JP2013030545A - Method of manufacturing phthalocyanine nanowire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a phthalocyanine nanowire without decomposition of a phthalocyanine derivative having a substituent group by acid, the phthalocyanine nanowire having a wire-shaped crystal comprising unsubstituted phthalocyanine and phthalocyanine with a substituent group that are representative organic semiconductors, in particular, a nanosize fine-line-shaped structure in which a width (a minor axis) of a wire is 100 nm or less, a ratio of a length to the minor axis (the length/the minor axis) of the wire being 10 or more.SOLUTION: After dissolving only unsubstituted phthalocyanine in acid, microfabricated unsubstituted phthalocyanine obtained by deposition to a poor solvent is mixed with a phthalocyanine derivative having a substituent group, and placed in a solvent or in a solvent vapor atmosphere.

Description

  The present invention relates to a method for producing phthalocyanine nanowires.

  In recent years, there has been a demand for a “lightly inexpensive information terminal that is hard to break” that anyone can use in any location. For this realization, it is desired to use a soft material having a cost merit in a transistor as a key device of an information terminal. However, conventionally used inorganic materials such as silicon cannot sufficiently satisfy such demands.

  Under such circumstances, an “organic transistor (OFET)” using an organic substance in the semiconductor portion of the transistor is attracting attention (see Non-Patent Document 1). A semiconductor made of such an organic substance (organic semiconductor) is soft and can be processed at a low temperature, and generally has a high affinity with a solvent. For this reason, organic semiconductors have the advantage of being able to produce OFETs on a flexible plastic substrate using a wet process such as coating or printing at a low price, which will lead to the realization of a "lightweight and inexpensive information terminal that is hard to break." Is expected as an indispensable material for electronic devices.

  Phthalocyanines such as unsubstituted phthalocyanine or phthalocyanine having a substituent are one of typical organic semiconductors, and may exhibit good transistor characteristics by controlling the higher order structure, that is, the molecular arrangement and aggregation state. It is known (see Non-Patent Document 2). However, since phthalocyanines have low solvent solubility, it is difficult to produce an element by a wet process, and when used for an electronic element, a dry process such as vacuum deposition or sputtering is generally used. Since such a dry process is complicated, it is difficult to provide a low-cost electronic element that is one of the characteristics of an organic semiconductor.

  In order to solve this problem, a technique is also disclosed in which a transistor is manufactured by a wet process by introducing a soluble substituent into phthalocyanines to enhance solvent solubility (see Patent Document 1). However, in this method, since the phthalocyanine molecules are not sufficiently arranged and the higher order structure cannot be controlled, the transistor characteristics are inferior as compared with the dry process. In order to show good semiconductor properties, it is important that the phthalocyanine molecules have a dimensional structure and a crystal structure arranged in a certain direction. Among them, a one-dimensional wire crystal is particularly useful. is there. Moreover, in order to use for the application to an electronic device, it is preferable that this wire-like crystal is a nanowire whose wire diameter is 1 micrometer or less, Preferably it is 100 nm or less.

  Crystals of phthalocyanines are widely used as colorants for paints of printing inks, and many techniques for controlling the crystal size and shape are also known. For example, a solvent salt milling method (for example, Patent Document 2) in which an inorganic salt and an organic solvent are mixed with metal phthalocyanine, and the pigment is finely pulverized by a grinding apparatus, or a large amount of metal phthalocyanine is dissolved in sulfuric acid. Although micronization is performed by a method such as crystallization that precipitates in water (for example, Patent Literature 3), nanowire-like crystals of phthalocyanines cannot be obtained using these methods.

  As a method for controlling the higher-order structure of phthalocyanines, the present inventors have already disclosed a method for producing phthalocyanine nanowires (Patent Document 4). In this production method, an unsubstituted phthalocyanine and a substituent are included. It was necessary to obtain a crystallization complex by dissolving both the phthalocyanine derivative having acid in an acid and then precipitating it in a poor solvent. However, in the production method, in the step of dissolving the phthalocyanine derivative having a substituent in an acid, depending on the type of the substituent that the derivative has, (partial) decomposition of the derivative with an acid occurs, There is a possibility of contamination by degradation products, and depending on the type of substituent, it is decomposed by alkali, so it cannot be neutralized after the step of dissolving in the above-mentioned acid and washed to a predetermined acid concentration or less. In order to do so, a large amount of water was required, and the problem of increased wastewater treatment remained.

Advanced Materials 2002, No. 14, P.I. 99 Applied Physics Letters 2005, 86, p. 22103 Japanese Laid-Open Patent Publication No. 2008-303383 JP 2002-121420 PR JP 2004-091560 A WO 2010/122921

  In view of the above, the present invention provides an unsubstituted phthalocyanine that suppresses the generation of impurities in the system and simplifies the washing process without decomposing the phthalocyanine derivative having a substituent that is a constituent component of the nanowire in the manufacturing process. It aims at providing the manufacturing method of the wire-like crystal which consists of a phthalocyanine which has a substituent, especially the phthalocyanine nanowire which has a nano-sized fine wire-like structure whose width | variety (short axis) of a wire is 100 nm or less.

  As a result of diligent studies to solve the above-mentioned problems, the present invention does not dissolve both an unsubstituted phthalocyanine and a substituted phthalocyanine derivative in an acid, but only an unsubstituted phthalocyanine is dissolved in an acid. A precipitate obtained by precipitation in a poor solvent is mixed with a phthalocyanine derivative having a substituent, and placed in a solvent or in a solvent vapor atmosphere, so that the wire width (short axis) is nano-sized with a width of 100 nm or less. The inventors have found that a phthalocyanine nanowire having a fine wire structure is obtained, and have completed the present invention.

  That is, the present invention is a method for producing a phthalocyanine nanowire having excellent semiconductor characteristics comprising unsubstituted phthalocyanine and a substituted phthalocyanine, which suppresses the generation of impurities in the system and simplifies the cleaning process. A method for producing a phthalocyanine nanowire that is possible can be provided.

2 is a transmission electron micrograph of phthalocyanine nanowires in Example 1. FIG. 2 is a scanning electron micrograph of phthalocyanine nanowires in Example 2. FIG. 4 is a scanning electron micrograph of phthalocyanine nanowires in Example 3.

