hydroxyl value)
The hydroxyl value was measured according to JIS K1557. In addition, the measurement was performed with respect to the sample which stirred the reaction mixture of a fluorene containing polyester-type resin and a depolymerizer in boiling water for 4 hours.

[Component abbreviations]
FBP1: fluorene-containing polyester resin [manufactured by Osaka Gas Chemical Co., Ltd., a block copolymer having a unit represented by the above formula (3a) and a unit represented by the following formula (4a) (in the formula (3a) , H1 and h2 are 0, a copolymer represented by the unit represented by formula (3a) / unit represented by formula (4a) (unit number ratio) = 70/30, weight average molecular weight: 34,685 ]]
FBP2: fluorene-containing polyester resin [manufactured by Osaka Gas Chemical Co., Ltd., a block copolymer having a unit represented by the above formula (3b) and a unit represented by the following formula (4b) (in the formula (3b) , H1 and h2 are 0, a unit represented by formula (3b) / unit represented by formula (4b) (unit number ratio) = 80/20, weight average molecular weight: 33,850 ]]
CNT: carbon nanotube (carbon nanotube manufactured by Shenzhen Nanotechport Co., Ltd., diameter 10-20 nm)

Example 1
After 100 parts by weight of a fluorene-containing polyester-based resin (FBP1) was put into a lab plast mill (“TDR100-500 X3 type” manufactured by Toshin Co., Ltd.) set at a temperature of 280 ° C., and melted under an argon gas stream 13 parts by weight of trimethylolpropane was added. A fluorene polyester oligomer was obtained by performing melt kneading for 5 minutes. The fluorene polyester oligomer had a weight average molecular weight of 15000 and a hydroxyl value of 22.4 mgKOH / g.

(Examples 2 to 4)
A fluorene-based polyester oligomer was obtained in the same manner as in Example 1 except that the time for melt kneading was 7.5 minutes, 10 minutes, and 20 minutes, respectively, and the weight average molecular weight and hydroxyl value were measured.

(Comparative Example 1)
The weight average molecular weight and the hydroxyl value were measured without reacting the fluorene-containing polyester resin (FBP1) with trimethylolpropane.

  The results of Examples 1 to 4 and Comparative Example 1 are shown in Table 1. Moreover, the relationship between melt-kneading time and the weight average molecular weight of the fluorene-type polyester oligomer obtained is shown in FIG.

  As is clear from Table 1, the fluorene-based polyester oligomers of the examples had a very large hydroxyl value as compared with the comparative examples, the hydroxyl groups were effectively introduced, and the reactivity was improved. Moreover, the fluorene-type polyester oligomer which has arbitrary molecular weights was able to be manufactured by controlling kneading | mixing time.

(Examples 5-7)
Instead of 13 parts by weight of trimethylolpropane, 3.3 parts by weight were used, and a fluorene-based polyester oligomer was obtained in the same manner as in Example 1 except that the melt-kneading times were 10 minutes, 20 minutes, and 30 minutes, respectively. The average molecular weight, number average molecular weight and hydroxyl value were measured.

  The results are shown in Table 2.

(Examples 8 to 11 and Comparative Example 2)
A fluorene-based polyester oligomer was obtained in the same manner as in Example 1 except that FBP2 was used instead of the fluorene-containing polyester-based resin (FBP1), and the melt-kneading times were 10 minutes, 20 minutes, 30 minutes, and 60 minutes, respectively. The average molecular weight, number average molecular weight and hydroxyl value were measured. In Comparative Example 2, the weight average molecular weight, number average molecular weight and hydroxyl value were measured without reacting FBP2 with trimethylolpropane.

  The results are shown in Table 3.

  As is apparent from Table 3, the fluorene-based polyester oligomer of the example had a hydroxyl value that was much higher than that of the comparative example, the hydroxyl group was effectively introduced, and the reactivity was improved. Moreover, the fluorene-type polyester oligomer which has arbitrary molecular weights was able to be manufactured by controlling kneading | mixing time.

(Examples 12 and 13)
A fluorene-based polyester oligomer was obtained in the same manner as in Example 8 except that 13 parts by weight of cyclohexanedicarboxylic acid was used in place of trimethylolpropane, and the melt-kneading time was 10 minutes and 20 minutes, respectively. Average molecular weight was measured.

