JP2012082544A - Carbon nanofiber and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a simple and efficient carbon nanofiber and a carbon nanofiber aggregate, and to provide a carbon nanofiber and a carbon nanofiber aggregate manufactured by the manufacturing method.SOLUTION: A phthalocyanine nanowire having a minor diameter of 100 nm or less and a ratio of the length to the minor diameter (length/minor diameter) of 10 or more is heated and calcined. A composition comprising the phthalocyanine nanowire and an organic solvent is dried in a container having any shape and calcined to form a carbon nanofiber aggregate having any external appearance shape. And, the composition is applied on a heat-resistant substrate such as glass and ceramic and then subjected to calcination.

Description

The present invention relates to a carbon nanofiber, a method for producing a carbon nanofiber, a carbon nanofiber aggregate, and a method for producing a carbon nanofiber aggregate.

Carbon nanofibers are those with a diameter of about 10 to several hundreds of nanometers in fibrous carbon materials, and those with 10 nm are called carbon nanotubes. Collectively called carbon nanofiber. In recent years, the excellent properties of carbon nanofibers have attracted attention and are actively researched.

  For example, it is used as a filler for the purpose of imparting conductivity to the resin material or improving the mechanical properties of the resin material, and also a gas storage material utilizing hydrogen absorption, release ability and methane absorption ability, Applications to negative electrode materials for fuel cells and electron emission materials for displays are expected.

As a method for producing such carbon nanofibers, arc discharge (for example, Patent Documents 1 and 2), laser sublimation (for example, Patent Document 3), chemical vapor phase (CVD) method (for example, Patent Documents 4 to 8). A manufacturing method using a gas phase method such as the above is well known. However, these gas phase methods have the disadvantages of low productivity and poor fiber shape controllability.
On the other hand, in order to improve this, a method is known in which a carbon fiber is obtained by spinning a thermo-carbonizable polymer material into a fiber and firing it. In this method, for example, carbon fibers are obtained by carbonizing fibers such as phenolic resins and acrylonitrile-based polymers. However, since these polymer fibers alone are difficult to spin with a small diameter or stretch after spinning, Only thick fibers on the order of μm could be obtained.

  Therefore, as a means to obtain thinned carbon nanofibers, a blend polymer that combines a thermal carbonizable polymer with a thermally decomposable polymer or solvent-soluble polymer is spun and heated or solvent extracted from this fiber. Has disclosed a method of obtaining carbon nanofibers by carbonization after removing the thermally decomposable polymer and solvent-soluble polymer part (Patent Documents 9-11). However, these methods involve a complicated process in which two or more polymer materials are melt-kneaded, spun and formed into a fiber shape, and then a part thereof is removed and further carbonized to obtain carbon nanofibers. It was a thing.

  In addition, when carbon nanofibers obtained by conventional methods are deposited on a substrate such as glass or ceramics to form a conductive film, the carbon nanofibers themselves have poor solvent dispersibility. Further, it was necessary to perform a dispersion process.

JP 7-165406 A JP-A-7-197325 Japanese Patent Laid-Open No. 10-273308 Sho 60-54998 Sho 60-27700 Japanese Patent No. 2778434 Japanese Patent Publication No. 3-64606 Japanese Patent Publication No. 3-77288 JP 2001-73226 A JP 2004-176236 A JP 2005-163329 A

In view of the above, the problem of the present invention is to provide a simpler and more efficient carbon nanofiber and carbon nanofiber aggregate production method, and carbon nanofibers produced using the production method, And providing a carbon nanofiber assembly.

As a result of intensive studies to solve the above problems, the present inventors have found that the short diameter is 100 nm or less and the ratio of the length to the short diameter (length / short diameter) is 10 or more. By heating and baking, a good carbon nanofiber can be obtained, and a composition comprising the phthalocyanine nanowire and an organic solvent is dried in a container of an arbitrary shape, and this is fired to have an arbitrary appearance. A carbon nanofiber aggregate having a shape can be formed, and the composition is applied on a heat-resistant substrate such as glass or ceramics, and then baked and then easily conducted on the substrate. The present inventors have found that a film can be formed and completed the present invention.

According to the present invention, it is possible to easily and efficiently produce carbon nanofibers and aggregates thereof, and the carbon nanofibers and carbon nanofiber aggregates produced by the production method are used as resin materials. It can be used as a filler for the purpose of imparting electrical conductivity or improving the mechanical properties of the resin material. Further, it can be used as a gas storage material utilizing hydrogen absorption, emission ability and methane absorption ability, and a negative electrode material for fuel cells, and is also useful as an electron emission material for displays and a catalyst carrier.

2 is a transmission electron micrograph of phthalocyanine nanowires in Example 1. FIG. 2 is a transmission electron micrograph of phthalocyanine nanowires in Example 1. FIG. 2 is a scanning electron micrograph of the carbon nanofiber aggregate obtained in Example 1. FIG. 2 is a scanning electron micrograph of the carbon nanofiber aggregate obtained in Example 1. FIG. Scanning transmission electron micrograph (a) of the carbon nanofiber aggregate obtained in Example 1 (a), copper element presence mapping diagram at a position corresponding to (a), and a position corresponding to (a) It is a carbon element presence mapping diagram (c). 2 is an AFM image of a carbon nanofiber aggregate formed on a quartz substrate in Example 2. FIG. 4 is an AFM image of a carbon nanofiber aggregate formed on a quartz substrate in Example 3. FIG. 4 is a transmission electron micrograph of phthalocyanine nanowires in Example 4. 4 is a transmission electron micrograph of phthalocyanine nanowires in Example 4. 4 is a scanning electron micrograph of the carbon nanofiber aggregate obtained in Example 4. FIG. 4 is a scanning electron micrograph of the carbon nanofiber aggregate obtained in Example 4. FIG. 2 is a scanning electron micrograph of phthalocyanine nanowires obtained in Example 5. FIG. 2 is a scanning electron micrograph of phthalocyanine nanowires obtained in Example 5. FIG. 6 is a scanning electron micrograph of the carbon nanofiber aggregate obtained in Example 5. FIG. 6 is a scanning electron micrograph of the carbon nanofiber aggregate obtained in Example 5. FIG. 6 is a scanning electron micrograph of the sintered body obtained in Example 6. 6 is a scanning electron micrograph of the sintered body obtained in Example 6. 4 is a scanning electron micrograph of a sintered body obtained in Comparative Example 2. 4 is a scanning electron micrograph of a sintered body obtained in Comparative Example 2.

That is, the present invention
(1) a first step of obtaining a phthalocyanine nanowire (A) having a minor axis of 100 nm or less and a ratio of the length to the minor axis (length / minor axis) of 10 or more;
(2) a second step of firing the phthalocyanine nanowire (A),
The present invention provides a method for producing carbon nanofibers.
The present invention also provides:
(1) a first step of obtaining a phthalocyanine nanowire (A) having a minor axis of 100 nm or less and a ratio of the length to the minor axis (length / minor axis) of 10 or more;
(2) a second step of obtaining a composition (B) comprising phthalocyanine nanowires and an organic solvent as essential components;
(3) The third step of drying the phthalocyanine nanowire aggregate (C1) by drying the composition (B) on an arbitrary substrate or in a container, and the fourth step of firing the phthalocyanine nanowire aggregate,
A method for producing a carbon nanofiber aggregate characterized by comprising:
Furthermore, the present invention provides
(1) a first step of obtaining a phthalocyanine nanowire (A) having a minor axis of 100 nm or less and a ratio of the length to the minor axis (length / minor axis) of 10 or more;
(2) a second step of obtaining a composition (B) comprising phthalocyanine nanowires and an organic solvent as essential components;
(3) Third step (c) to obtain the phthalocyanine nanowire aggregate film (C2) by applying and drying the composition (B) on an arbitrary heat-resistant substrate.
(4) Fourth step (d) for firing the phthalocyanine nanowire assembly film (C2),
And a method for producing a carbon nanofiber aggregate film.
The present invention further uses a phthalocyanine nanowire (A) having a minor axis of 100 nm or less and a ratio of the length to the minor axis (length / minor axis) of 10 or more as a precursor, which is fired. To provide carbon nanofibers and carbon nanofiber aggregates

The present invention is described in detail below.
In the present invention, the carbon nanofiber means a fibrous carbon material having a diameter of 10 to several hundred nm, and the carbon nanofiber aggregate exists in a state where a plurality of the carbon nanofibers are aggregated. Means what to do. Moreover, the carbon nanofibers, carbon nanofibers aggregate, be identified by having characteristic peaks at Raman spectrum 1580~1590cm ^-1 (G-band), the carbon material in the vicinity of 1350～1360Cm ^-1 Can do. Further, the carbon nanofibers and the carbon nanofiber aggregates may contain or carry metal fine particles on the surface or inside thereof.

In the manufacturing method of the carbon nanofiber of this invention and a carbon nanofiber aggregate | assembly, it has the 1st process of manufacturing a phthalocyanine nanowire in the 1st process using a phthalocyanine and a phthalocyanine derivative.

(Phthalocyanine contained in phthalocyanine nanowires)
As the phthalocyanine contained in the phthalocyanine nanowire produced in the first step of the present invention, a known and commonly used metal phthalocyanine having a central metal atom and a metal-free phthalocyanine having no central metal atom can be used. The central metal atom is not limited as long as it constitutes a nanowire. However, copper atom, zinc atom, cobalt atom, nickel atom, tin atom, lead atom, magnesium atom, silicon atom, iron atom, titanyl (TiO2) ), Vanadyl (VO), aluminum chloride (AlCl) and the like, among which a copper atom, a zinc atom, and an iron atom are particularly preferable.

