JP2011116936A - Phthalocyanine nanowire, ink composition and electronic element each containing the same, and method for producing phthalocyanine nanowire - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a phthalocyanine nanowire which has a nanosized thin-line-like structure with the width (minor diameter) of wire of not more than 100 nm and a ratio of the length to the minor diameter (length/minor diameter) of not less than 10; to provide an ink composition including the phthalocyanine nanowire; and to provide a low-cost electronic element obtained by forming an ink composition including the phthalocyanine nanowire into a film by a wet process such as coating, printing, etc. <P>SOLUTION: The phthalocyanine nanowire has a diameter of not more than 100 nm and a ratio of length to minor diameter (length/minor diameter) of not less than 10. The ink composition includes the phthalocyanine nanowire and an organic solvent as essential components. The formed film includes the phthalocyanine nanowire. The electronic element has the film. A method for producing the phthalocyanine nanowire is provided, the nanowire being used for the ink composition, the film and the electronic element. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a phthalocyanine nanowire and an ink composition / electronic device containing the same, and further relates to a method for producing the phthalocyanine nanowire.

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 these 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, it has the advantage of being able to be produced on a flexible plastic substrate using a wet process such as coating or printing at a low price. For electronic devices that are indispensable for the realization of a lightweight, inexpensive information terminal that is hard to break. Expected as a material.

Phthalocyanines such as phthalocyanine or phthalocyanine derivatives are one of typical organic semiconductors, and are known to exhibit good transistor characteristics by controlling the higher order structure, that is, the molecular arrangement and assembly state ( 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 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.

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

In view of the above, the present invention has a wire-like crystal of phthalocyanines, which is a typical organic semiconductor, particularly a nano-sized fine wire structure in which the wire width (minor axis) is 100 nm or less, and the length of the wire relative to the minor axis. An object of the present invention is to provide a phthalocyanine nanowire having a thickness ratio (length / minor axis) of 10 or more, and an ink composition containing the phthalocyanine nanowire.
Another object of the present invention is to provide a low-cost electronic device by forming a film by a wet process such as coating or printing using the ink composition containing the phthalocyanine nanowire.

The present invention provides a phthalocyanine nanowire 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, and the phthalocyanine nanowire and an organic solvent. Is an essential component, and an ink composition is provided.
Moreover, this invention provides the film | membrane characterized by containing the said phthalocyanine nanowire.
The present invention also provides an electronic device comprising the film.
Furthermore, this invention provides the manufacturing method of the phthalocyanine nanowire used for the said ink composition, a film | membrane, and an electronic device.

According to the present invention, a nano-sized wire-like crystal having excellent semiconductor characteristics, in particular, has a nano-sized fine wire-like structure with a wire width (minor axis) of 100 nm or less, with respect to the minor axis of the wire. A phthalocyanine nanowire having a length ratio (length / minor axis) of 10 or more can be provided. In addition, since the ink composition containing the nanowire can be formed into a film by a wet process such as coating or printing, it is possible to provide a lightweight and inexpensive electronic device that is hard to break on a flexible plastic substrate. .