The present invention includes an unsubstituted phthalocyanine and a substituted phthalocyanine, and a method for producing a phthalocyanine nanowire having a minor axis of 100 nm or less,
(1) Step (a) of obtaining unsubstituted phthalocyanine precipitate (A) by dissolving unsubstituted phthalocyanine in an acid and then precipitating it in a poor solvent.
(2) Step (b) of obtaining a mixture (B) of the unsubstituted phthalocyanine precipitate (A) obtained in the step (a) and a phthalocyanine derivative having a substituent,
(3) Step (c) of converting the mixture (B) obtained in the step (b) into a nanowire in a solvent or in a solvent vapor atmosphere,
It provides the manufacturing method of the phthalocyanine nanowire characterized by including these.
Details of the present invention will be described below.

(Unsubstituted phthalocyanine contained in phthalocyanine nanowires)
As the unsubstituted phthalocyanine of the present invention, a phthalocyanine represented by the general formula (1) or a metal-free phthalocyanine represented by the general formula (2) can be used.

  In general formula (1), X is not limited as long as it constitutes a phthalocyanine nanowire by the nanowire production method described later, but a copper atom, zinc atom, cobalt atom, nickel atom, tin atom, lead atom Metal atoms such as magnesium atom, silicon atom, iron atom and palladium atom, or metal oxides and metal halides such as titanyl (TiO), vanadyl (VO) and aluminum chloride (AlCl). A copper atom, a zinc atom, and an iron atom are particularly preferable.

(Phthalocyanine having a substituent contained in phthalocyanine nanowires)
The phthalocyanine nanowire of the present invention is a phthalocyanine nanowire containing the unsubstituted phthalocyanine and a phthalocyanine having a substituent represented by the following general formula (3) or (4).

(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. )

  The metal atom X that forms a complex with the phthalocyanine having a substituent of the present invention is not particularly limited as long as it is known and commonly used as the central metal of metal phthalocyanine, but preferred metal atoms include copper, zinc, cobalt, nickel, tin And any one metal atom selected from lead, magnesium, silicon, and iron. As X, metal phthalocyanine coordinated with titanyl (TiO), vanadyl (VO), or aluminum chloride (AlCl) can also be used. Here, like the phthalocyanine having a substituent represented by the general formula (4), a compound not containing the central metal X can also be used as the phthalocyanine having a substituent of the present invention.

In the general formula (3) or (4), Y ₁ to Y ₄ can be used without particular limitation as long as they are a linking group that bonds 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 an indoyl group and a pyridinyl group, and a methyl 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 oxalate [60]. A fullerene (PCBM) etc. can be mentioned.

  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. In addition, at least one is not 0 among the numbers a to d of the substituents substituted on the phthalocyanine ring.

  Specific examples of the phthalocyanine having a substituent represented by the general formula (3) of the present invention include the following, but are not limited thereto. Here, the number next to the parentheses in the formula of the substituted phthalocyanine represents the average number of functional groups introduced into the phthalocyanine molecule. The reason why this number is a decimal number is that the number of introduced substituents for each molecule is an integer, but in actual use, different numbers of introduced substituents were mixed, and the average value was expressed. Because it is a thing.

(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 (4), the phthalocyanine which has a substituent in which a central metal does not exist in said formula (Formula 5)-(Formula 13) can also be used.

  General formula (5) of the present invention

(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.)
Examples of the phthalocyanine having a substituent represented by formula (1) include a compound in which the phthalocyanine ring is substituted with at least one sulfamoyl group. 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 having a substituent represented by the general formula (1) used in the present invention can be obtained by combining, for example, copper phthalocyanine sulfonyl chloride and a polyether amine having an amine at the end of the polyether main chain by combining known methods. 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 having a substituent represented by the general formula (5) used in the present invention include, but are not limited to, a compound of the formula (17).

(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 of introduced polyalkylene oxide chains bonded to phthalocyanine through a sulfamoyl bond is 4 in phthalocyanine. 0.2 to 3.0 for one benzene ring.)

  The phthalocyanine having a substituent that can be used in the present invention may have a group represented by the general formula (b) in addition to the phthalocyanine having the substituent.

  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 examples of the phthalocyanine having a preferable substituent include the following.

Moreover, among the phthalocyanines having a substituent represented by the general formula (3), the groups represented by R _{1 to} R ₄ may have SO ₃ H or CO ₂ H, ₃ H or CO ₂ and is not limited 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 which has a substituent represented by General formula (5), 1-4 can be mentioned more preferably. These groups may have one type of group or two types of groups. The phthalocyanine having these substituents can be synthesized by a known and usual method.

The number next to the parentheses in the formula of the phthalocyanine having the above substituent represents the average number of functional groups introduced into the phthalocyanine molecule, and the preferred number of functional groups introduced is 0.2 from the viewpoint of the nanowire formation mechanism described later. To 3.0, more preferably 0.5 to 2.0.

The above phthalocyanines having various substituents 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 17) can be synthesized by the above-described method, and the sulfonated copper phthalocyanine described in (Chemical Formula 5), (Chemical Formula 6), and (Chemical Formula 7) can produce copper phthalocyanine. It can be obtained by heating in (sulfur trioxide concentration: 20%), and the compound of (Chemical Formula 10) can be synthesized, for example, by the method disclosed in Patent Document (US Pat. No. 2,761,868).

The phthalocyanine having the substituent can also be obtained by a known publicly used phthalocyanine synthesis method described in, for example, JP-A No. 2005-145896 and JP-A No. 2007-39561. For example, 4-phenoxy-phthalonitrile and 4 Various phthalonitrile compounds such as -phenylthio-phthalonitrile and 4- (1,3-benzothiazol-2-yl) -phthalonitrile are mixed at an arbitrary ratio with respect to orthophthalonitrile having no substituent. , 8-diazabicyclo [5,4,0] undec-7-ene and the like by heating in ethylene glycol with a metal salt such as copper (II) sulfate or zinc (II) chloride in the presence of an organic base. A phthalocyanine having a substituent having various functional groups in any ratio can be synthesized. Here, the number of the functional groups having a phthalocyanine having a substituent 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 phthalocyanine having a substituent having one functional group per phthalocyanine molecule on average, the mixture of the phthalonitrile derivative and orthophthalonitrile may be 1: 3. When it is desired to introduce 1.5, it can be synthesized at a ratio of 3: 5 using the method described in the patent literature. A phthalocyanine having a substituent 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. For example, Japanese Patent Application Laid-Open No. 2007-516636, paragraph 2 of 0001, and Japanese Patent Application Laid-Open No. 2007-526881. The phthalonitrile derivative described in paragraph 0006 of JP-A-2006-143680, and the phthalonitrile derivative linked to the oligothiophenes described in paragraph 2 of paragraph 0014 of JP-A-2006-143680, A phthalonitrile derivative in which the fullerenes described in Chemical Formula 9 in the paragraph are linked is also included as a raw material for synthesizing a phthalocyanine having a substituent that can be used in the present invention.