(Phthalocyanine derivatives contained in phthalocyanine nanowires)
The phthalocyanine nanowire manufactured by the 1st process of this invention is a phthalocyanine nanowire containing the said phthalocyanine and the phthalocyanine derivative which is the following general formula (1) or (2).

However, in the formula, X is a copper atom, a zinc atom, a cobalt atom, a nickel atom, a tin atom, a lead atom, a magnesium atom, a silicon atom, an iron atom, titanyl (TiO), vanadyl (VO), aluminum chloride (AlCl). Y ₁ to Y ₄ are each selected from the group consisting of: a linking group that connects the phthalocyanine skeleton and R _{1 to} R ₄ ;
When Y ₁ to Y ₄ are not present as a linking group, R _{1 to} R ₄ may have SO ₃ H, CO ₂ H, an alkyl group that may have a substituent, or a substituent ( (Oligo) aryl group, optionally substituted (oligo) heteroaryl group, optionally substituted phthalimide group or optionally substituted fullerene,
Y ₁ to Y ₄ are — (CH ₂ ) _n — (n represents an integer of 1 to 10), —CH═CH—, —C≡C—, —O—, —NH—, —S—, When it is a bonding group represented by —S (O) — or —S (O) ₂ —, R _{1 to} R ₄ have an alkyl group which may have a substituent, and a substituent. (Oligo) aryl group which may have a substituent, (oligo) heteroaryl group which may have a substituent, phthalimide group which may have a substituent or fullerenes which may have a substituent, b, c and d each independently represent an integer of 0 to 4, but at least one of them is not 0.

  The metal atom X that forms a complex with the phthalocyanine derivative of the present invention is not particularly limited as long as it is commonly used as the central metal of metal phthalocyanine, but preferred metal atoms include copper, zinc, cobalt, nickel, tin, lead, Any one kind of metal atom selected from magnesium, silicon, and iron can be exemplified. As X, metal phthalocyanine coordinated with titanyl (TiO), vanadyl (VO), or aluminum chloride (AlCl) can also be used. Here, like the phthalocyanine derivative represented by the general formula (2), a compound not containing the central metal X can also be used as the phthalocyanine derivative of the present invention.

Y ₁ to Y ₄ can be used without particular limitation as long as they are linking groups that bind the phthalocyanine ring and R _{1 to} R ₄ . Examples of such linking groups include alkylene groups, arylene groups, heteroarylene groups, vinylene bonds, ethynylene, sulfide groups, ether groups, sulfoxide groups, sulfonyl groups, urea groups, urethane groups, amide groups, amino groups, imino groups. Group, ketone group, ester group, and the like. More specifically, — (CH ₂ ) _n — (n represents an integer of 1 to 10), —CH═CH—, —C≡C— , -O-, -NH-, -S-, -S (O)-or -S (O) _2- . In addition, fullerenes can also be used as the linking group of the present invention.

R _{1 to} R ₄ are functional groups that can be bonded to the phthalocyanine ring via the bonding groups Y ₁ to Y ₄ . Examples of such functional groups include alkyl groups, alkyloxy groups, amino groups, mercapto groups, carboxy groups, sulfonic acid groups, silyl groups, silanol groups, boronic acid groups, nitro groups, phosphoric acid groups, aryl groups, Examples include heteroaryl groups, cycloalkyl groups, heterocycloalkyl groups, nitrile groups, isonitrile groups, ammonium salts or fullerenes, phthalimide groups, and more specifically, aryl groups such as phenyl groups and naphthyl groups, And heteroaryl groups such as indoyl group and pyridinyl group and meryl group. Among these, specifically preferred groups include SO ₃ H, CO ₂ H, an alkyl group, an alkyl group having an ether group or an amino group, an aryl group which may have a substituent, and a substituent. Examples include a heteroaryl group, a phthalimide group which may have a substituent, or a fullerene which may have a substituent.

Examples of the alkyl group that may have a substituent include an alkyl group having 1 to 20 carbon atoms, and a lower alkyl group such as a methyl group, an ethyl group, or a propyl group is particularly preferable. Further, an alkyl group having an ether group or an amino group is also preferable.

(M is an integer of 1 to 20, and R and R ′ are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group.)
The group represented by can also be used.

  The (oligo) aryl group which may have a substituent is preferably a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or a substituent. An oligophenylene group or an oligonaphthyl group which may have a substituent can be exemplified. Examples of the substituent include conventionally known substituents that can be substituted on the aryl group.

  The (oligo) heteroaryl group which may have a substituent is preferably a pyrrole group which may have a substituent, a thiophene group which may have a substituent, or a substituent. Examples thereof include a good oligopyrrole group and an oligothiophene group which may have a substituent. Examples of the substituent include conventionally known substituents that can be substituted on the heteroaryl group.

In addition, examples of fullerenes which may have a substituent include fullerenes having a generally known substituent in fullerenes, such as C60 fullerene, C70 fullerene and phenyl C61-methyl butyrate [60] fullerene. (PCBM).
Examples of the phthalimide group that may have the substituent include, for example,

(Here, q is an integer of 1 to 20.)
The group represented by these can be mentioned. Examples of the substituent include a generally known substituent that can be substituted on the phthalimide group.

A, b, c and d each independently represents an integer of 0 to 4, and represents the number of substituents Y ₁ R ₁ to Y ₄ R ₄ substituted on the phthalocyanine ring. Note that at least one of the numbers a to d of the substituents substituted on the phthalocyanine ring is not zero.

Specific examples of the phthalocyanine derivative represented by the general formula (1) of the present invention include, but are not limited to, the following. Here, the number next to the parentheses in the formula of the phthalocyanine derivative represents the average number of functional groups introduced into the phthalocyanine molecule (in actual use, different numbers of substituents introduced are mixed).

(Here, X is a copper atom or a zinc atom, n is an integer of 1 to 20, and m is a numerical value of 1 to 4 representing the average number of functional groups introduced.)

(Where X is a copper atom or zinc atom, n is an integer of 1 to 20, m is a numerical value of 1 to 4 representing the average number of introduced functional groups, and R ₁ to R ₄ are each independently Represents a hydrogen atom, halogen, an alkyl group having 1 to 20 carbon atoms, an alkyloxy group or an alkylthio group.)

(Where X is a copper atom or zinc atom, n is an integer of 1 to 20, m is a numerical value of 1 to 4 representing the average number of introduced functional groups, and R ₁ to R ₂ are each independently Represents a hydrogen atom, halogen, an alkyl group having 1 to 20 carbon atoms, an alkyloxy group or an alkylthio group.)
Moreover, as a specific compound represented by General formula (2), the phthalocyanine derivative in which a central metal does not exist in said formula (4)-(12) can also be used.

  General formula (3) of the present invention

(Wherein, X is a copper atom, zinc atom, cobalt atom, nickel atom, tin atom, lead atom, magnesium atom, silicon atom, iron atom, titanyl (TiO), vanadyl (VO), aluminum chloride (AlCl)) Z is a group represented by the following formula (a) or (b), and a, b, c and d each independently represents an integer of 0 to 4, At least one of them is not 0.)

(Here, n is an integer of 4 to 100, Q is each independently a hydrogen atom or a methyl group, and Q 'is an acyclic hydrocarbon group having 1 to 30 carbon atoms.)

(Here, m is an integer of 1 to 20, and R and R ′ are each independently an alkyl group having 1 to 20 carbon atoms.)
In the phthalocyanine derivative represented by the formula, a compound in which the phthalocyanine ring is substituted with at least one sulfamoyl group can be exemplified. The sulfamoyl group to be introduced can be used without particular limitation as long as it is at least one per phthalocyanine ring, but is preferably 1 or 2, more preferably 1. The position to be substituted is not particularly limited.

The molecular weight of the general formula (a) is not particularly limited, and may be various functional groups such as an alkyl group or an ether group, an oligomer in which these functional groups have several repeating units, or a polymer having many repeating units. In the case of a polymer, the number average molecular weight is preferably 10,000 or less because, in the formation of nanowires, crystal growth of phthalocyanine due to steric hindrance is not inhibited, and sufficiently long nanowires can be obtained. Examples of the polymer include a polymer made of a polymer of an alkyl group or a vinyl compound, a polymer having a urethane bond, an ester bond, or an ether bond.
As the most preferable chain compound Z of the present invention, a polyalkylene oxide copolymer represented by the general formula (a) can be mentioned, and any polyalkylene oxide such as an ethylene oxide polymer and an ethylene oxide / propylene oxide copolymer is block-polymerized. Those that are randomly polymerized can also be used.
Here, Q ′ may be a linear hydrocarbon group or a branched hydrocarbon group as a non-cyclic hydrocarbon group having 1 to 30 carbon atoms, and the hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Either hydrogen group may be used. Examples of such an acyclic hydrocarbon group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-octyl group, 2 Examples thereof include linear or branched saturated hydrocarbon groups such as -ethyl-hexyl group, n-dodecyl group, stearyl group, n-tetracosyl group and n-triacontyl group.

In addition, as the linear or branched unsaturated hydrocarbon group, the hydrocarbon group may have a double bond or a triple bond, for example, a vinyl group, a propenyl group, an isopropenyl group, a butenyl group, a pentenyl group. , Linear or branched unsaturated hydrocarbon groups such as isoprene group, hexenyl group, heptenyl group, octenyl group, decenyl group, geranyl group, ethynyl group, 2-propynyl group, 2-penten-4-ynyl group be able to.