1 is a schematic view of a membrane according to the present invention. It is a schematic cross section of the transistor which is an electronic device by this invention. 1 is a schematic plane equivalent circuit diagram of a transistor array including a transistor as an electronic element according to the present invention. It is a schematic cross section regarding one pixel in the transistor array containing the transistor which is an electronic element by this invention. 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 transmission electron micrograph of phthalocyanine nanowires in Example 2. FIG. 2 is a transmission electron micrograph of phthalocyanine nanowires in Example 2. FIG. 4 is a transmission electron micrograph of phthalocyanine nanowires in Example 3. 4 is a transmission electron micrograph of phthalocyanine nanowires in Example 3. 4 is a transmission electron micrograph of phthalocyanine nanowires in Example 4. 6 is a transmission electron micrograph of phthalocyanine nanowires in Example 5. FIG. 6 is a transmission electron micrograph of phthalocyanine nanowires in Example 5. FIG. 6 is a transmission electron micrograph of phthalocyanine nanowires in Example 6. 6 is a transmission electron micrograph of phthalocyanine nanowires in Example 6. 7 is a transmission electron micrograph of phthalocyanine nanowires in Example 7. FIG. 4 is a transmission electron micrograph of phthalocyanine nanowires in Example 8. 4 is a transmission electron micrograph of phthalocyanine nanowires in Example 9. 4 is a transmission electron micrograph of phthalocyanine nanowires in Example 9. 2 is a scanning electron micrograph of phthalocyanine nanowires in Example 10. FIG. 2 is a scanning electron micrograph of phthalocyanine nanowires in Example 10. FIG. 2 is a transmission electron micrograph of phthalocyanine nanowires in Example 11. 2 is a transmission electron micrograph of phthalocyanine nanowires in Example 11. It is a transmission electron microscope photograph of the sample wire-treated with copper phthalocyanine alone. It is a transmission electron microscope photograph of the sample wire-treated with copper phthalocyanine alone. It is the schematic of a transistor evaluation system.

That is, the present invention
1. A phthalocyanine nanowire containing a phthalocyanine and a phthalocyanine derivative, wherein the minor axis is 100 nm or less, and the ratio of the length to the minor axis (length / minor axis) is 10 or more. ,
2.1. An ink composition comprising the phthalocyanine nanowire and the organic solvent as described in essential components,
3.1. A film characterized by containing the phthalocyanine nanowire described in
4.3. An electronic device comprising the film according to claim 1,
5.1. In the method for producing a phthalocyanine nanowire described in
(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) Step (c) of obtaining a dispersion by dispersing the finely divided composite in an organic solvent;
(4) A method for producing a phthalocyanine nanowire comprising the step (d) of forming the dispersion into a nanowire.

(Phthalocyanine contained in phthalocyanine nanowires)
As the phthalocyanine 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 of the present invention is a phthalocyanine nanowire containing the phthalocyanine and a phthalocyanine derivative represented by 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 2, of which at least one is 1.

  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 2, and represents the number of substituents Y ₁ R ₁ to Y ₄ R ₄ substituted on the phthalocyanine ring. As for the number of substituents, at least one of the phthalocyanine rings is 1.

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, 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 represent an integer of 0 to 2, At least one of them is 1.)

(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 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 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.

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, and the sulfonated copper phthalocyanine described in [Chemical Formula 4], [Chemical Formula 5], and [Chemical Formula 6] converts copper phthalocyanine into fuming sulfuric acid. 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.

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 phthalocyanine and a phthalocyanine derivative with a compounding quantity suitably.

(Ink composition)
An ink composition can be 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. it can.

The solvent type used in the ink composition of the present invention is not particularly limited as long as it stably disperses 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 an ink 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. be able to.
Examples of the halogen organic solvent include organic solvents such as chloroform, methylene chloride, and dichloroethane.

In the ink composition of the present invention, the content of phthalocyanine nanowires in the ink composition is preferably 0.05 to 20% by mass in order to impart printability and to form a good film. It is preferable to set it as 1-10 mass%.

In order to impart printing or coating suitability to the ink composition of the present invention and to impart film quality (film forming) properties after printing or coating, a resin component is added as a rheology adjustment or binder component. be able to. The resin is not particularly limited as long as it is a commonly used resin, and it may be a single resin or a combination of two or more resins. Polymethyl methacrylate or polystyrene, polycarbonate, polyvinyl Carbazole, polythiophenes, polyphenylene vinylenes and the like are preferable.