The nanowire of this invention has the characteristics which can obtain the various phthalocyanine nanowire from which length and a short axis differ by mix | blending the said unsubstituted phthalocyanine and the phthalocyanine which has a substituent with a compounding quantity suitably.

(Method for producing phthalocyanine nanowire)
Next, the manufacturing method of the phthalocyanine nanowire of this invention is demonstrated.

<Manufacturing method>
This manufacturing method
(1) Step (a) of obtaining unsubstituted phthalocyanine precipitate (A) by dissolving unsubstituted phthalocyanine in an acid and then precipitating it in a poor solvent;
(2) A step (b) of obtaining a mixture (B) of the unsubstituted phthalocyanine precipitate (A) and a phthalocyanine derivative having a substituent;
(3) The step (c) comprises forming the mixture (B) into a nanowire in a solvent or in a solvent vapor atmosphere.

・ Process (a)
In general, it is known that phthalocyanines are soluble in an acid solvent such as sulfuric acid. In the phthalocyanine nanowire manufacturing method of the present invention, the unsubstituted phthalocyanine is first converted into sulfuric acid, chlorosulfuric acid, methanesulfonic acid, trifluoro Dissolve in an acid solvent such as acetic acid. Then, it is put into a poor solvent such as water to obtain the unsubstituted phthalocyanine precipitate (A).

  The amount of the unsubstituted phthalocyanine 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. 20 mass% or less is preferable.

  When the solution in which the unsubstituted phthalocyanine is dissolved is poured into a poor solvent such as water to precipitate the unsubstituted phthalocyanine, the solution has a range of 0.01% by mass to 50% by mass with respect to the poor solvent. preferable. If it is 0.01% by mass or more, the concentration of the precipitate (A) is sufficiently high, so that solids can be easily recovered. If it is 50% by mass or less, all the unsubstituted phthalocyanines are solid precipitates. It becomes (A), there is no dissolved component, and collection becomes easy.

  There is no particular limitation as long as the unsubstituted phthalocyanine is an insoluble or hardly soluble liquid with respect to the poor solvent, but water or water having a low environmental burden can be mainly used, since the homogeneity of the precipitate (A) can be kept high. An aqueous solution as a component can be mentioned as the most preferable poor solvent.

  The unsubstituted phthalocyanine precipitate (A) is filtered using a filter paper and a Buchner funnel to remove acidic water, and is washed with water until the filtrate is neutral. A) can be recovered.

Here, the unsubstituted phthalocyanine precipitate (A) is dehydrated and dried to remove moisture, or even in a water-containing state, the phthalocyanine having a substituent in the next step as described later. Can be mixed with derivatives.
・ Process (b)
The method is not particularly limited as long as the unsubstituted phthalocyanine precipitate (A) obtained through the step (a) and the phthalocyanine derivative having a substituent can be mixed uniformly. The wet mixing method Alternatively, any of dry mixing methods can be used. Among these, the wet mixing method is particularly preferable because the process can be simplified when the nanowire forming process described later is taken into consideration.
In the case of the wet mixing method, a media-type disperser represented by a wet disperser using fine beads such as a bead mill or a paint conditioner, or a T.I. K. Using a medialess disperser such as a wet mix mill represented by Fillmix and Nanomizer, together with a solvent such as water or an organic solvent and a water-containing organic solvent, a precipitate of the unsubstituted phthalocyanine obtained in step (a) ( A) and a phthalocyanine derivative having a substituent can be mixed.

The order of mixing the phthalocyanine precipitate (A), the phthalocyanine derivative having a substituent and the solvent is not particularly limited, and the phthalocyanine precipitate (A) and the phthalocyanine derivative having a substituent may be added simultaneously to the solvent. It is also possible to add a phthalocyanine derivative having a substituent after kneading the phthalocyanine precipitate (A) in a solvent in advance, or pre-kneading a phthalocyanine derivative having a substituent in a solvent before precipitation of phthalocyanine. Body (A) may be added.
The organic solvent is not particularly limited. For example, amide solvents, aromatic organic solvents, glycol ethers, and glycol esters having high affinity with phthalocyanines are preferable, and specifically, affinity with phthalocyanine is particularly high. N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, toluene, xylene, ethylbenzene, chlorobenzene, orthodichlorobenzene, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3- Methoxy-3-methyl-1-butanol, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate , May be mentioned diethylene glycol monomethyl ether acetate as the most preferable organic solvents. Although the said organic solvent can also be used independently, it can also be mixed and used for arbitrary ratios, Furthermore, it can also be used in combination with another organic solvent.

  Organic solvents that can be used in combination with amide solvents, aromatic organic solvents, glycol ethers, and glycol esters include alcohols such as methanol, ethanol, and isopropanol, glycols such as ethylene glycol and diethylene glycol, and ketones such as acetone and methyl ethyl ketone. And halogenated carbons such as dichloromethane, chloroform and carbon tetrachloride.

  The mass ratio of the unsubstituted phthalocyanine precipitate (A) and the substituted phthalocyanine derivative to the solvent is not particularly limited, but the solid content concentration is in the range of 1% by mass to 30% by mass from the viewpoint of mixing efficiency. It is preferable to carry out a mixing treatment. For the mixing treatment, it is preferable to use fine media such as zirconia beads, and the bead diameter is preferably in the range of 0.01 mm to 2 mm in view of the degree of micronization of the unsubstituted phthalocyanine and the phthalocyanine derivative having a substituent. In addition, from the viewpoint of mixing efficiency and recovery efficiency, the micro media is most preferably used in the range of 100% by mass to 1000% by mass with respect to the mixture of the unsubstituted phthalocyanine precipitate and the phthalocyanine derivative having a substituent. In addition, a precipitate of unsubstituted phthalocyanine and a phthalocyanine derivative having a substituent can be mixed.

In addition, when the precipitate (A) of unsubstituted phthalocyanine and the phthalocyanine derivative having a substituent are mixed in a solvent, the solvent can be removed by mixing, drying, or the like as necessary after mixing. The method for removing the solvent and drying is not particularly limited, and examples thereof include filtration, centrifugation, and evaporation using a rotary evaporator. Further, after removing the solvent, drying may be performed using a vacuum dryer or the like until the solvent is completely removed.
Here, the mixing ratio of the substituted phthalocyanine derivative to the unsubstituted phthalocyanine precipitate (A) 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 having the substituent has a function of a functional group or a polymer side chain, so that the crystal grows in one direction through a process described later and is well formed into a 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 the crystal growth. It will never be.