The repeating number n of the polyalkylene oxide moiety is not particularly limited, but it is preferably 4 or more and 100 or less, more preferably from the viewpoint of the affinity with the dispersion solvent, that is, the dispersion stability of the resulting nanowires. It is 5 or more and 80 or less, and more preferably 10 or more and 50 or less.
The phthalocyanine derivative represented by the general formula (1) used in the present invention can be obtained by combining, for example, a copper phthalocyanine sulfonyl chloride and a polyether amine having an amine at the end of the polyether main chain (hereinafter, “ It can be produced by reacting with “polyether monoamine”.

Copper phthalocyanine sulfonyl chloride as a raw material can be obtained by reaction of copper phthalocyanine with chlorosulfonic acid or thionyl chloride. The polyether monoamine which is the other raw material can be obtained by a known and conventional method. For example, the hydroxyl group at the end of the polyether skeleton can be obtained by reductive amination using a nickel / copper / chromium catalyst, and the hydroxyl group at the end of the polyether skeleton can be obtained by Mitsunobu reaction (reference document: Synthesis). , 1-28 (1981)), and then amination by hydrazine reduction (reference document: Chem. Commun., 2062-2063 (2003)).
Polyether monoamine is also available as a commercial product, for example, “JEFFAMINE (trade name) M series” from Huntsman Corporation.
Examples of the phthalocyanine derivative represented by the general formula (3) used in the present invention include a compound represented by [Chemical Formula 16], but are not limited thereto.

(However, in the formula, Q and R represent a hydrogen atom or a methyl group. N is an integer of 4 to 100. In addition, the number m of polyalkylene oxide chains bonded to the phthalocyanine via a sulfamoyl bond is included in the phthalocyanine. (It is a numerical value of 0 to 4 representing the average number of functional groups introduced for four benzene rings.)
The phthalocyanine derivative that can be used in the present invention may have a group represented by the general formula (b) in addition to the phthalocyanine derivative.
This derivative may be reacted with an amine represented by the following formula instead of the polyetheramine used for introducing the group represented by the general formula (a).

(Here, m is an integer of 1 to 20, and R and R ′ are each independently an alkyl group having 1 to 20 carbon atoms.)
Preferred examples of R and R ′ include a lower alkyl group, particularly a methyl group, and m is preferably an integer of 1 to 6. Specific preferred phthalocyanine derivatives include the following. Here, the number next to the parentheses in the formula of the phthalocyanine derivative represents the average number of functional groups introduced into the phthalocyanine molecule (in actual use, different numbers of substituents introduced are mixed).

Moreover, among the phthalocyanine derivatives represented by the general formula (1), the group represented by R _{1 to} R ₄ may have a group that is SO ₃ H or CO ₂ H, and SO ₃ H or CO ₂ is a no limit to the number of group H, but 1-4, more preferably can be exemplified one or two a. These groups may have one type of group or two types of groups. Introduction of SO ₃ H or CO ₂ H can be performed by a known and conventional method.
Although there is no restriction | limiting in the number of sulfamoyl groups of the phthalocyanine derivative represented by General formula (3), 1-4 can be mentioned more preferably. These groups may have one type of group or two types of groups. These phthalocyanine derivatives can be synthesized by a known and commonly used method.

The number next to the parentheses in the formula of the above phthalocyanine derivative represents the average number of functional groups introduced into the phthalocyanine molecule, and the preferred number of functional groups introduced is 0.2 to 3. 0, more preferably in the range of 0.5 to 2.0.
The various phthalocyanine derivatives can be synthesized by introducing side chains or functional groups into the phthalocyanine ring. For example, the copper phthalocyanine sulfamoyl compound described in [Chemical Formula 16] can be synthesized by the above-described method. It can be obtained by heating in (sulfur trioxide concentration: 20%), and the compound of [Chemical 9] can be synthesized, for example, by the method disclosed in the patent document (US Pat. No. 2,761,868).

The phthalocyanine derivative can also be obtained, for example, by a publicly known phthalocyanine synthesis method described in JP-A-2005-145896 and JP-A-2007-39561. For example, 4-phenoxy-phthalonitrile and 4-phenylthio- Various phthalonitrile compounds such as phthalonitrile and 4- (1,3-benzothiazol-2-yl) -phthalonitrile are mixed at an arbitrary ratio with respect to orthophthalonitrile having no substituent, and 1,8- By heating in ethylene glycol with a metal salt such as copper (II) sulfate or zinc (II) in the presence of an organic base such as diazabicyclo [5,4,0] undec-7-ene, the above various functional groups Can be synthesized in any ratio. Here, the number of the functional groups of the phthalocyanine derivative that can be synthesized using the phthalonitrile compound as one of the raw materials can be arbitrarily changed by changing the mixing ratio of the phthalonitrile compound and orthophthalonitrile, For example, when it is desired to synthesize a phthalocyanine derivative having one functional group per phthalocyanine molecule on average, the mixture of the phthalonitrile derivative and orthophthalonitrile may be 1: 3, and an average of 1.5 is desired to be introduced. In this case, the compound can be synthesized at a ratio of 3: 5 using the method described in the patent document. A phthalocyanine derivative having a plurality of types of functional groups can be synthesized from two or more types of phthalonitrile compounds and orthophthalonitrile.

Further, the phthalonitrile derivative having a substituent includes various known and commonly used phthalonitrile derivatives in addition to the above. As an example, Japanese Patent Application Laid-Open No. 2007-519636, paragraph 0001, Japanese Patent Application Laid-Open No. 2007-526881 The phthalonitrile derivative described in paragraph 0014 of the publication of Japanese Patent Application Laid-Open No. 2006-143680, and the phthalonitrile derivative linked with the oligothiophene described in the chemical formula 2 of paragraph 0014 of the publication of Japanese Patent Application Laid-Open No. 2006-143680, The phthalonitrile derivative linked with the fullerenes described in Chemical Formula 9 in the paragraph is also included as a raw material for synthesizing the phthalocyanine derivative that can be used in the present invention.

First step (Phthalocyanine nanowire (A) manufacturing process)
The production methods (I) to (III) of the phthalocyanine nanowire, which is the first step of the present invention, will be described.

<Manufacturing method (I)>
This manufacturing method
(1) Step (a) of obtaining a composite by dissolving phthalocyanine and a phthalocyanine derivative in an acid, and then precipitating in a poor solvent;
(2) Step (b) of obtaining a finely divided composite by making the composite fine particles;
(3) a step (c) of obtaining a dispersion by dispersing the micronized composite in an organic solvent;
(4) A step (d) of forming the dispersion into a nanowire.

・ Process (a)
In general, phthalocyanines are known to be soluble in an acid solvent such as sulfuric acid. In the method for producing phthalocyanine nanowires of the present invention, the phthalocyanine and the phthalocyanine derivative are first combined with sulfuric acid, chlorosulfuric acid, methanesulfonic acid. And dissolved in an acid solvent such as trifluoroacetic acid. Thereafter, it is poured into a poor solvent such as water to precipitate a complex of the phthalocyanine and phthalocyanine derivative.

Here, the mixing ratio of the phthalocyanine derivative to the phthalocyanine is preferably in the range of 5% by mass to 200% by mass, and more preferably 30% by mass to 120% by mass. When the mixing ratio is 5% by mass or more, there is a tendency that the phthalocyanine derivative has a functional group or a side chain of the polymer, so that the crystal grows in one direction through the steps described later and becomes a good nanowire. On the other hand, if it is in the range of 200% by mass or less, the functional group and the polymer side chain are not so many as to inhibit crystal growth, and therefore, the nanowire is successfully formed through unidirectional crystal growth to become an amorphous state or a particulate state. There is no.

The amount of the phthalocyanine and phthalocyanine derivative added to the acid solvent is not particularly limited as long as there is no undissolved content and the concentration can be completely dissolved, but the range in which the solution has sufficient fluidity is maintained. Is preferably 20% by mass or less.

When the solution in which the phthalocyanine and the phthalocyanine derivative are dissolved is poured into a poor solvent such as water to precipitate the complex of the phthalocyanine and the phthalocyanine derivative, the solution is added from 0.01% by mass with respect to the poor solvent. A range of 50% by mass is preferred. If it is 0.01% by mass or more, the concentration of the complex to be precipitated is sufficiently high, so that the solid content can be easily recovered. If it is 50% by mass or less, all the phthalocyanine and phthalocyanine derivatives are precipitated to form a solid. It becomes a complex and has no dissolved components and is easy to recover.
There is no particular limitation as long as the phthalocyanine and the phthalocyanine derivative are insoluble or sparingly soluble liquid with respect to the poor solvent, but the homogeneity of the complex to be precipitated can be kept high, and an environment suitable for the miniaturization process described later. The most preferable poor solvent may be water with a small load or an aqueous solution containing water as a main component.
From the observation result with a transmission electron microscope, it confirmed that the composite body of the phthalocyanine and phthalocyanine derivative obtained at the said process (a) existed uniformly in an amorphous state.

The composite can be filtered using a filter paper and a Buchner funnel to remove acidic water and washed with water until the filtrate becomes neutral to recover the water-containing composite. The recovered complex may be dehydrated and dried to remove moisture, or may be kept in a water-containing state when it is microparticulated by a wet dispersion method in the next step.