If the content of these resins is too high, the ink viscosity will increase excessively, affecting printability and film-forming properties by coating. In addition, these resins may have electrical properties such as polymethyl methacrylate, polystyrene, and polycarbonate. In the case of using an inactive resin, if the content is too high, the concentration of phthalocyanine nanowires decreases, so that the semiconductor characteristics expressed by the material are reduced. Accordingly, the content of the resin in the ink composition is preferably 20% by mass or less, particularly 10% by mass or less when an electrically inactive resin such as polymethyl methacrylate, polystyrene, or polycarbonate is used. Is preferred.
Further, the ink composition of the present invention can be used by adding various surfactants and the like as needed mainly for constitutional components, ink surface tension adjustment and leveling improvement.

As the constitutional component, a known and commonly used color pigment alone, fine particle powder alone, a pigment dispersion obtained by previously dispersing these color pigment alone or fine particle powder in a dispersant or an organic solvent, as long as the semiconductor characteristics of the film can be maintained. One kind or two or more kinds can be used. Specifically, EXCEDIC BLUE0565, EXCEDIC RED 0759, EXCEDIC YELLOW 0599, EXCEDIC GREEN 0358, EXCEDIC YELLOW 0648 (trade name made by DIC), Aerosil series (trade name made by Evonik), Cylicia, Silo , Silopure, Thylosphere, Silo Mask, Silwell, Fuji Balloon (trade name, manufactured by Fuji Silysia), PMA-ST, IPA-ST (trade name, Nissan Chemical), NANOBIC 3600 series, NANOBIC 3800 series (trade name, manufactured by Big Chemie), etc. There is no particular limitation. These may be used alone or in combination of two or more. Further, depending on the structure of an electronic element using the present film, the surface smoothness of the film is required. For this reason, the average particle diameter of the constitutional component added to the ink is preferably 1 to 150 nm, and more preferably 5 to 50 nm. PMA-ST, IPA-ST (trade name, manufactured by Nissan Chemical Co., Ltd.), and NANOBIC 3600 series trade name, manufactured by Big Chemie, which are fine particle silica dispersion and alumina dispersion are preferable. The volume average particle diameter can be easily measured by, for example, a dynamic light scattering method. These constitutional components are contained in the total solid content of 90% by mass or less, preferably 70% by mass or less.

As the surfactant, hydrocarbon-based, silicon-based, fluorine-based, or a mixed system of two or more of these surfactants can be applied. 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 Corporation), etc., there is no particular limitation. These may be used alone or in combination of two or more. These surfactants are contained in the total ink composition as active ingredients in an amount of 5.0% by mass or less, preferably 1.0% by mass or less as active ingredients.

(Preparation of a film containing phthalocyanine nanowires)
The ink composition thus obtained was formed into a film by printing or coating (wet process), and dried, whereby the minor axis was 100 nm or less and the ratio of the length to the minor axis (length) A film containing phthalocyanine nanowires having a / minor axis) of 10 or more can be obtained.

As a film forming method of the ink composition of the present invention, a known and commonly used method can be adopted without any particular limitation, and 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.

FIG. 1 is a schematic diagram of the film 1 containing phthalocyanine nanowires obtained in this manner and 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. Shown in The film 1 can be formed of only the phthalocyanine nanowire 2, but the binder resin 3 is further contained in order to fix and hold the phthalocyanine nanowire 2 and to ensure electrical stability. Is preferred.

In this film 1 as well, as described above, the binder resin 3 is not particularly limited as long as it is a publicly known one, and two or more kinds of resins may be used in combination even if they are single resins. Although it does not matter, polymethyl methacrylate or polystyrene, polycarbonate, polyvinyl carbazole, polythiophenes, polyphenylene vinylenes, etc., or a combination of these resins is particularly preferred.

In this case, from the viewpoint of preventing the reduction of the semiconductor characteristics expressed by the phthalocyanine nanowire, when an electrically inactive resin such as polymethyl methacrylate, polystyrene, or polycarbonate is used for the binder resin 3 in the film 1, The rate is preferably 95% by mass or less, and particularly preferably 40% by mass or less.