・ Process (c)
The mixture of the unsubstituted phthalocyanine precipitate (A) obtained in step (b) and the substituted phthalocyanine derivative (B) in an organic solvent (in a liquid phase) or in a solvent vapor atmosphere (in a gas phase) , (Heating) is allowed to stand to produce phthalocyanine nanowires. At this time, the solvent may be stirred to the extent that nanowire formation is not hindered, or solvent vapor may be circulated. When stirring the solvent, the step (b) for obtaining the mixture (B) may also serve as the nanowire-forming step (c).
Among these, considering the solvent dispersion of nanowires, which will be described later, the process can be simplified, and therefore, a method of forming nanowires in the liquid phase is preferable.

  In particular, when the mixture (B) is already dispersed in an organic solvent used for nanowire formation, such as N-methylpyrrolidone or orthodichlorobenzene, by wet mixing, the nanowire can be left by standing (heating). Can be In addition, when the powder of the mixture (B) is nanowired in an organic solvent (in a liquid phase), the mixture powder (B) may be added to a container to which an organic solvent has been added in advance, or the mixture powder You may add an organic solvent to the container which installed (B) later. Further, when nanowire formation is performed in a solvent vapor (in the gas phase), the mixture powder (B) may be added later to a container filled with the solvent vapor, or the mixture powder (B) is added. Vapor generation may be performed by adding an organic solvent later in a state where it is not in direct contact with the container, and the mixture powder (B) and the organic solvent are separately prepared at two separate tips such as a Y-tube. A method of generating steam can also be used.

  The temperature for forming the nanowire is preferably in the range of 5 ° C to 250 ° C, more preferably 20 ° C to 200 ° C. If the temperature is 5 ° 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. In the present invention, the phthalocyanine nanowire is a rod-shaped one having a length ratio (length / minor axis) of less than 10 to a long linear one having a ratio of 10 or more. Including. There is no particular limitation on the (heating) standing time required for nanowire formation, and it may be appropriately selected according to the purpose. However, when obtaining a phthalocyanine nanowire having a length of 100 nm or more, at least 10 minutes (heating) ) It is preferable to stand still.

  The organic solvent is not particularly limited as long as it does not have low affinity with phthalocyanines. The amide solvent, aromatic organic solvent, glycol ether, glycol ester described in the wet mixing method in the step (b) Specifically, N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, toluene, xylene, ethylbenzene, chlorobenzene, orthodichlorobenzene, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene Glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether Tate, mention may be made of diethylene glycol monomethyl ether acetate as the most preferable organic solvents. Although the said organic solvent can also be used independently, it can also be mixed and used for arbitrary ratios, Furthermore, it can also be used in combination with another organic solvent.

  Examples of organic solvents that can be used in combination with amide organic solvents, aromatic organic solvents, glycol ethers, and glycol esters include alcohols such as methanol, ethanol, and isopropanol, glycols such as ethylene glycol and diethylene glycol, and ketones such as acetone and methyl ethyl ketone. And halogenated carbons such as dichloromethane, chloroform and carbon tetrachloride. These organic solvents may be added after immersing the mixture (B) in an amide organic solvent, an aromatic organic solvent, a glycol ether, or a glycol ester, or after mixing with the organic solvent in advance, the mixture. (B) may be input.

  When nanowire formation is performed in a solvent, the organic solvent of the mixture (B) has an appropriate fluidity with respect to the amount of the organic solvent added to the mixture (B) and from the viewpoint of preventing aggregation. The solid content concentration is in the range of 0.1% to 20%, more preferably 1% to 10%.

The nanowire obtained through the step (c) can be shortened (decreasing the aspect ratio). Although the method for shortening is not particularly limited, the nanowire is stirred in an organic solvent, dispersed and stirred, dispersed and uniform, ultrasonic irradiation, ultrasonic and uniform processing. The methods such as ultrasonic dispersion treatment and laser irradiation treatment can be carried out by one kind or a combination of plural kinds.
In step (c), the nanowires obtained in the organic solvent (in the liquid phase) are agitated, dispersed and agitated, dispersed and homogenized, ultrasonically irradiated, ultrasonically agitated, ultrasonically uniform, and ultrasonic. By performing a combination of one or more methods such as dispersion treatment and laser irradiation treatment, the nanowires in an aggregated state in an organic solvent can be solved, and the solvent dispersibility of the nanowires can be improved.

  By treating from the step (a) to the step (c), a phthalocyanine nanowire having a width (minor axis) of 100 nm or less can be produced. Although the unsubstituted phthalocyanine precipitate (A) obtained in the step (a) and the phthalocyanine having a substituent are mixed in the step (b) and the nanowire formation in the step (c) is not necessarily clear, It can be presumed that nanowire formation proceeds by a cycle in which nanowire formation proceeds from the interface between the organic solvent and the mixture (B), the generated nanowires migrate into the solvent, and a new interface is thereby formed. At this time, the organic solvent in the step (c) functions as a good dispersion medium for the phthalocyanine nanowires, and it is considered that the cycle is further promoted.

(Application to ink composition)
The phthalocyanine nanowire obtained by the production method of the present invention can be dispersed in an organic solvent after wire formation, and the dispersion is an ink composition suitable for a wet process (printing or coating), particularly an electronic It can be suitably used as an element (transistor or photoelectric conversion element) material.

  The kind of the organic solvent in which the nanowires are dispersed is not particularly limited as long as the phthalocyanine nanowires are stably dispersed, and even if it is a single organic solvent, an organic solvent in which two or more kinds are mixed is used. However, amide solvents are preferred from the viewpoint that phthalocyanine nanowires can be dispersed favorably and stably. Specifically, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl is preferred. Pyrrolidone, N, N-diethylformamide and the like can be mentioned, among which N-methylpyrrolidone is particularly preferable.

  Further, the solvent constituting the ink composition can be appropriately selected depending on the type of phthalocyanine having a substituent contained in the phthalocyanine nanowire. For example, a phthalocyanine nanowire containing a derivative of (Chemical Formula 10) is good. In addition to amide solvents, preferred organic solvents that can be stably dispersed include, for example, toluene, xylene, ethylbenzene, halogenated aromatic organic solvents such as chlorobenzene, orthodichlorobenzene, and the like as aromatic solvents. Examples of halogen-based organic solvents include chloroform, methylene chloride, dichloroethane, and other organic solvents. Of these, orthodichlorobenzene is particularly preferred. Further, preferred organic solvents that can disperse phthalocyanine nanowires containing a derivative of the formula (Chemical Formula 17) well and stably are preferably glycol ethers and glycol esters. Specifically, diethylene glycol monomethyl ether, Examples include ethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, and diethylene glycol monomethyl ether acetate.