  The results are shown in Table 4.

  As is clear from Table 4, the fluorene-based polyester oligomers of the examples were reduced in molecular weight by the depolymerizing agent. Moreover, the fluorene-type polyester oligomer which has arbitrary molecular weights was able to be manufactured by controlling kneading | mixing time.

(Example 14 and Comparative Examples 3 to 4)
100 parts by weight of a commercially available polyethylene terephthalate resin (manufactured by Toyobo, “PET-MAX”) and 25 parts by weight of the fluorene-based polyester oligomer obtained in Example 3 were manufactured by Labo Plast Mill (manufactured by Toshin Co., Ltd., “TDR100-500”). X3 type ") was used for melt kneading at 280 ° C for 10 minutes. After kneading, the film was molded at 260 ° C. and 20 MPa using a hot press (manufactured by Techno Supply Co., Ltd.) to produce a film having a thickness of 0.2 mm. The obtained film was subjected to differential scanning calorimetry (DSC) measurement. In Comparative Example 3, FBP1 was used in place of the fluorene polyester oligomer, and in Comparative Example 4, the same procedure as in Example 14 was used except that only a commercially available polyethylene terephthalate resin (“PET-MAX” manufactured by Toyobo Co., Ltd.) was used. A film was prepared, and the obtained film was subjected to differential scanning calorimetry (DSC) measurement. The results are shown in Table 5. In the table, Tg is a glass transition temperature, Tc is a crystallization temperature, Tm is a melting temperature, ΔHc is a crystallization enthalpy, ΔHm is a melting enthalpy, and ΔHm (PET) is a polyethylene terephthalate resin component. The value converted into the amount of heat is shown.

  Subsequently, the cross section of the film obtained in Example 14 and Comparative Example 3 was observed with a scanning electron microscope (SEM). The micrographs are shown in FIG. 2 (Example 14) and FIG. 3 (Comparative Example 3).

  As is apparent from Table 5, crystallization started at 189.6 ° C. in Comparative Example 3 and 195 ° C. in Comparative Example 4, whereas crystallization started at 210.8 ° C. in Example 14. . As in Example 14, crystallization of the polyethylene terephthalate resin containing the fluorene polyester oligomer of the present invention is promoted, and the fluorene polyester oligomer of the present invention is useful as a crystal nucleating agent. It was. As is clear from FIGS. 2 and 3, in Example 14, the compatibility with the polyethylene terephthalate resin was improved.

(Examples 15 to 17)
The fluorene-based polyester oligomer obtained in Example 1 was dissolved in chloroform to prepare a 30% by weight oligomer solution. Carbon nanotubes (CNT) were dissolved in chloroform to prepare a 1 wt% CNT solution. The oligomer solution and the CNT solution were mixed, and the CNT content was adjusted to 10% by weight, 30% by weight, and 50% by weight with respect to the fluorene-based polyester oligomer, respectively. Chloroform was removed from the resulting mixed solution and formed into a thin film. The conductivity (resistance value) of the obtained film was measured using a Custom digital multimeter CDM-11D (manufactured by Custom Co., Ltd.). In Example 15, the film surface was observed with a scanning electron microscope (SEM). An electron micrograph of the film surface of Example 15 is shown in FIG.

(Examples 18 to 20)
A thin film was formed in the same manner as in Examples 15 to 17 except that the fluorene polyester oligomer obtained in Example 3 was used instead of the fluorene polyester oligomer obtained in Example 1, and the conductivity of the obtained film was The property (resistance value) was measured.

(Comparative Examples 5-7)
A thin film was formed in the same manner as in Examples 15 to 17 except that FBP1 was used instead of the fluorene polyester oligomer obtained in Example 1, and the conductivity (resistance value) of the obtained film was measured. In Comparative Example 5, the film surface was observed with a scanning electron microscope (SEM). An electron micrograph of the film surface of Comparative Example 5 is shown in FIG.

  The results of Examples 15 to 20 and Comparative Examples 5 to 7 are shown in FIG. As is clear from FIG. 6, in the film of the example, the volume resistivity value was reduced and the conductivity was improved. Further, as apparent from FIGS. 4 and 5, the voids observed around the CNTs in FIG. 5 (Comparative Example 5) were not observed in FIG. 4 (Example 15). From these results, it was found that the fluorene-based polyester oligomer having a reduced molecular weight has greatly improved dispersibility of CNTs.