・ Process (b)
The method is not particularly limited as long as the composite obtained through the step (a) can be formed into fine particles, but the composite is preferably formed into fine particles by a wet dispersion method. For example, a wet disperser using microbeads such as a bead mill or a paint conditioner is used for the composite obtained in the step (a), or T.I. K. Using a medialess disperser typified by Fillmix, wet dispersion is performed together with a dispersion solvent such as water or an organic solvent and a water-containing organic solvent, and the composite is made into fine particles. Although there is no restriction | limiting in particular regarding the mass ratio with respect to the dispersion solvent of this composite here, from a viewpoint of dispersion | distribution efficiency, it is preferable to carry out a dispersion process in solid content concentration in the range of 1 mass% to 30 mass%. When using micro media such as zirconia beads for the dispersion treatment, it may be considered that the bead diameter is in the range of 0.01 mm to 2 mm in view of the degree of micronization of the composite. In addition, from the viewpoint of the efficiency of microparticulation and recovery efficiency, the micromedia can be most preferably microparticulated in the range of 100% by mass to 1000% by mass with respect to the dispersion of the composite.

  It is preferable to remove the water by dehydrating and drying the obtained aqueous dispersion of the micronized composite. Although there is no restriction | limiting in particular about the method of dehydration and drying, Filtration, centrifugation, evaporation by a rotary evaporator etc. can be mentioned. Further, after dehydration, drying may be further performed using a vacuum dryer or the like until moisture is completely removed. Further, after drying the water-containing composite (a) and completely removing moisture, it may be wet-dispersed in an organic solvent such as N-methylpyrrolidone or dichlorobenzene to obtain a micronized composite.

・ Process (c)
The microparticulate complex obtained through the step (b) is dispersed in an organic solvent used for nanowire formation such as N-methylpyrrolidone. The organic solvent is not particularly limited as long as it does not have low affinity with phthalocyanines. For example, amide solvents and aromatic organic solvents having high affinity with phthalocyanines are preferable. Specifically, phthalocyanines N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, toluene, xylene, ethylbenzene, chlorobenzene and dichlorobenzene, which have particularly high affinity, can be mentioned as the most suitable organic solvent. The amide organic solvent and the aromatic organic solvent can be used alone, but the amide organic solvent and the aromatic organic solvent can be used in a mixture at an arbitrary ratio. It can also be used in combination with a solvent.

Organic solvents that can be used in combination with amide organic solvents and aromatic organic solvents include ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, and diethylene glycol from the point that nanowire formation can be promoted in the steps described below. Mention may be made of glycol esters such as monoethyl ether acetate. These organic solvents may be added after the micronized complex is dispersed in an amide organic solvent and an aromatic organic solvent, or after mixing with the organic solvent in advance, the micronized complex is added and dispersed. Also good.

With respect to the amount of the organic solvent added to the above-mentioned micronized composite, the solid content concentration of the micronized composite with respect to the organic solvent is 0.1% from the viewpoint of appropriate fluidity and prevention of aggregation. It is in the range of 20%, more preferably 1% to 10%.

Here, when the micronized complex is obtained by water dispersion in the step (b), the micronized complex dehydrated by centrifugation or the like can be dispersed in the organic solvent described above, Even if it contains, a nanowire can be obtained by the process mentioned later.

・ Process (d)
A phthalocyanine nanowire can be produced by heating, stirring, or leaving the organic solvent dispersion of the micronized composite obtained through the step (c). In the production of nanowires in this step, heating may or may not be performed. When heating is performed, the heating temperature is preferably in the range of 50 ° C to 250 ° C, more preferably 100 ° C to 200 ° C. If the heating temperature is 50 ° C. or higher, the crystal growth of phthalocyanines can be sufficiently induced, and can be grown into nanowires by the desired unidirectional crystal growth. Aggregation and fusion are hardly observed, and the crystal grows in the width direction and does not become coarse. There is no particular limitation on the heating time, but it is preferable to heat for at least 10 minutes until the length of the phthalocyanine nanowire grows to 100 nm or more.

By treating from the step (a) to the step (d), a phthalocyanine nanowire having a width (minor axis) of 100 nm or less and a wire length ratio (length / minor axis) of 10 or more is obtained. Can be manufactured. Although the phthalocyanine and the phthalocyanine derivative are complexed by crystallization in the step (a), and further through the micronized complex in the step (b), the mechanism for forming the nanowire in the step (d) is not necessarily clear, but the step ( The particle size of the micronized composite obtained in b) is 10 nm to 20 nm, and the micronized composite particles are connected in the crystal plane direction of phthalocyanine by the step (d) to grow crystals only in one direction. Thus, it can be assumed that the nanowire is formed. At this time, the organic solvent in the step (c) functions as a good dispersion medium for phthalocyanine, and it is considered that nanowire formation is further promoted by inducing unidirectional crystal growth. Alternatively, it can be assumed that phthalocyanine and a phthalocyanine derivative are once dissolved from the fine particle composite by heating and recrystallized on the surface of the composite to form nanowires. At this time, there is a domain in which a large amount of phthalocyanine having a relatively low solubility remains on the surface of the composite, and since this domain is nano-sized, it is considered that a crystal having a nano-sized diameter can be obtained.

<Production method (II)>
This manufacturing method
1. (1) Step (a) of obtaining a composite (A1) by dissolving phthalocyanine and a phthalocyanine derivative in an acid, and then precipitating them in a poor solvent;
(2) Step (b) of obtaining a fine particle composite (A2) by making the composite (A1) into fine particles;
(3) having the step (c) of applying the micronized composite (A2) on the substrate and (4) the step (d) of exposing the organic solvent vapor to grow nanowires on the substrate. A phthalocyanine nanowire and a method for producing a nanowire aggregate.

  In the steps (a) to (b) of the production method (II), the micronized composite (b) can be obtained through the same steps as in the production method (I).

・ Process (c)
The finely divided composite (A2) obtained through the step (b) is applied to a substrate as a powder or an organic solvent dispersion to obtain a finely divided composite-coated substrate. The method for applying the fine composite powder is not particularly limited, and a known and commonly used method can be employed. Specific examples include electrostatic powder coating, a friction transfer method, and a rubbing method. On the other hand, the method of forming the organic solvent dispersion of the micronized composite (A2) is not particularly limited, and a known and commonly used method can be employed. Specifically, the inkjet method, the gravure method, the gravure offset, and the like. Method, offset method, letterpress method, letterpress inversion method, screen method, microcontact method, reverse method, air doctor coater method, blade coater method, air knife coater method, roll coater method, squeeze coater method, impregnation coater method, transfer roll coater Method, kiss coater method, cast coater method, spray coater method, die coater method, spin coater method, bar coater method, slit coater method, drop cast method and the like.

In the step (c), when the organic solvent dispersion of the micronized composite (A2) is applied to the substrate, the micronized composite obtained through the step (b) is dispersed in an organic solvent and used. The organic solvent for preparing the dispersion is not particularly limited as long as it does not have low affinity with phthalocyanines, but for example, amide solvents and aromatic organic solvents with high affinity with phthalocyanines are preferable, Specifically, N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, toluene, xylene, ethylbenzene, chlorobenzene, and dichlorobenzene, which have a particularly high affinity with phthalocyanine, are the most suitable organic solvents for dispersion. Can be mentioned. The amide organic solvent and the aromatic organic solvent can be used alone, but the amide organic solvent and the aromatic organic solvent can be used in a mixture at an arbitrary ratio. It can also be used in combination with a solvent.

Examples of the organic solvent that can be used in combination with the amide organic solvent and the aromatic organic solvent include glycol esters such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl ether acetate. These organic solvents may be added after the finely divided complex (A2) is dispersed in an amide organic solvent and an aromatic organic solvent, or may be added in advance after mixing with the organic solvent. It may be dispersed.

With respect to the amount of the organic solvent added to the above-described finely divided composite (A2), the solid content concentration of the finely divided composite with respect to the organic solvent is 0. It is in the range of 1% to 20%, more preferably 1% to 10%.
Here, when the micronized complex (A2) is obtained by water dispersion in the step (b), the micronized complex dehydrated by centrifugation or the like can be dispersed in the organic solvent.

The substrate on which the fine particle composite (A2) is applied is not particularly limited as long as the fine particle composite is fixed on the base material by coating. Metal, glass, inorganic oxide, and polymer material may be used. Can be used. As the metal, for example, iron, aluminum, gold, silver, copper, nickel, tungsten, silicon can be used, and as the inorganic oxide, for example, aluminum oxide, titanium oxide, zirconium oxide, zinc oxide, Silica or the like can be used. Examples of the polymer material include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC). , Cellulose triacetate (TAC), cellulose acetate propionate (CAP), and the like.

・ Process (d)
The phthalocyanine nanowires are grown on the substrate by exposing the vaporized organic solvent to the substrate for applying the micronized composite obtained through the step (c). In the step (d), the organic solvent used for exposure is not particularly limited as long as it does not have low affinity with phthalocyanines. For example, amide solvents and aromatic organic solvents having high affinity with phthalocyanines. Specifically, N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, toluene, xylene, ethylbenzene, chlorobenzene and dichlorobenzene, which have a particularly high affinity with phthalocyanine, are the most suitable organic solvents. Can be mentioned. The amide organic solvent and the aromatic organic solvent can be used alone, but the amide organic solvent and the aromatic organic solvent can be used in a mixture at an arbitrary ratio. It can also be used in combination with a solvent.

Examples of organic solvents that can be used in combination with amide organic solvents and aromatic organic solvents include glycol esters such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, acetone, and methyl ethyl ketone. Mention may be made of halogenated carbons such as ketones, dichloromethane, chloroform and carbon tetrachloride.