  The phthalocyanine nanowire obtained in the present invention can be suitably dispersed in the dispersion solvent at a nanowire content of 0.05 to 20% by mass in the composition. In order to impart process suitability (printing or coating) and film forming property (film quality after printing or coating), it is preferable to disperse at a ratio of 0.1 to 10% by mass.

  The dispersion method of the phthalocyanine nanowire is not particularly limited, but after adding the nanowire to the solvent in a desired ratio, it may be dispersed in the solvent using a method of a known and common method such as stirring treatment. it can.

  The ink composition obtained by dispersing the phthalocyanine nanowires obtained in the present invention in the solvent includes, for example, a π-conjugated polymer, a non-π-conjugated polymer exhibiting semiconducting properties, and a low molecular organic semiconductor other than the phthalocyanine nanowire. It may contain a compound or the like. Here, examples of the π-conjugated polymer include polythiophenes, poly-p-phenylene vinylenes, poly-p-phenylenes, polyfluorenes, polypyrroles, polyanilines, polyacetylenes, polythienylene vinylenes, and the like. Examples of the non-π conjugated polymer exhibiting a physical property include polyvinyl carbazole, and examples of the low molecular organic semiconductor compound include a phthalocyanine having a soluble or solvent dispersible substituent, a soluble or solvent dispersible porphyrin derivative, and the like. Among these, the polymer-based material also has an effect of imparting wet process (printing or coating) suitability and film forming property (film quality after printing or coating) to the ink composition.

Moreover, the ink composition in which the phthalocyanine nanowires obtained in the present invention are dispersed may contain an electron-accepting material typified by fullerenes. As a result, the photoelectric conversion layer can be formed by forming the photoelectric conversion element once and forming it once. Examples of the electron-accepting material that can be used in the present invention include naphthalenes, perylenes, oxazole derivatives, triazole derivatives, phenanthroline derivatives, phosphine oxide derivatives, fullerenes, carbon nanotubes (CNT), modified graphenes, poly- Derivatives (CN-PPV) in which a cyano group is introduced into p-phenylene vinylene, Boramer (trade name, manufactured by TDA Research), known conventional low-molecular or high-molecular organic semiconductor materials in which a CF ₃ group or an F group is introduced It is done.

  Here, as naphthalenes, 1,4,5,8-naphthalene tetracarboxyl diimide (NTCDI), N, N′-dialkyl-1,4,5,8-naphthalene tetracarboxyl diimide (NTCDI-R) (R is an alkyl group having 1 to 20 carbon atoms), 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTCDA) and the like, and perylenes include 3,4,9,10-perylenetetracarboxylic dian Hydride (PTCDA), 3,4,9,10-perylenetetracarboxylic bisbenzimidazole (PTCBI), 3,4,9,10-perylenetetracarboxylic diimide (PTCDI), N, N′-dialkyl-3, 4,9,10-perylenetetracarboxylic diimide (PTCD) -R) (R is an alkyl group having 1 to 20 carbon atoms) and the oxazole derivatives include 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole Examples of triazole derivatives such as (PBD) and 2,5-di (1-naphthyl) -1,3,4-oxadiazole (BND) include 3- (4-biphenylyl) -4-phenyl-5- (4 -T-butylphenyl) -1,2,4-triazole (TAZ) and the like, phenanthroline derivatives such as bathocuproin (BCP), bathophenanthroline (Bphen) and the like, and fullerenes such as C60, C70, C76, C78 and C82. , C84, C90, C94 and the like, [6,6] -phenyl C61 butyric acid methyl ester (PCBM), [5,6] -phenyl C61 Butyric acid methyl ester ([5,6] -PCBM), [6,6] -phenyl C61 butyric acid hexyl ester ([6,6] -PCBH), [6,6] -phenyl C61 butyric acid dodecyl ester ([6,6 ] -PCBD), phenyl C71 butyric acid methyl ester (PC70BM), phenyl C85 butyric acid methyl ester (PC84BM), and the like.

In order to impart wet process suitability (printing or coating) and film forming property (film quality after printing or coating) to the ink composition obtained by dispersing the phthalocyanine nanowires obtained in the present invention, a resin component is added. It may be added as a rheology adjustment or binder component. The resin is not particularly limited as long as it is a publicly known one, and it may be a single resin or two or more resins may be used in combination. Polymethyl methacrylate, polystyrene, polycarbonate, etc. may be used. preferable.

In the ink composition in which the phthalocyanine nanowires obtained in the present invention are dispersed, the constitutional components and the main components are mainly improved for wet process (printing or coating) suitability and film forming property (film quality after printing or coating). Various surfactants and the like may be added as necessary.
As the constitutional component, a well-known and commonly used fine particle powder alone, a dispersion obtained by dispersing these fine particle powder alone in a dispersant or an organic solvent can be used, and these can be used alone or in combination of two or more. It doesn't matter. Specifically, Aerosil series (trade name, manufactured by Evonik), Silicia, Silo Hobic, Silo Pute, Silopage, Silo Pure, Thyrosphere, Silo Mask, Silwell, Fuji Balloon (trade name, manufactured by Fuji Silysia), PMA- There are ST, IPA-ST (trade name, manufactured by Nissan Chemical Co., Ltd.), NANOBIC 3600 series, NANOBIC 3800 series (trade name, manufactured by Big Chemie), etc., but there is no particular limitation. These may be used alone or in combination of two or more.

  Examples of the surfactant include hydrocarbons, silicons, and fluorines, and these can be used alone or in combination of two or more. Among them, a preferred fluorosurfactant is a nonionic fluorosurfactant having a linear perfluoroalkyl group and having a chain length of C6 or more, more preferably C8 or more. Specifically, for example, Mega Fuck F-482, Mega Fuck F-470 (R-08), Mega Fuck F-472SF, Mega Fuck R-30, Mega Fuck F-484, Mega Fuck F-486, Mega Although there is a fuck F-172D, a mega-fuck F178RM (above, trade name, manufactured by DIC), etc., there is no particular limitation. These may be used alone or in combination of two or more. These surfactants are contained in the ink composition in an amount of 5.0% by mass or less, preferably 1.0% by mass or less as an active ingredient, as an active ingredient.

  When the ink composition is constituted by mixing the materials described above with the phthalocyanine nanowires obtained in the present invention, the mixing method is not particularly limited, but the materials described above at a desired ratio. What is necessary is just to mix by a well-known and usual method after adding to a solvent.