(Electronic device characterized by having a film containing phthalocyanine nanowires)
A film composed of phthalocyanine nanowires or a film containing phthalocyanine nanowires (phthalocyanine nanowire film) having a minor axis of 100 nm or less and a ratio of length to minor axis (length / minor axis) of 10 or more As an organic transistor (OFET), a film formed of the ink composition according to the present invention and a source electrode and a drain electrode connected to the film were formed on a substrate, and a gate electrode was formed thereon via a gate insulating film. A top gate type can be mentioned.

In addition, a bottom electrode type in which a gate electrode is first formed on a substrate, and a film formed from the ink composition according to the present invention through a gate insulating film, and a source electrode and a drain electrode connected to the film, can be formed. .

FIG. 2 has a film (phthalocyanine nanowire film 1) containing phthalocyanine nanowires 2 having a minor axis of 100 nm or less and a ratio of length to the minor axis (length / minor axis) of 10 or more. A schematic diagram of a transistor 4 configured as a bottom gate bottom contact type as an electronic element is shown. Here, the thickness of the phthalocyanine nanowire film 1 can be appropriately set, and can be set to, for example, 50 to 10,000 nm. Here, it is preferable that most of the arrangement state in the length direction of the phthalocyanine nanowires 2 in the phthalocyanine nanowire film 10 is the direction between the source electrode 5 and the drain electrode 6. Moreover, about the short diameter of a phthalocyanine nanowire, since the electric current per unit electrode width can be enlarged, Preferably it is 10-100 nm, More preferably, it is 20-100 nm. The ratio of the length to the minor axis (length / minor axis) is preferably 40 or more, more preferably 80 or more, in order to ensure the carrier path between the electrodes (channel).

The substrate 7 is made of silicon, glass, or a flexible resin sheet. For example, a plastic film can be used as the sheet. Examples of the plastic film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), Examples thereof include films made of cellulose triacetate (TAC), cellulose acetate propionate (CAP), and the like. Thus, by using a plastic film, the weight can be reduced as compared with the case of using a glass substrate, the portability can be improved, and the resistance to impact can be improved.

The material for forming the source electrode 5, the drain electrode 6 and the gate electrode 8 is not particularly limited as long as it is a conductive material. Platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, tantalum, indium, Palladium, tellurium, rhenium, iridium, aluminum, ruthenium, germanium, molybdenum, tungsten, tin oxide / antimony, indium tin oxide (ITO), fluorine-doped zinc oxide, zinc, carbon, graphite, glassy carbon, silver paste and carbon paste , Lithium, beryllium, sodium, magnesium, potassium, calcium, scandium, titanium, manganese, zirconium, gallium, niobium, sodium-potassium alloy, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum Arm mixtures, magnesium / indium mixture, aluminum / aluminum oxide mixture, can be used lithium / aluminum mixture, etc., in particular, platinum, gold, silver, copper, aluminum, indium, ITO and carbon are preferable. In addition, a known conductive polymer whose conductivity is improved by doping or the like, for example, conductive polyaniline, conductive polypyrrole, conductive polythiophene, a complex of polyethylenedioxythiophene and polystyrenesulfonic acid, or the like is also preferably used. Among them, those having low electrical resistance at the contact surface with the semiconductor layer are preferable.

As a method for forming an electrode, a method for forming an electrode through a pattern mask or the like using a method such as vapor deposition or sputtering using the above-mentioned material as a raw material, or a conductive thin film formed using a method such as vapor deposition or sputtering is known. There are a method of forming an electrode using the photolithographic method and a lift-off method, and a method of etching using a resist such as thermal transfer or ink jet on a metal foil such as aluminum or copper. Alternatively, the conductive polymer solution or dispersion, or the conductive fine particle dispersion may be directly patterned by inkjet, or may be formed from the coating film by lithography, laser ablation, or the like. Furthermore, a method of patterning an ink containing a conductive polymer or conductive fine particles, a conductive paste, or the like by a printing method such as a letterpress, intaglio, planographic, screen printing, letterpress inversion method, or microcontact method can also be used.