The vapor temperature of the organic solvent is preferably in the range of 0 ° C to 200 ° C, more preferably 20 ° C to 100 ° C. When the vapor temperature is 0 ° C. or higher, an organic solvent vapor having a concentration sufficient for nanowire formation can be generated. There is no particular limitation on the exposure time, but it is preferable to expose at least 10 minutes before the length of the phthalocyanine nanowire grows to 100 nm or more.
By performing the processes from the step (a) to the step (d), the minor axis on the substrate is 100 nm or less, and the ratio of the length to the minor axis (length / minor axis) is 10 or more. Certain phthalocyanine nanowires can be made. Further, when any stress is applied during the application of the micronized composite (A2), the minor diameter is 100 nm or less, which is oriented and grown in the stress direction, and the ratio of the length to the minor diameter (length / minor diameter). ) Is a phthalocyanine nanowire aggregate film having 10 or more.

In the present invention, the stress generated at the time of application is, for example, spin coating, along the radial liquid flow generated from the center of the substrate to the outer edge during application rotation, and application by a bar coat or applicator. Then, it refers to the stress generated in the direction of movement of the bar or applicator. Further, after applying the micronized composite (A2) on the base material, a stress in a certain direction may be applied to the surface by pressing another base material and moving it from above.

Further, even when no stress is applied to the applied micronized composite film, it is possible to grow phthalocyanine nanowires in a certain direction by performing exposure by flowing solvent vapor in a certain direction.
The method for producing carbon nanofibers and carbon nanofiber aggregates of the present invention includes a step of firing phthalocyanine nanowires or phthalocyanine nanowire aggregates, as will be described later. The present phthalocyanine nanowire, the phthalocyanine nanowire obtained by the method (II) for producing a phthalocyanine nanowire aggregate, or the phthalocyanine nanowire aggregate is formed on a base material and subjected to a subsequent baking process. Alternatively, the composition described later may be prepared by peeling from the substrate.

<Production method (III)>
This production method is characterized in that an isoindoline compound and a metal ion are reacted in a water-soluble polyhydric alcohol in the presence of a phthalocyanine derivative.

That is, in this production method, a phthalocyanine derivative, an isoindoline compound, and a metal ion are dissolved in a water-soluble polyhydric alcohol and sufficiently stirred to obtain a uniform mixed solution.
When the temperature at the time of stirring is higher than 80 ° C., the phthalocyanine compound having a non-uniform shape may be generated in a part where mixing is insufficient, or the yield may be reduced. Preferably it is done.

  After the polyhydric alcohol solution of the phthalocyanine derivative, the isoindoline compound, and the metal salt is mixed at a temperature of 80 ° C. or lower to obtain a mixed solution, the mixed solution is heated to 80 to 200, 100 to 180 ° C. while stirring. By doing so, the isoindoline compound and the metal ion are reacted to obtain a solid reaction product.

  Alternatively, the mixed polyhydric alcohol solution containing the isoindoline compound and the metal salt is dropped into the water-soluble polyhydric alcohol solution in which the phthalocyanine derivative is dissolved, and the isoindoline compound is set in the same temperature range as described above. And a metal ion can be reacted to obtain a solid reaction product.

  The mixing ratio of the isoindoline compound and the metal salt is preferably adjusted so that the metal ion is 1 to 4 mol with respect to 4 mol of the starting phthalonitrile compound from the stoichiometric viewpoint.

  Water-soluble polyhydric alcohols that can be used in the present invention are α-glycols such as ethylene glycol, propylene glycol, 1,2-butanediol, 2,3-butanediol, and glycerin, and two of their molecular structures. Or what adjoins the carbon atom which three hydroxyl groups couple | bond is good.

  Examples of the phthalocyanine derivative used in the present invention include a compound in which the phthalocyanine ring is substituted with at least one sulfamoyl group and is soluble in a polyhydric alcohol. The compound represented by (3) can be mentioned.

Z in the general formula (3) in this production method is not particularly limited as long as it is a water-soluble polymer chain having a number average molecular weight of 1000 or more, and more preferably a water-soluble polymer having a number average molecular weight of 1000 or more and 10,000 or less. As such a water-soluble polymer chain, any water-soluble polymer chain can be used without particular limitation as long as it is water-soluble and has an affinity for water-soluble polyhydric alcohols. Residue of polymer having partial structure is mentioned, more specifically, polymer chain having partial structure of all polyalkylene oxides such as ethylene oxide polymer and ethylene oxide / propylene oxide copolymer, block polymerization or random polymerization But it can also be used. Preferably, Z is a polymer chain derived from an alkylene oxide copolymer which is a group represented by the general formula 14 (a), and the hydrophilicity or lipophilicity of the polymer chain depends on the solubility in the polyhydric alcohol used. It is desirable to optimize. Here, each Q is independently a hydrogen atom or a methyl group, and Q ′ may be either a linear hydrocarbon group or a branched hydrocarbon group as an acyclic hydrocarbon group having 1 to 30 carbon atoms, The hydrocarbon group may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. Examples of such an acyclic hydrocarbon group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-octyl group, 2 Examples thereof include linear or branched saturated hydrocarbon groups such as -ethyl-hexyl group, n-dodecyl group, stearyl group, n-tetracosyl group and n-triacontyl group.

  In addition, as the linear or branched unsaturated hydrocarbon group, the hydrocarbon group may have a double bond or a triple bond, for example, a vinyl group, a propenyl group, an isopropenyl group, a butenyl group, a pentenyl group. , Linear or branched unsaturated hydrocarbon groups such as isoprene group, hexenyl group, heptenyl group, octenyl group, decenyl group, geranyl group, ethynyl group, 2-propynyl group, 2-penten-4-ynyl group be able to.

  The repeating number n of the polyalkylene oxide moiety is preferably 4 or more and 100 or less, more preferably 5 or more and 80 or less, and even more preferably 10 or more and 50 or less. If the repeating number n is less than 4, the affinity with the dispersion medium is insufficient, and if it exceeds 100, the dispersion stability tends to be lowered.

The phthalocyanine derivative represented by the general formula (3) can be obtained by carefully combining known and commonly used methods, for example, copper phthalocyanine sulfonyl chloride and a polyether amine having an amine at the end of the polyether main chain (hereinafter referred to as “polyether”). It can be produced by reacting "monoamine" and abbreviated). The raw material copper phthalocyanine sulfonyl chloride can be obtained by reaction of copper phthalocyanine with chlorosulfonic acid and / or thionyl chloride. The polyether monoamine which is the other raw material can be obtained by a known and conventional method. For example, the hydroxyl group at the end of the polyether skeleton can be obtained by reductive amination using a nickel / copper / chromium catalyst, and the hydroxyl group at the end of the polyether skeleton can be obtained by Mitsunobu reaction (reference document: Synthesis). , 1-28 (1981)), and then amination by hydrazine reduction (reference document: Chem. Commun., 2062-2063 (2003)). Polyether monoamine is also available as a commercial product, for example, “JEFFAMINE (trade name) M series” from Huntsman Corporation. Examples of the phthalocyanine derivative represented by the general formula (3) used in the present invention include, but are not limited to, the compound of Chemical Formula 16 above.
(In the formula, Q represents a hydrogen atom or a methyl group, propylene oxide / ethylene oxide = 30/70 (molar ratio), and average value of n = 47.)
The isoindoline compound used in the present invention can be synthesized by a known method. For example, while dissolving a phthalonitrile compound such as orthophthalonitrile in a polyhydric alcohol such as α-glycol or glycerin while heating, 1,8-diazabicyclo [5.4.0] undec-7-ene (hereinafter referred to as “DBU”). The reaction is performed in the presence or absence of an organic base such as a metal alkoxide or the like to synthesize a phthalonitrile compound soluble in a water-soluble polyhydric alcohol and the polyhydric alcohol reaction product. The structure of the reaction product has already been estimated as an isoindoline compound by our research. For this reason, in the present invention, the reaction product is hereinafter referred to as an isoindoline compound.

  The phthalonitrile compound that can be used in the present invention includes orthophthalonitrile and those having two —CN groups at the ortho position of the benzene ring or naphthalene ring. For example, the following formula [Chemical Formula 197]

(Ring A in the formula represents a benzene ring or a naphthalene ring which may have a substituent of an alkyl group, an alkoxy group, an alkylthio group, or a halogen group.)
Is mentioned. When ring A is a benzene ring, a functional group such as a halogen atom or an alkyl group may be introduced at other sites.

  If the reaction temperature of the phthalonitrile compound and the water-soluble polyhydric alcohol is 80 ° C. or higher when no organic base or metal alkoxide is added, a metal-free phthalocyanine compound is produced at a high temperature, so a process such as filtration is necessary. It is not preferable. In addition, since the reaction may take a long time when the temperature is low, the reaction is preferably carried out in the range of 100 ° C. to 130 ° C. for 15 minutes to 8 hours, more preferably 1 hour to 3 hours. . It is preferable that the obtained solution containing the isoindoline compound is immediately cooled to 80 ° C. or lower immediately after the completion of the reaction to stop the further progress of the reaction. Further, during the reaction, it is preferable to avoid mixing moisture in the air, such as by placing in a nitrogen atmosphere, and it is preferable to dehydrate the water-soluble polyhydric alcohol in advance.