  Hereinafter, the present invention will be described more specifically based on examples. In addition, this invention is not limited to the following Example.

Example 1
・ Process (a) (crystallization process)
2.00 g of copper phthalocyanine (manufactured by DIC Corporation, Fastogen Blue 5380E) was completely dissolved in 64 g of concentrated sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) to prepare a concentrated sulfuric acid solution. Subsequently, the concentrated sulfuric acid solution was poured into 584 g of ice-cooled distilled water to precipitate copper phthalocyanine.

  The obtained precipitate was collected by filtration and sufficiently washed with distilled water to collect a water-containing copper phthalocyanine precipitate. This hydrous copper phthalocyanine precipitate was vacuum dried to remove moisture, and 1.83 g of copper phthalocyanine precipitate powder was obtained.

・ Process (b) (mixing process)
1.5 g of the phthalocyanine precipitate powder obtained above and 0.75 g of the copper phthalocyanine derivative represented by (Chemical Formula 10) are put together with 20.25 g of orthodichlorobenzene into a polypropylene container having a capacity of 50 mL, and then φ0. 60 g of 5 mm zirconia beads were added, and a mixing step was performed for 2 hours using a paint shaker. Subsequently, the mixture was separated and recovered from zirconia beads, and further orthodichlorobenzene was added to obtain a mixed solution having a solid concentration of 2%.

・ Process (c) (nanowire process)
The mixed solution was put into a stainless steel pressure cell and heated in an oven to 200 ° C. At this time, the temperature was raised at 2 ° C./min from 30 ° C. to 100 ° C., the temperature was raised at 1 ° C./min from 100 ° C. to 200 ° C., and was maintained at 200 ° C. for 30 minutes after reaching 200 ° C. After cooling, the solid in orthodichlorobenzene was taken out and observed using a transmission electron microscope (model name: JEM-1400, manufactured by JEOL Ltd.). The minor axis was about 25 nm and the major axis was 20 It was confirmed to have a nanowire shape grown to more than double. Furthermore, it was confirmed by X-ray diffraction (using RINT-ULTIMA + manufactured by Rigaku Corporation) that the obtained nanowire showed a peak specific to the phthalocyanine compound and had high crystallinity. In addition, the nanowire dispersion was collected with a glass capillary, spotted on a TLC plastic plate (Merck: silica gel 60F254), and developed with hexane: ethyl acetate = 1: 1. I couldn't see it.

(Example 2)
After obtaining a precipitate of copper phthalocyanine in step (a) of Example 1, neutralizing with sodium hydroxide and washing with distilled water, and in step (b), a phthalocyanine precipitate powder. Copper phthalocyanine nanowires were obtained in the same manner as in Example 1 except that 5 g and 0.75 g of the copper phthalocyanine derivative represented by (Chemical Formula 10) were mixed with 20.25 g of orthodichlorobenzene in a mortar. When the solid in orthodichlorobenzene was taken out and observed using a scanning electron microscope (model name: Hitachi, Ltd., S-800), the minor axis was about 25 nm and the major axis was more than 20 times the minor axis. It was confirmed to have a nanowire shape grown up to. Furthermore, it was confirmed by X-ray diffraction (using RINT-ULTIMA + manufactured by Rigaku Corporation) that the obtained nanowire showed a peak specific to the phthalocyanine compound and had high crystallinity. In addition, the nanowire dispersion was collected with a glass capillary, spotted on a TLC plastic plate (Merck: silica gel 60F254), and developed with hexane: ethyl acetate = 1: 1. Was not seen.

(Example 3)
Example 1 except that 1.0 g of the phthalocyanine derivative of the formula (Chemical Formula 6) is used instead of the formula (Chemical Formula 10) in Example 1 and N-methylpyrrolidone is used instead of the orthodichlorobenzene in the step (b). Similarly, copper phthalocyanine nanowires were obtained. When the solid in N-methylpyrrolidone was taken out and observed using a scanning electron microscope (model name: Hitachi, Ltd., S-800), the minor axis was about 25 nm and the major axis was 20 times or more the minor axis. It was confirmed to have a nanowire shape grown up to. Furthermore, it was confirmed by X-ray diffraction (using RINT-ULTIMA + manufactured by Rigaku Corporation) that the obtained nanowire showed a peak specific to the phthalocyanine compound and had high crystallinity. In addition, the nanowire dispersion was collected with a glass capillary, spotted on a TLC plastic plate (Merck: silica gel 60F254), and developed with hexane: ethyl acetate = 1: 1. Was not seen.

Example 4
In Example 1, instead of the chemical formula (10), a phthalocyanine derivative of the formula (chemical formula 17) (R represents a methyl group, Q represents a hydrogen atom or a methyl group, propylene oxide / ethylene oxide = 29/6 (molar ratio), n The copper phthalocyanine nanowire was obtained in the same manner as in Example 1 except that 1.0 g was used and propylene glycol monomethyl ether acetate was used instead of orthodichlorobenzene in step (b). . When the solid in propylene glycol monomethyl ether acetate was taken out and observed using a scanning electron microscope (model name: Hitachi, Ltd., S-800), the minor axis was about 25 nm and the major axis was 10 times the minor axis. It was confirmed to have a nanowire shape grown to the above. Furthermore, it was confirmed by X-ray diffraction (using RINT-ULTIMA + manufactured by Rigaku Corporation) that the obtained nanowire showed a peak specific to the phthalocyanine compound and had high crystallinity. In addition, the nanowire dispersion was collected with a glass capillary, spotted on a TLC plastic plate (Merck: silica gel 60F254), and developed with hexane: ethyl acetate = 1: 1. Was not seen.

(Example 5)
In Example 1, zinc phthalocyanine instead of copper phthalocyanine, phthalocyanine derivative of formula (Chemical Formula 5) instead of (Chemical Formula 10), and N-methylpyrrolidone instead of orthodichlorobenzene in step (b) are used. Zinc phthalocyanine nanowires were obtained in the same manner as in Example 1. When the solid in N-methylpyrrolidone was taken out and observed using a scanning electron microscope (model name: Hitachi, Ltd., S-800), the minor axis was about 25 nm and the major axis was 10 times or more the minor axis. It was confirmed to have a nanowire shape grown up to. Furthermore, it was confirmed by X-ray diffraction (using RINT-ULTIMA + manufactured by Rigaku Corporation) that the obtained nanowire showed a peak specific to the phthalocyanine compound and had high crystallinity. In addition, the nanowire dispersion was collected with a glass capillary, spotted on a TLC plastic plate (Merck: silica gel 60F254), and developed with hexane: ethyl acetate = 1: 1. Was not seen.