Various insulating films can be used as the gate insulating layer 9. In view of cost merit, it is preferable to use a polymer organic material, and in order to obtain high characteristics, it is preferable to use an inorganic oxide having a high relative dielectric constant. Examples of the polymer organic material include polyimide, polyamide, polyester, polyacrylate, photo radical polymerization system, photo cation polymerization system photo-curing resin, copolymer containing acrylonitrile component, polyvinyl phenol, polyvinyl alcohol, novolac resin, Known and conventional polymers such as epoxy resins and cyanoethyl pullulan can be used. Examples of inorganic oxides include silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, tin oxide, vanadium oxide, barium strontium titanate, barium zirconate titanate, lead zirconate titanate, lead lanthanum titanate, strontium titanate, Examples include barium titanate, barium magnesium fluoride, bismuth titanate, strontium bismuth titanate, strontium bismuth tantalate, bismuth tantalate niobate, and yttrium trioxide. Of these, silicon oxide, aluminum oxide, tantalum oxide, and titanium oxide are preferable. Inorganic nitrides such as silicon nitride and aluminum nitride can also be suitably used.

As a method of forming the insulating film, a dry process such as a vacuum deposition method, a molecular beam epitaxial growth method, an ion cluster beam method, a low energy ion beam method, an ion plating method, a CVD method, a sputtering method, an atmospheric pressure plasma method, Inkjet method, gravure method, gravure offset 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, etc. When patterning is required, an ink jet method, letterpress reverse method, include wet process such as micro contact method, may be appropriately used depending on the material.

The wet process of inorganic oxide is a method of applying and drying a liquid in which inorganic oxide fine particles are dispersed in an arbitrary organic solvent or water using a dispersion aid such as a surfactant as required. A so-called sol-gel method in which a solution of a precursor, for example, an alkoxide body is applied and dried can be used.

The dry film thickness of these insulating films is 0.1 to 2 μm, preferably 0.3 to 1 μm.

The transistor as the electronic element according to the present invention can constitute an electronic component module by integration. Examples of the electronic component module include a transistor array as a back substrate such as a display, an inverter as a RFID logic circuit, and a ring oscillator. 3 and 4 are a schematic plane equivalent circuit diagram of the transistor array and a schematic cross-sectional view relating to one pixel in the transistor array.

In FIG. 3, the transistor array has a large number of transistors A arranged in a matrix. B is a gate bus line connected to the gate electrode of the transistor, and C is a source bus line connected to the source electrode of the transistor A. An output element D is connected to the drain electrode of each transistor A. The output element D corresponds to a display element, such as a liquid crystal or an electrophoretic element.

In FIG. 4, a sealing layer 10 is provided on the phthalocyanine nanowire film 1 and covered with a light shielding film 11. Further, the entire structure is covered with the interlayer insulating film 12.

(Method for producing phthalocyanine nanowire)
Next, production methods (I) to (II) of the phthalocyanine nanowire 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) Step (c) of obtaining a dispersion by dispersing the finely divided 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, 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 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 (1) can be mentioned.

Y in the general formula (1) in the present 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 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, Y is a polymer chain derived from an alkylene oxide copolymer which is a group represented by the general formula (2), and its hydrophilicity and lipophilicity are optimized according to the solubility in the polyhydric alcohol used. It is desirable to do. 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 (1) can be obtained by, for example, combining copper phthalocyanine sulfonyl chloride and a polyether amine having an amine at the end of the polyether main chain (hereinafter referred to as “polyether”) by carefully combining known and commonly used methods. 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 (1) used in the present invention include the compound of the above formula (3), but are not limited thereto.
(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, 1,2-diazabicyclo (5.4.0) undecene-7 (hereinafter referred to as “DBU”) while dissolving a phthalonitrile compound such as orthophthalonitrile in a polyhydric alcohol such as α-glycol or glycerin while heating. The reaction is carried out in the presence or absence of an organic base such as a metal alkoxide 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.