(Example 21)
5 parts by weight of the fluorene polyester oligomer obtained in Example 3 was dissolved in 5 parts by weight of dimethylformamide (manufactured by Aldrich, DMF) to prepare an oligomer solution, and 1.4 parts by weight of isophorone diisocyanate (IPDI) was added to the oligomer solution. Was added and mixed well under nitrogen. This mixed solution was dropped on the glass plate 1 and DMF was removed by evaporation at 100 ° C., followed by heating at 120 ° C. for 2 hours to cure. As shown in FIG. 7, the obtained cured product 2 was colorless and transparent and had a hard glass shape. When the infrared absorption spectrum of the surface of the cured product 2 was measured, the absorbance (ABS _NCO ) at the characteristic absorption wavelength (2255 nm) of the isocyanate group (NCO) and the characteristic absorption wavelength of the carbonyl group (CO) contained in the polyester The ratio (ABS _NCO / ABS _CO ) to the absorbance (ABS _CO ) at (1717 nm) was 0.396. The fluorene polyester oligomer obtained in Example 3 was highly reactive, and it was found that most of the isocyanate groups of the added isophorone diisocyanate were reacted.

FIG. 1 shows the relationship between the melt-kneading time in Examples 1 to 4 and Comparative Example 1 and the weight average molecular weight of the resulting fluorene-based polyester oligomer. FIG. 2 shows a scanning electron micrograph (1500 times) of the film cross section obtained in Example 14. The scale bar in the table indicates 20 μm. FIG. 3 shows a scanning electron micrograph (1500 times) of the film cross section obtained in Comparative Example 3. The scale bar in the table indicates 20 μm. FIG. 4 shows a scanning electron micrograph (20,000 times) of the film surface obtained in Example 15. The scale bar in the table indicates 2 μm. FIG. 5 shows a scanning electron micrograph (20,000 times) of the film surface obtained in Comparative Example 5. The scale bar in the table indicates 2 μm. FIG. 6 shows the relationship between the CNT content and the volume resistivity value in Examples 15 to 20 and Comparative Examples 5 to 7. FIG. 7 is a schematic diagram of the cured product obtained in Example 21.

Explanation of symbols

1 ... Glass plate 2 ... Hardened material

Claims (2)

A conductive composition comprising a fluorene-based polyester oligomer obtained by depolymerizing a fluorene-containing polyester-based resin containing a 9,9-bis (hydroxyaryl) fluorene skeleton with a depolymerizing agent, and a conductive agent,
The fluorene-containing polyester resin has at least the following formula (1)
(In the formula, Z ¹ and Z ² are the same or different and each represents an aromatic hydrocarbon group. R ^1a and R ^1b represent the same or different alkylene group, and R ^2a and R ^2b represent the same or different hydrocarbon. Group, alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group or substituted amino group, R ^3a and R ^3b are the same or different and carbonized A hydrogen group, an alkoxy group, a halogen atom, a nitro group, a cyano group or a substituted amino group, wherein m and n are the same or different and are 0 or an integer of 1 or more, and h1 and h2 are the same or different and represent 0-4. An integer, j1 and j2 are the same or different and are integers of 0 to 4)
And a diol component represented by the following formula (2)
HO—R ^1c —OH (2)
(In the formula, R ^1c represents an alkylene group.)
A diol component represented by:
The ratio (molar ratio) of the diol component represented by the formula (1) and the diol component represented by the formula (2) is the former / the latter = 99/1 to 50/50 using the dicarboxylic acid component as a polymerization component. A resin that is
The depolymerizing agent is at least one selected from diols and tri- or higher functional polyols;
The depolymerizer contains a tri- or higher functional polyol,
A conductive composition in which a fluorene-based polyester oligomer is used as an optical material having a weight average molecular weight of 5000 to 30000 and a hydroxyl value of 50 to 400 mgKOH / g. The proportion of the conductive agent relative to 100 parts by weight of the fluorene-based polyester oligomer, claim 1 Symbol placement of the electrically conductive composition is 1 to 200 parts by weight.