(Example 6)
In Example 1, tin phthalocyanine nanowires were prepared in the same manner as in Example 1 except that tin phthalocyanine was used instead of copper phthalocyanine, and a phthalocyanine derivative containing a phthalimidomethyl group whose central metal is tin in the chemical formula (10) was used. Obtained. When the solid in orthodichlorobenzene was taken out and observed using a scanning electron microscope (model name: Hitachi, Ltd., S-800), the minor axis was about 25 nm and the major axis was more than 10 times the minor axis. It was confirmed to have a nanowire shape grown up to. Furthermore, it was confirmed by X-ray diffraction (using RINT-ULTIMA + manufactured by Rigaku Corporation) that the obtained nanowire showed a peak specific to the phthalocyanine compound and had high crystallinity. In addition, the nanowire dispersion was collected with a glass capillary, spotted on a TLC plastic plate (Merck: silica gel 60F254), and developed with hexane: ethyl acetate = 1: 1. Was not seen.

(Example 7)
In Example 1, in place of copper phthalocyanine, metal-free phthalocyanine, in place of formula (Chemical Formula 10), 3 parts of orthophthalonitrile, 1 part of 4- (2 ′, 6′-dimethylphenoxy) phthalonitrile, In the same manner as in Example 1 except that a metal-free phthalocyanine derivative containing a dimethylphenoxy group synthesized in N, N-dimethylformamide was used with 1,3,3,3-hexamethyldisilazane as a catalyst A phthalocyanine nanowire was obtained. When the solid in orthodichlorobenzene was taken out and observed using a scanning electron microscope (model name: Hitachi, Ltd., S-800), the minor axis was about 25 nm and the major axis was more than 10 times the minor axis. It was confirmed to have a nanowire shape grown up to. Furthermore, it was confirmed by X-ray diffraction (using RINT-ULTIMA + manufactured by Rigaku Corporation) that the obtained nanowire showed a peak specific to the phthalocyanine compound and had high crystallinity. In addition, the nanowire dispersion was collected with a glass capillary, spotted on a TLC plastic plate (Merck: silica gel 60F254), and developed with hexane: ethyl acetate = 1: 1. Was not seen.

(Example 8)
Using ortho-dichlorobenzene containing copper phthalocyanine nanowire obtained in Example (1) using an ultrasonic homogenizer (trade name: US300, manufactured by Nippon Seiki Seisakusho), using a 7φ horn under ice cooling, an output of 10 For 30 minutes. The dispersion thus obtained was collected, and the solid content was observed with a scanning electron microscope. As a result, a rod-shaped solid having a minor axis of about 20 nm or less and a ratio of the length to the minor axis of 5 or less. confirmed. The dispersion was collected with a glass capillary, spotted on a TLC plastic plate (Merck: silica gel 60F254), and developed with hexane: ethyl acetate = 1: 1. Spots estimated to be derived from impurities were found. There wasn't.

Example 9
45 mg of nanowire obtained in Example 1, 45 mg of PCBM (manufactured by Frontier Carbon) and 4500 mg of orthodichlorobenzene were put into a sample bottle, and subjected to ultrasonic irradiation for 30 minutes in an ultrasonic cleaning machine (47 kHz). A product (1) was obtained.

An ITO transparent conductive layer serving as a positive electrode was deposited to a thickness of 100 nm on a glass substrate by sputtering, and this was patterned into a strip shape having a width of 2 mm by photolithography-etching. The obtained glass substrate with pattern ITO was subjected to ultrasonic cleaning three times for 15 minutes each in the order of neutral detergent, distilled water, acetone and ethanol, and then UV / ozone treatment for 30 minutes, and PEDOT: PSS on this. A buffer layer 1 made of PEDOT: PSS was formed to a thickness of 60 nm on the ITO transparent electrode layer by spin coating an aqueous dispersion (AI4083 (trade name, manufactured by HC Starck)). After drying this on a hot plate heated to 100 ° C. for 5 minutes, the ink composition (1) is spin-coated on the PEDOT: PSS layer, and the organic semiconductor derived from the ink composition (1) having a film thickness of 100 nm. A layer was formed. Thereafter, the “substrate on which the organic semiconductor layer is formed” and a metal mask for vapor deposition (for forming a 2 mm strip pattern) are installed in a vacuum vapor deposition apparatus, and the degree of vacuum in the apparatus is reduced to 5 × 10 ⁻⁴ Pa. After the increase, aluminum serving as a negative electrode was deposited by vapor deposition so as to form a strip pattern having a width of 2 mm (thickness: 80 nm) by resistance heating. As described above, the photoelectric conversion element (1) having an area of 2 mm × 2 mm (a portion where the strip-like ITO layer and the aluminum layer intersect) was manufactured.

The positive and negative electrodes of the photoelectric conversion element (1) are connected to a digital multimeter (6241A, product name (manufactured by ADC)), and the spectrum shape: AM1.5, irradiation intensity: 100 mW / cm2 pseudo sunlight (simple type) Under the irradiation of solar simulator XES151S (product name, manufactured by Mitsunaga Electric Manufacturing Co., Ltd.) (irradiation from the ITO layer side), the voltage was swept from −0.1 V to +0.8 V in the atmosphere, and the current value was measured. At this time, the short-circuit current density (the value of the current density when the applied voltage is 0 V. Hereinafter, Jsc) is 5.08 mA / cm2, and the open-circuit voltage (the value of the applied voltage when the current density is 0. Hereinafter, Voc. ) Was 0.54 V, the fill factor (FF) was 0.31, and the photoelectric conversion efficiency (PCE) calculated from these values was 0.84%. FF and PCE were calculated by the following formula.

FF = JVmax / (Jsc × Voc)
(Here, JVmax is the product of the current density and the applied voltage at the point where the product of the current density and the applied voltage is maximum when the applied voltage is between 0 V and the open-circuit voltage value.)

PCE = [(Jsc × Voc × FF) / pseudo sunlight intensity (100 mW / cm 2)] × 100 (%)

(Example 10)
45 mg of nanowires obtained in Example 1 and 9000 mg of orthodichlorobenzene were put into a sample bottle and subjected to ultrasonic irradiation for 30 minutes in an ultrasonic cleaner (47 kHz) to obtain an ink composition (2).