(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 the mass in a range of 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 nanowire of the present invention mentioned above, the production method (I) is more preferable.

(Example 1) <Production of phthalocyanine nanowire ink composition>
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.

・ Process (1) (crystallization process)
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.

・ Process (2) (Water dispersion process)
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.

-Step (3) (dispersing step in an 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.

・ Process (4) (nanowire process)
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.

The heated dispersion was filtered using a membrane filter (pore size: 0.1 μm), and the residue was thoroughly washed with N-methylpyrrolidone. The filter residue was put into N-methylpyrrolidone so that the solid concentration would be 2%, and shaken well to obtain a copper phthalocyanine nanowire ink composition (1) (N-methylpyrrolidone dispersion).

When the solid content of the phthalocyanine nanowire ink composition (1) obtained here was observed using a transmission electron microscope, the short diameter was about 6 nm, and the ratio of the length to the short diameter was increased to 80 or more. It was confirmed to have a wire shape (see FIGS. 5 and 6). 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 ink composition (1) was extremely stable, and no precipitation of phthalocyanine nanowires was observed.

<Manufacture of organic transistors>
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. The said phthalocyanine nanowire ink composition (1) was spin-coated here, and the semiconductor film was formed. Next, a source / drain electrode made of a gold thin film was patterned by vapor deposition to produce an organic transistor (1). The channel length L (source electrode-drain electrode interval) was 75 μm, and the channel width W was 5.0 mm.

(Example 2) <Production of phthalocyanine nanowire ink composition>
A copper phthalocyanine nanowire ink composition (Example 1) was used except that 1.67 g of copper phthalocyanine and 0.83 g of a phthalocyanine derivative of the [Chemical Formula 5] formula were used instead of the [Chemical Formula 20] formula ( 2) was obtained. When the phthalocyanine nanowire in the phthalocyanine nanowire ink composition obtained here was observed using a transmission electron microscope, the short diameter was about 10 nm, and the ratio of the length to the short diameter grew to 50 or more. It was confirmed to have a wire shape (see FIGS. 7 and 8). 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.
<Manufacture of organic transistors>
An organic transistor (2) was produced in the same manner as in Example 1 except that the phthalocyanine nanowire ink composition (1) used for the semiconductor film production was changed to the phthalocyanine nanowire ink composition (2).

(Example 3)
A copper phthalocyanine nanowire 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 6] formula were used instead of the [Chemical 20] formula in Example 1. When the phthalocyanine nanowire obtained here was observed using a transmission electron microscope, it was confirmed that it had a nanowire shape in which the minor axis was about 25 nm and the ratio of the length to the minor axis was 10 or more. (See FIGS. 9 and 10). 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.

Example 4
A copper phthalocyanine nanowire 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 7] formula were used instead of the [Chemical 20] formula in Example 1. When the phthalocyanine nanowire obtained here was observed using a transmission electron microscope, it was confirmed that it had a nanowire shape in which the minor axis was about 30 nm and the ratio of the length to the minor axis was 10 or more. (See FIG. 11). 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.

(Example 5) <Production of phthalocyanine nanowire ink composition>
A copper phthalocyanine nanowire ink composition (Example 1) except that 1.67 g of copper phthalocyanine and 0.83 g of a phthalocyanine derivative of the [Chemical 9] formula are used instead of the [Chemical 20] formula ( 5) was obtained. 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.
<Manufacture of organic transistors>
An organic transistor (5) was produced in the same manner as in Example 1 except that the phthalocyanine nanowire ink composition (1) used for the production of the semiconductor film was changed to the phthalocyanine nanowire ink composition (5).