  When an organic base such as DBU is added to react a phthalonitrile compound with a polyhydric alcohol, the reaction can be carried out at a lower temperature than when the organic base is not used, thereby suppressing generation of a metal-free phthalocyanine compound. It is convenient to do. Specifically, the reaction may be performed in the range of 30 ° C. to 100 ° C. for 10 minutes to 2 hours.

  Although there is no particular limitation on the mass ratio when the phthalonitrile compound and the water-soluble polyhydric alcohol are reacted, when the concentration of the phthalonitrile compound is lower than 2%, the productivity when the metal phthalocyanine compound is synthesized later When the viscosity is higher than 40%, the viscosity of the obtained solution is remarkably increased, and the amount of metal-free phthalocyanine compound produced may increase, so that the concentration of the phthalonitrile compound is 2% by mass to 40%. It is preferable to set it in the range of 5% by mass, particularly 5% by mass to 20% by mass.

Examples of metal ions that can be used in the present invention include all metal ions that can be a central metal of metal phthalocyanine, and specifically include copper ions, zinc ions, cobalt ions, nickel ions, iron ions, and the like. . These metal ions are usually subjected to the reaction by dissolving a metal salt in a water-soluble polyhydric alcohol. Examples of the salt include halides and sulfates. For example, in the case of a copper salt, copper chloride (II) and copper sulfate (II) can be mentioned as preferable salts.
When an isoindoline compound and a metal ion are reacted in the presence of a phthalocyanine derivative, a glycol solvent may be added to a water-soluble polyhydric alcohol solution containing these compound and metal ion. The glycol-based solvent is particularly preferably a glycol ester-based solvent in consideration of the affinity with the metal phthalocyanine nanowire to be generated and the heatable temperature. Specific examples of the solvent include, but are not limited to, propylene glycol monomethyl ether acetate. A glycol-based solvent is preferred because it can promote unidirectional crystal growth for making the phthalocyanine of the present invention into a nanowire.

Of the production methods of the phthalocyanine nanowires of the present invention mentioned above, the production methods (I) and (II) are preferred, and the production method (I) is more preferred from the viewpoint of productivity. By adjusting the blend of the phthalocyanine and the phthalocyanine derivative, various phthalocyanine nanowires having different lengths and minor diameters can be appropriately obtained.
In one form of the manufacturing method of the carbon nanofiber of this invention, and a carbon nanofiber aggregate | assembly, in the 2nd process, the composition (B) which has a phthalocyanine nanowire and an organic solvent as an essential component is obtained. And

(Composition)
Carbon nanofibers and carbon nanofibers are obtained by dispersing phthalocyanine nanowires having a minor axis of 100 nm or less and a ratio of length to minor axis (length / minor axis) of 10 or more in an organic solvent. A composition for producing an aggregate can be obtained.
The solvent species used in the composition (B) is not particularly limited as long as it can stably disperse phthalocyanine nanowires. Even if it is a single organic solvent, an organic solvent in which two or more types are mixed is used. Although it may be used, an amide solvent is preferred from the viewpoint that phthalocyanine nanowires can be dispersed favorably and stably. Specifically, N, N-dimethylacetamide, N, N-dimethylformamide, N- Examples thereof include methyl pyrrolidone and N, N-diethylformamide, and N-methyl pyrrolidone is particularly preferable.

Moreover, the solvent which comprises a composition can be suitably selected with the kind of phthalocyanine derivative contained in a phthalocyanine nanowire, for example, the phthalocyanine nanowire containing the derivative of [Chemical 9] is disperse | distributed favorably and stably. Examples of preferable organic solvents that can be used include, in addition to amide solvents, for example, aromatic solvents such as toluene, xylene, ethylbenzene, and halogenated aromatic organic solvents such as chlorobenzene and dichlorobenzene. Can do.
Examples of the halogen organic solvent include organic solvents such as chloroform, methylene chloride, and dichloroethane.

In the composition of the present invention, the content of phthalocyanine nanowires in the composition is preferably 0.05 to 20% by mass, particularly 0.1% for imparting printability and forming a good film. It is preferable to set it as -10 mass%.

In one form of the manufacturing method of the carbon nanofiber of this invention, and the carbon nanofiber aggregate | assembly, the composition (B) produced in the 2nd process is dried on arbitrary base materials or a container, and a phthalocyanine It has the 3rd process of obtaining a nanowire aggregate | assembly (C1), It is characterized by the above-mentioned.

(Preparation of phthalocyanine nanowire assembly film)
The composition obtained as described above is formed into a film on an arbitrary substrate by printing or coating (wet process), and this is dried, so that the minor axis is 100 nm or less and the length relative to the minor axis. An aggregate film containing phthalocyanine nanowires having a thickness ratio (length / minor axis) of 10 or more can be obtained.
As the film forming method of the composition (B), a known and commonly used method can be adopted without any particular limitation. Specifically, an inkjet method, a gravure method, a gravure offset method, an offset method, a letterpress method, a letterpress inversion Method, screen method, micro contact method, reverse method, air doctor coater method, blade coater method, air knife coater method, roll coater method, squeeze coater method, impregnation coater method, transfer roll coater method, kiss coater method, cast coater method, spray Examples include a coater method, a die coater method, a spin coater method, a bar coater method, a slit coater method, and a drop cast method. When precise patterning is required, an ink jet method, a letterpress inversion method, and a microcontact method are preferable.

  There is no particular limitation on the drying after the film formation of the composition (B), and it may be appropriately selected according to the components of the organic solvent constituting the ink. Heat drying under pressure, heat drying under an air current, drying under reduced pressure, and the like can be appropriately selected.

  The base material to which the composition (B) is applied is not particularly limited as long as it is a material that is not damaged by the organic solvent constituting the ink, and any material can be used. Glass, metal, metal oxide It is possible to use a base material such as a polymer material, but when forming carbon nanofibers or carbon nanofiber aggregates on the base material, there is no damage due to temperature in the baking process described later. It is necessary to use a heat-resistant substrate.

  Examples of the heat-resistant substrate in the present invention include glass, metal, ceramics and the like, and particularly, quartz glass, alumina, titanium oxide and the like that are not easily affected by heat can be preferably used.

(Preparation of phthalocyanine nanowire assembly)
The container used for obtaining the phthalocyanine nanowire aggregate (C1) by drying the composition obtained as described above in an arbitrary container must be a material that is not damaged by the organic solvent constituting the ink. In particular, it can be used without limitation, and a container of glass, metal, metal oxide, or polymer material can be used. Moreover, there is no restriction | limiting in particular also about the shape of a container, The thing of arbitrary shapes can be used conveniently.
Drying can be appropriately selected from drying methods such as heating at normal temperature, freeze-drying, drying under reduced pressure, drying under reduced pressure, etc., in addition to a method of leaving the container open and leaving it at room temperature and normal pressure.

The production of the phthalocyanine aggregate may be performed, for example, by spreading the composition (B) on a filter paper or a filter such as glass or polymer by filtration. In this case, it is sufficient to perform the vacuum filtration because the working efficiency is improved.

  In addition, in the manufacturing method (II) of the phthalocyanine nanowire and the phthalocyanine nanowire aggregate, when the phthalocyanine nanowire and the phthalocyanine nanowire aggregate are formed on the base material, the substrate is directly baked in the subsequent stage. It can be used in the process.

(Calcination process of phthalocyanine nanowires and phthalocyanine nanowire aggregates)
The carbon nanofiber and the method for producing a carbon nanofiber aggregate of the present invention include a step of firing the phthalocyanine nanowire or the phthalocyanine nanowire aggregate obtained as described above.

  In the method for producing carbon nanofibers and carbon nanofiber aggregates of the present invention, the heating and firing temperature is preferably 500 ° C. to 1800 ° C., but if the firing temperature is too low, the phthalocyanine nanowires are not sufficiently carbonized. If the formation failure of the carbon fiber occurs and the firing temperature is too high, the decomposition reaction occurs and the carbon fiber disappears. Therefore, the more preferred firing temperature is 600 ° C. to 1500 ° C., more preferably 700 It is the range of ° C to 1200 ° C.

  In the method for producing the carbon nanofibers and the carbon nanofiber aggregate of the present invention, the firing step is preferably performed in an environment with little oxygen in order to prevent the phthalocyanine nanowires from being thermally decomposed and lost. Specifically, it is preferably performed in a nitrogen atmosphere or an argon atmosphere.

  The firing step can be performed using known and commonly used equipment and techniques. In addition to various known firing furnaces such as a muffle furnace, an atmospheric furnace, and an infrared furnace, a microwave oven can also be used. it can.

(Carbon nanofibers and carbon nanofiber aggregates)
One embodiment of the present invention is a carbon nanofiber obtained by performing the above-described steps, and an aggregate of the carbon nanofiber. The carbon nanofiber has a short diameter of 100 nm or less and a long length relative to the short diameter. The thickness ratio (length / minor axis) is 10 or more.

  The aggregate of carbon nanofibers reflects the appearance structure of the aggregate of phthalocyanine nanowires in the manufacturing process. That is, the external structure formed by the drying process of the composition (B) containing the phthalocyanine nanowire and the organic solvent is reflected. Specifically, when the composition (B) is applied on a substrate, a carbon nanofiber aggregate is formed on the substrate in a film shape and dried in a cylindrical container such as a sample tube. Then, the fired product becomes a carbon nanofiber aggregate having a cylindrical appearance. Moreover, the carbon nanofiber aggregate obtained by firing the phthalocyanine nanowire aggregate formed on the filter by filtration exhibits a disk-like appearance. The appearance of the carbon nanofibers may be selected as appropriate depending on the purpose of use.