  An n-type silicon substrate was prepared and used as a gate electrode, and the surface layer was thermally oxidized to form a gate insulating film made of silicon oxide. Here, the ink composition (2) was spin-coated to form a semiconductor film. Next, a source / drain electrode made of a gold thin film was patterned by vapor deposition to produce a transistor (1). The channel length L (source electrode-drain electrode interval) was 75 μm, and the channel width W was 5.0 mm.

The transistor characteristics were evaluated by applying a -80V to the transistor (1) while sweeping the voltage (Vg) 0 to -80V to the gate electrode using a digital multimeter (Keithley 237). The measurement was performed by measuring the current (Id) between the drain electrodes. As a result, the mobility was 10 ⁻⁴ cm ² / V · s, and the ON / OFF ratio was 10 ⁴ . The mobility was determined by a known method from the slope of √Id−Vg. The ON / OFF ratio was determined by (maximum value of absolute value of Id) / (minimum value of absolute value of Id).

(Example 11) to (Example 35)
Thereafter, in the same manner as in the above examples, the following Examples (11) to (35) are performed to prepare phthalocyanine nanowires containing various unsubstituted phthalocyanines and substituted phthalocyanines, and using a scanning electron microscope. It was confirmed that nanowires were obtained. (In the table, examples to be referred to in the production of phthalocyanine nanowires are described.)

However, among the substituents of phthalocyanine in the table, sulfonic acid represents the substituent described in (Chemical Formula 6), imide represents the substituent described in (Chemical Formula 10), and sulfamoyl represents the substituent described in (Chemical Formula 17). .

(Comparative Example 1)
1.67 g of copper phthalocyanine and 0.83 g of a copper phthalocyanine derivative represented by (Chemical Formula 10) are completely dissolved in 80 g of concentrated sulfuric acid (manufactured by Kanto Chemical Co., Inc.), and then the concentrated sulfuric acid solution is cooled with ice. A copper phthalocyanine nanowire was obtained in the same manner as in Example (1) except that 2.25 g of the precipitate obtained by charging in 730 g was washed with water and vacuum-dried and mixed with orthodichlorobenzene. . The amount of distilled water used in this washing was 3 times the amount of distilled water used in the same step of (Example 2). In addition, the nanowire dispersion was collected with a glass capillary, spotted on a TLC plastic plate (Merck: silica gel 60F254), and developed with hexane: ethyl acetate = 1: 1. It was observed.

(Comparative Example 2)
Copper phthalocyanine derivative represented by 1.5 g of copper phthalocyanine and (Chemical formula 17) (R represents a methyl group, Q represents a hydrogen atom or a methyl group, propylene oxide / ethylene oxide = 29/6 (molar ratio), average value of n = 35.) Heating was carried out in the same manner as in Comparative Example 1 except that 1.0 g was used and N-methylpyrrolidone was used instead of orthodichlorobenzene. The obtained nanowire dispersion is collected with a glass capillary, spotted on a TLC plastic plate (Merck: silica gel 60F254), and developed with hexane: ethyl acetate = 1: 1. It was observed.

  According to the production method of the present invention, a phthalocyanine nanowire containing an unsubstituted phthalocyanine and a substituted phthalocyanine and having a minor axis of 100 nm or less is produced without the problem of decomposition of the substituted phthalocyanine derivative by acid or alkali. be able to.

Claims (11)

In the method for producing a phthalocyanine nanowire having an unsubstituted phthalocyanine and a substituted phthalocyanine having a minor axis of 100 nm or less,
(1) Step (a) of obtaining unsubstituted phthalocyanine precipitate (A) by dissolving unsubstituted phthalocyanine in an acid and then precipitating it in a poor solvent.
(2) Step (b) of obtaining a mixture (B) of the unsubstituted phthalocyanine precipitate (A) obtained in the step (a) and a phthalocyanine derivative having a substituent,
(3) Step (c) of converting the mixture (B) obtained in the step (b) into a nanowire in a solvent or in a solvent vapor atmosphere,
A method for producing a phthalocyanine nanowire, comprising: The method for producing a phthalocyanine nanowire according to claim 1, wherein the unsubstituted phthalocyanine is represented by the general formula (1) or (2).

(In the formula, X is selected from the group consisting of copper atom, zinc atom, cobalt atom, nickel atom, tin atom, lead atom, magnesium atom, silicon atom, iron atom, palladium atom, TiO, VO and AlCl. Either) The manufacturing method of the phthalocyanine nanowire of Claim 1 or 2 with which the phthalocyanine which has a substituent is represented by General formula (3) or (4).

(Wherein, X is selected from the group consisting of copper atom, zinc atom, cobalt atom, nickel atom, tin atom, lead atom, magnesium atom, silicon atom, iron atom, palladium atom, TiO, VO, and AlCl. Y ₁ to Y ₄ each represents a linking group that binds 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. A good (oligo) aryl group, a (oligo) heteroaryl group which may have a substituent, a phthalimide group which may have a substituent or a fullerene which may have a substituent,
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. ) The alkyl group which may have a substituent is a methyl group, an ethyl group or a propyl group, and the (oligo) aryl group which may have a substituent may have a substituent (oligo) phenylene An (oligo) naphthylene group which may have a group or a substituent, and an (oligo) heteroaryl group which may have a substituent may have a (oligo) pyrrole group or a substituent The (oligo) thiophene group which may have a substituent, the (oligo) benzopyrrole group which may have a substituent or the (oligo) benzothiophene group which may have a substituent, The phthalocyanine of Claim 3 A method for producing nanowires. The manufacturing method of the phthalocyanine nanowire of Claim 1 or 2 with which the phthalocyanine which has a substituent is represented by General formula (5) or (6).

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

(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.) The method for producing a phthalocyanine nanowire according to claim 1, wherein the acid in the step (a) is sulfuric acid, chlorosulfuric acid, methanesulfonic acid, or trifluoroacetic acid. The method for producing a phthalocyanine nanowire according to claim 1, wherein the organic solvent in the step (c) is an amide organic solvent, an aromatic organic solvent, a glycol ether, or a glycol ester. The method for producing phthalocyanine nanowires according to claim 7, wherein the amide organic solvent is N-methylpyrrolidone, N, N-dimethylformamide, N, N-diethylformamide, or N, N-dimethylacetamide. The method for producing a phthalocyanine nanowire according to claim 7, wherein the aromatic organic solvent is toluene, xylene, ethylbenzene, chlorobenzene, or dichlorobenzene. The method for producing a phthalocyanine nanowire according to claim 7, wherein the glycol ether is diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, or 3-methoxy-3-methyl-1-butanol. The method for producing a phthalocyanine nanowire according to claim 7, wherein the glycol ester is ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, or diethylene glycol monomethyl ether acetate.

Images