(Example 6)
<Production of phthalocyanine nanowire ink composition>
Paint a composite crystallized with sulfuric acid in the same manner as in Example 1 except that 1.67 g of copper phthalocyanine in Example 1 and 0.83 g of a phthalocyanine derivative of [Chemical 9] formula are used instead of [Chemical 20] formula After finely pulverizing with a shaker, the finely divided complex obtained by filtration was dispersed in 60 g of orthodichlorobenzene, stirred for 2 hours, then added with 60 g of N-methylpyrrolidone, and further stirred for 2 hours. Thereafter, nanowires were formed in the same manner as 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. 14 and 15). 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.

(Example 7)
A zinc phthalocyanine nanowire was obtained in the same manner as in Example 1 except that 1.67 g of zinc phthalocyanine and 0.83 g of a phthalocyanine derivative of the [Chemical Formula 4] formula were used instead of the [Chemical Formula 20] formula. When the phthalocyanine nanowire obtained here was observed using a transmission electron microscope, it was confirmed that it had a nanowire shape in which the minor axis was grown to about 25 nm and the ratio of the length to the minor axis was 20 or more. (See FIG. 16). 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.

(Example 8)
In Example 1, except that 1.67 g of metal-free phthalocyanine and 0.83 g of a phthalocyanine derivative of [Chemical formula 5] instead of [Chemical formula 20] are used, copper phthalocyanine and metal-free phthalocyanine are used in the same manner as in Example 1. A composite nanowire was obtained. When the phthalocyanine nanowire obtained here was observed using a transmission electron microscope, it was confirmed that it had a nanowire shape in which the minor axis was grown to about 20 nm and the ratio of the length to the minor axis was 20 or more. (See FIG. 17). 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.

Example 9
A water-containing composite was obtained through the crystallization step of Example 1 except that 1.6 g of copper phthalocyanine and 1.2 g of a phthalocyanine derivative of the formula [Chemical 9] were used instead of the formula [Chemical 20] in Example 1. . This was vacuum-dried at 50 ° C. for 48 hours using a vacuum dryer to remove moisture, and 2.61 g of a composite was obtained. The composite was put together with 23.49 g of orthodichlorobenzene into a polypropylene container having a capacity of 50 mL, 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 complex was separated and recovered from the zirconia beads, and further orthodichlorobenzene was added to obtain a finely divided complex dispersion having a solid concentration of 2%. 1 g of the dispersion was collected, 1 g of orthodichlorobenzene was further added, and the dispersion was added to a stainless steel pressure cell having a capacity of 2 mL as a dispersion having a solid concentration of 1%, and this was heated to 200 ° C. in an oven. At this time, by raising the temperature from 30 ° C. to 100 ° C. at 2 ° C./min, from 100 ° C. to 200 ° C. by raising the temperature at 1 ° C./min and holding 200 ° C. for 30 minutes after reaching 200 ° C. A phthalocyanine nanowire was obtained.

Then, the phthalocyanine nanowire was recovered from the pressure cell by cooling and observed using a transmission electron microscope. The nanowire shape was grown to a short diameter of about 10 nm and a length ratio to the short diameter of 50 or more. (See FIGS. 18 and 19). 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.

Subsequently, 1 g of the obtained orthodichlorobenzene dispersion of the phthalocyanine nanowire was fractionated, and 1 g of chloroform was further added to obtain a phthalocyanine nanowire ink composition. The ink composition was formed on a 2 cm square glass plate using a spin coater. The film forming conditions at this time were increased to 1200 rpm in 10 seconds, and then held at 1200 rpm for 60 seconds.
When the film | membrane which consists of obtained phthalocyanine nanowire was observed using the laser microscope, the flat and uniform film | membrane was obtained and the film thickness was 150 nm.