Among the carbon nanofiber aggregates having various appearance shapes, thin-film carbon nanofiber aggregates formed on a heat-resistant transparent glass substrate such as quartz glass can be expected to be applied as a transparent conductive film.

(Metal particle-supported carbon nanofibers, metal particle-supported carbon nanofiber assemblies)
Since the carbon nanofiber and the carbon nanofiber aggregate of the present invention are obtained by firing the phthalocyanine nanowire and the phthalocyanine nanowire aggregate, the central metal of the phthalocyanine and the phthalocyanine derivative constituting the phthalocyanine nanowire By selecting (X), metal fine particles derived from the central metal (X) of the phthalocyanine molecule can be appropriately supported on the carbon nanofiber surface.

As described above, the central metal (X) of the phthalocyanine molecule constituting the phthalocyanine nanowire that can be used for the production of the carbon nanofiber and the carbon nanofiber aggregate of the present invention is a copper atom, a zinc atom, a cobalt atom, A nickel atom, a tin atom, a lead atom, a magnesium atom, a silicon atom, an iron atom, titanyl (TiO), vanadyl (VO), aluminum chloride (AlCl), etc. can be suitably used. Carbon nanofibers carrying fine metal particles such as cobalt, nickel, tin, lead, magnesium, iron, titanyl, vanadyl, and aluminum can be produced.

  In the production of the carbon nanofiber and the carbon nanofiber aggregate of the present invention, the metal particle-supported carbon nanofiber or the carbon that does not support the metal particle by removing the metal particle from the metal particle-supported carbon nanofiber aggregate. Nanofibers or carbon nanofiber aggregates can also be used. For this purpose, it is possible to use a solvent in which the supported metal particles dissolve, for example, an acidic cleaning agent. Examples of the acidic cleaning agent include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, sulfamic acid, phosphoric acid, and hydrofluoric acid, and organic acids such as oxalic acid, tartaric acid, citric acid, formic acid, glycolic acid, and acetic acid as necessary. Can be used.

  By using the production method of the present invention, it is possible to easily and efficiently produce carbon nanofibers and aggregates thereof. The carbon nanofibers and carbon nanofiber aggregates produced by the production method are It can be used as a filler for the purpose of imparting electrical conductivity to the resin material or improving the mechanical properties of the resin material. It can also be used as a gas storage material utilizing hydrogen absorption, emission ability and methane absorption capacity, anode material for fuel cells, transparent conductive film material, and further, electron emission material for display, catalyst carrier, Useful as.

  Details of the present invention will be described below with reference to examples, but the present invention is not limited thereto. In the following examples, morphology observation of the produced carbon nanofiber aggregates was performed using a VE-9800 real surface view microscope (SEM) manufactured by Keyence Corporation. Moreover, the surface probe microscope (SPI-4000, SPA-400) by SII nanotechnology Co., Ltd. was used for the morphology observation of the carbon nanofiber aggregate produced on the base material.

(Example 1) First step <Production of phthalocyanine nanowire>
As polyether monoamine, 692 parts by mass of “Surfamine B-200” (trade name) (primary amine-terminated poly (ethylene oxide / propylene oxide) (5/95) copolymer, number average molecular weight of about 2,000) manufactured by Huntsman Corporation) To a mixture of 66 parts by mass of sodium carbonate and 150 parts by mass of water, 210 parts by mass of copper phthalocyanine sulfonyl chloride (degree of sulfonation = 1) was added and reacted at 5 ° C. to room temperature for 6 hours. The obtained reaction mixture was heated to 90 ° C. under vacuum to remove water to obtain a copper phthalocyanine sulfamoyl compound represented by the following [Chemical Formula 20].

In the compound, Q represents a hydrogen atom or a methyl group, and propylene oxide / ethylene oxide = 29/6 (molar ratio), and the average value of n = 35.

・ (Crystallization)
Copper phthalocyanine (DIC Co., Ltd., Fastogen Blue 5380E) 1.0 g and phthalocyanine derivatives of copper phthalocyanine sulfamoyl compound represented by [Chemical Formula 20] 1.5 g of concentrated sulfuric acid (manufactured by Kanto Chemical Co., Inc.) The solution was poured into 81 g and completely dissolved to prepare a concentrated sulfuric acid solution. Subsequently, 730 g of distilled water was put into a 1000 mL beaker, which was sufficiently cooled with ice water, and the concentrated sulfuric acid solution prepared above was added while stirring the distilled water, and copper phthalocyanine and [Chemical Formula 20] were used. A composite consisting of the copper phthalocyanine sulfamoyl compound represented was precipitated.
Subsequently, the obtained composite was filtered using a filter paper, washed sufficiently with distilled water, and the composite containing water was recovered. The weight of this water-containing composite was measured and found to be 12.4 g.

・ (Water dispersion)
12.4 g of a hydrous composite containing 2.5 g of a composite composed of the copper phthalocyanine obtained in step (1) and the copper phthalocyanine sulfamoyl compound represented by [Chemical Formula 20] is charged into a polypropylene container having a capacity of 50 mL. Further, 4.3 g of distilled water was added so that the weight ratio of the composite to water was 15%, and then 60 g of zirconia beads having a diameter of 0.5 mm were added and finely dispersed for 2 hours using a paint shaker. Subsequently, the finely divided composite was separated and recovered from the zirconia beads, and distilled water was further added to obtain a finely divided composite aqueous dispersion (solid concentration 5%) having a weight of 50 g.

・ (Dispersion in organic solvent)
10 g was taken from the finely divided composite aqueous dispersion obtained in step (2), 0.5 g of 5N hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was rotated at 2000 rpm for 1 hour. When centrifuged, the micronized complex was precipitated. The hydrochloric acid solution in the supernatant was removed, and 4.5 g of N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the hydrated micronized complex and shaken well. The dispersion was charged into a 100 mL eggplant flask, and 5.0 g of ethylene glycol monomethyl ether acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was additionally charged and stirred for 1 hour.

(Nanowire)
The eggplant flask containing N-methylpyrrolidone and ethylene glycol monomethyl ether acetate in which the micronized complex was dispersed was heated using an oil bath and heated to 145 ° C. over 90 minutes. After reaching 145 ° C., heating was continued for 30 minutes at the same temperature.

Second step <Production of phthalocyanine nanowire composition>
The heated dispersion was filtered using a membrane filter (pore size: 0.1 μm), and the residue was thoroughly washed with N-methylpyrrolidone. The filtered residue was put into N-methylpyrrolidone so that the solid concentration was 2%, and shaken well to obtain a copper phthalocyanine nanowire composition (1) (N-methylpyrrolidone dispersion).
When the solid content of the phthalocyanine nanowire composition (1) obtained here was observed using a transmission electron microscope, the nanowire was grown to a minor axis of about 6 nm and a ratio of the length to the minor axis of 80 or more. It was confirmed to have a shape (see FIGS. 1 and 2). Furthermore, since the obtained phthalocyanine nanowire showed a sharp X-ray diffraction peak by X-ray diffraction (using RINT-ULTIMA + manufactured by Rigaku Corporation), it was confirmed that it had high crystallinity. Moreover, the phthalocyanine nanowire composition (1) was extremely stable, and no precipitation of phthalocyanine nanowires was observed.

3rd process-4th process The phthalocyanine nanowire composition (1) obtained by the 2nd process was vacuum-heat-dried at 80 degreeC in the glass container, and the phthalocyanine nanowire aggregate was obtained. This phthalocyanine nanowire aggregate was heated and baked at 800 ° C. in a nitrogen stream using an electric furnace to obtain a fibrous aggregate mainly having a diameter of 500 nm or less carrying fine particles on the surface (FIG. 3, 4). Measurement of the Raman spectrum of the fibrous ^aggregate, 1590 cm -1, a peak was observed at 1350 cm ^-1, the aggregate was confirmed that the carbon fibers. Further, it was confirmed by X-ray diffraction and elemental mapping of TEM observation (FIG. 5) that the fine particles present on the fiber surface were copper microcrystals.

(Example 2)
The phthalocyanine nanowire composition (1) obtained in Example 1 was formed by a spin coating method to obtain a phthalocyanine nanowire assembly film on a quartz substrate. When this blue film was heated and baked at 800 ° C. in a nitrogen stream using an electric furnace, the color on the quartz substrate became almost transparent. When AFM observation of this surface was performed, it was confirmed that a fiber-like aggregate having a diameter of 500 nm or less was present on the substrate surface (FIG. 6). Measurement of the Raman spectrum of this ^film, 1590 cm -1, a peak was observed at 1350 cm ^-1, fibrous aggregates on the surface it was confirmed that the carbon fiber.

(Example 3)
The phthalocyanine nanowire composition (1) obtained in Example 1 was formed by a casting method to obtain a phthalocyanine nanowire aggregate film on a quartz substrate. The blue film was heated and baked at 800 ° C. in a nitrogen stream using an electric furnace to obtain a light black translucent film. The transmittance of this film was 49.6%, and it was a conductive film having a surface resistance of 1.2 × 10 ⁵ Ω / □ measured by Loresta GP manufactured by Mitsubishi Chemical Corporation. When AFM observation of the film surface was performed, it was confirmed that a fiber-like aggregate having a diameter of 500 nm or less was present on the substrate surface (FIG. 7). Measurement of the Raman spectrum of this ^film, 1590 cm -1, a peak was observed at 1350 cm ^-1, fibrous aggregates on the surface it was confirmed that the carbon fiber.

Example 4
The copper phthalocyanine nanowire composition (2) was obtained in the same manner as in Example 1 except that 1.67 g of copper phthalocyanine and 0.83 g of a phthalocyanine derivative of the [Chemical 5] formula were used instead of the [Chemical 20] formula in Example 1. ) When the phthalocyanine nanowire solid content in the phthalocyanine nanowire composition obtained here was observed using a transmission electron microscope, the minor axis grew to about 10 nm and the ratio of the length to the minor axis increased to 50 or more. It was confirmed to have a nanowire shape (see FIGS. 8 and 9). Furthermore, since the obtained phthalocyanine nanowire showed a sharp X-ray diffraction peak, it was confirmed that the phthalocyanine nanowire had high crystallinity, the dispersion was extremely stable, and precipitation of the phthalocyanine nanowire was not observed.
The composition (2) was vacuum-heated and dried in a glass container in the same manner as in Example 1 to obtain a phthalocyanine nanowire aggregate, and then heated and fired at 800 ° C. using an electric furnace in a nitrogen stream. As a result, a fiber-like aggregate having a diameter of 200 nm or less with fine particles carried on the surface was obtained (FIGS. 10 and 11). Measurement of the Raman spectrum of the fibrous ^aggregate, 1590 cm -1, a peak was observed at 1350 cm ^-1, the aggregate was confirmed that the carbon fibers. In addition, X-ray diffraction and TEM elemental mapping confirmed that the fine particles present on the fiber surface were copper microcrystals.

(Example 5)
A copper phthalocyanine nanowire composition (3) was prepared in the same manner as in Example 1 except that 1.67 g of copper phthalocyanine and 0.83 g of a phthalocyanine derivative of the [Chemical 9] formula were used instead of the [Chemical 20] formula in Example 1. ) When the phthalocyanine nanowires in the phthalocyanine nanowire dispersion obtained here were observed using a transmission electron microscope, the nanowires grew to a short diameter of about 25 nm and a length ratio to the short diameter of 20 or more. It was confirmed to have a shape (see FIGS. 12 and 13). Furthermore, since the obtained phthalocyanine nanowire showed a sharp X-ray diffraction peak, it was confirmed that the phthalocyanine nanowire had high crystallinity, the dispersion was extremely stable, and precipitation of the phthalocyanine nanowire was not observed.

This composition (3) was vacuum-heated and dried in a glass container in the same manner as in Example 1 to obtain a Russianine nanowire aggregate, and then heated and fired at 800 ° C. using an electric furnace in a nitrogen stream. As a result, a fibrous aggregate having a diameter of 200 nm or less having fine particles supported on the surface was obtained (FIGS. 14 and 15). Measurement of the Raman spectrum of the fibrous ^aggregate, 1590 cm -1, a peak was observed at 1350 cm ^-1, the aggregate was confirmed that the carbon fibers. In addition, X-ray diffraction and TEM elemental mapping confirmed that the fine particles present on the fiber surface were copper microcrystals.

(Example 6)
The phthalocyanine nanowire composition (3) obtained in Example 5 was suction filtered using a membrane filter having a diameter of 2.5 cm and a pore diameter of 0.1 μm, and a disk-shaped phthalocyanine nanowire assembly having a diameter of about 2 cm was placed on the filter. Got. This disk-shaped phthalocyanine nanowire aggregate was heated and fired at 800 ° C. using an electric furnace in a nitrogen stream to obtain a black disk-shaped solid. When this solid was observed by SEM, a fiber-like aggregate mainly having a diameter of 500 nm or less carrying a large number of fine particles on the surface was obtained (FIGS. 16 and 17). Measurement of the Raman spectrum of the fibrous ^aggregate, 1590 cm -1, a peak was observed at 1350 cm ^-1, the aggregate was confirmed that the carbon fibers. Further, the elemental mapping of X-ray diffraction and TEM observation confirmed that the fine particles present on the fiber surface were copper microcrystals.

(Comparative Example 1)
A crystalline powder of copper phthalocyanine (manufactured by DIC Corporation, Fastogen Blue 5380E) was heated and fired at 800 ° C. using an electric furnace in a nitrogen stream to obtain a black powder. When SEM observation was performed, amorphous massive particles having a size of several μ to several tens μm were observed, and the presence of carbon nanofibers was not recognized.

(Comparative Example 2)
A black powder was obtained by baking the phthalocyanine derivative of the formula [9] at 800 ° C. using an electric furnace in a nitrogen stream. This powder was amorphous massive particles having a size of several μ to several tens of μm. When SEM observation was performed, fine particles were observed on the surface, but no carbon nanofibers were observed (FIGS. 18 and 19).

  The carbon nanofiber of the present invention can be used as a filler for the purpose of imparting electrical conductivity to a resin material or improving the mechanical properties of the resin material. In addition, it can be used as a gas storage material utilizing hydrogen absorption, emission ability and methane absorption ability, and a negative electrode material for fuel cells, and further as an electron emission material for display and a catalyst carrier.

Claims (5)

In carbon nanofibers obtained by firing phthalocyanine nanowires containing phthalocyanine and phthalocyanine derivatives,
(1) The phthalocyanine is copper phthalocyanine, zinc phthalocyanine or iron phthalocyanine,
(2) The phthalocyanine derivative is represented by the general formula (1), (2) or (3),

(Wherein, X is any one selected from the group consisting of copper atom, zinc atom, cobalt atom, nickel atom, tin atom, lead atom, magnesium atom, silicon atom, iron atom, Y ₁ to Y ₄ represents a linking group for bonding the phthalocyanine skeleton and R _{1 to} R ₄ ;
When Y ₁ to Y ₄ are not present as a linking group, R _{1 to} R ₄ may have SO ₃ H, CO ₂ H, an alkyl group that may have a substituent, or a substituent ( (Oligo) aryl group, optionally substituted (oligo) heteroaryl group, optionally substituted phthalimide group or optionally substituted fullerene,
Y ₁ to Y ₄ are — (CH ₂ ) _n — (n represents an integer of 1 to 10), —CH═CH—, —C≡C—, —O—, —NH—, —S—, When it is a bonding group represented by —S (O) — or —S (O) ₂ —, R _{1 to} R ₄ have an alkyl group which may have a substituent, and a substituent. (Oligo) aryl group which may have a substituent, (oligo) heteroaryl group which may have a substituent, phthalimide group which may have a substituent or fullerenes which may have a substituent, b, c and d each independently represents an integer of 0 to 4, but at least one of them is not 0. )

(In the formula, X is any one selected from the group consisting of a copper atom, a zinc atom, a cobalt atom, a nickel atom, a tin atom, a lead atom, a magnesium atom, a silicon atom, and an iron atom, and Z is the following formula ( a) or a group represented by (b), wherein a, b, c and d each independently represent an integer of 0 to 4, of which at least one is not 0.)

(Here, n is an integer of 4 to 100, Q is each independently a hydrogen atom or a methyl group, and Q ′ is an acyclic hydrocarbon group having 1 to 30 carbon atoms.)

(Here, m is an integer of 1 to 20, and R and R ′ are each independently an alkyl group having 1 to 20 carbon atoms.)
(3) The minor axis of the phthalocyanine nanowire is 100 nm or less, and the ratio of the length to the minor axis (length / minor axis) is 10 or more.
Carbon nanofiber characterized by that. The alkyl group which may have a substituent in the general formula (1) or (2) is a methyl group, an ethyl group or a propyl group, and the (oligo) aryl group which may have a substituent is substituted. An (oligo) phenylene group which may have a group or an (oligo) naphthylene group which may have a substituent, and an (oligo) heteroaryl group which may have a substituent has a substituent (Oligo) pyrrole group, which may have a substituent (oligo) thiophene group, which may have a substituent (oligo) benzopyrrole group or which may have a substituent (oligo) benzo The carbon nanofiber according to claim 1, which is a thiophene group. In the manufacturing method of the carbon nanofiber of Claim 1 or 2,
(1) A first step of obtaining a phthalocyanine nanowire (A) having a minor axis of 100 nm or less and a ratio of the length to the minor axis (length / minor axis) of 10 or more,
(2) a second step of firing the phthalocyanine nanowire (A),
A method for producing carbon nanofibers, comprising: In the manufacturing method of the aggregate | assembly of the carbon nanofiber of Claim 1 or 2,
(1) A first step of obtaining a phthalocyanine nanowire (A) having a minor axis of 100 nm or less and a ratio of the length to the minor axis (length / minor axis) of 10 or more,
(2) a second step of obtaining a composition (B) comprising phthalocyanine nanowires and an organic solvent as essential components;
(3) A third step of obtaining the phthalocyanine nanowire aggregate (C1) by drying the composition (B) on a substrate or in a container,
(4) a fourth step of firing the phthalocyanine nanowire aggregate,
The manufacturing method of the aggregate | assembly of the carbon nanofiber characterized by having. In the manufacturing method of the aggregate | assembly film | membrane of the carbon nanofiber of Claim 1 or 2,
(1) A first step of obtaining a phthalocyanine nanowire (A) having a minor axis of 100 nm or less and a ratio of the length to the minor axis (length / minor axis) of 10 or more,
(2) a second step of obtaining a composition (B) comprising phthalocyanine nanowires and an organic solvent as essential components;
(3) The third step (c) for obtaining the phthalocyanine nanowire aggregate film (C2) by coating and drying the composition (B) on a heat-resistant substrate,
(4) Fourth step (d) for firing the phthalocyanine nanowire assembly film (C2),
A method for producing an aggregate film of carbon nanofibers, comprising:

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