(Example 10)
1.65 g of copper phthalocyanine and 0.83 g of iron phthalocyanine tetrasulfonic acid were added to 81 g of concentrated sulfuric acid 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 iron phthalocyanine tetrasulfonic acid. A composite consisting of was deposited. Subsequently, the obtained composite was filtered using a filter paper, washed sufficiently with distilled water, and the composite containing water was recovered. When the weight of this water-containing composite was measured, it was 9.05 g. 1 g of the water-containing composite particles were collected, dispersed in 10 g of orthodichlorobenzene, and stirred for 30 minutes to obtain copper and iron mixed phthalocyanine nanowires. When the phthalocyanine nanowire obtained here was observed using a scanning electron microscope, it was confirmed that it had a nanowire shape in which the minor axis was about 100 nm and the ratio of the length to the minor axis was 20 or more. (See FIGS. 20 and 21).

(Example 11) <Synthesis of phthalocyanine derivative>
Orthophthalonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) (2.0 g) and ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) (38.0 g) were charged into a 50 mL round bottom flask, Five drops of 8-diazabicyclo [5,4,0] undec-7-ene were added, and orthophthalonitrile was dissolved by heating in an oil bath adjusted to 40 ° C. over 90 minutes. This solution was yellow and no undissolved orthophthalonitrile was observed.

4- (2 ′, 6′-dimethylphenoxy) -phthalonitrile (Tokyo Chemical Industry Co., Ltd.) (1.29 g) and ethylene glycol (24.51 g) were charged into a 50 mL round bottom flask, and then stirred with 1 , 8-diazabicyclo [5,4,0] undec-7-ene was added, and 4- (2 ′, 6′-dimethylphenoxy) -phthalonitrile was added in an oil bath adjusted to 120 ° C. over 30 minutes. Heated.

On the other hand, 0.70 g of copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) and 13.30 g of ethylene glycol were put into a 50 mL round bottom flask, and then the oil bath adjusted to 100 ° C. with stirring. Copper (II) chloride was heated and dissolved over 60 minutes to prepare an ethylene glycol solution of copper (II) chloride.

Next, the obtained two kinds of phthalonitrile solution and copper chloride solution were put into a 100 mL round bottom flask and mixed, and stirred at a temperature of 40 ° C. or lower for 10 minutes to obtain a uniform mixed solution. The flask was immersed in an oil bath heated to 150 ° C. in advance, and the reaction was continued for 15 minutes while stirring.

After completion of the reaction, the reaction mixture was cooled to 80 ° C. or lower, poured with 50 g of 1N hydrochloric acid aqueous solution, stirred for 30 minutes, and then the contents of the flask were filtered through a 0.1 μm membrane filter to obtain sodium hydroxide having a concentration of 5%. The filter residue was washed with an aqueous solution and then with methanol, and the residue was dried at 80 ° C. for 2 hours to obtain a blue solid as a phthalocyanine derivative (recovered amount: 1.8 g).

<Production of phthalocyanine nanowire ink composition>
Example 1 except that 1.67 g of copper phthalocyanine in Example 1 and 0.83 g of the phthalocyanine derivative having a 4- (2 ′, 6′-dimethylphenoxy group) synthesized earlier instead of the formula [Chemical Formula 20] are used. Copper phthalocyanine nanowires were obtained in the same manner as in Example 1. When the phthalocyanine nanowires obtained here were observed using a transmission electron microscope, the minor axis was about 25 nm and the ratio of the length to the minor axis was 20 or more. (See Fig. 22 and Fig. 23) The obtained nanowire shows a sharp X-ray diffraction peak, so that it can be confirmed that it has high crystallinity. The dispersion was very stable and no precipitation of phthalocyanine nanowires was observed.

(Example 12) <Production of phthalocyanine nanowire ink composition>
Polymethylmethacrylate (PMMA) (manufactured by Aldrich: molecular weight 120,000) was added to the phthalocyanine nanowire ink composition (1) of Example 1 so as to be 2% by mass with respect to the total ink composition, and the phthalocyanine nanowire ink composition Product (12) was produced.

<Manufacture of organic transistors>
An organic transistor (12)) was produced in the same manner as in Example 1 except that the phthalocyanine nanowire ink composition (1) used for the production of the semiconductor film was changed to the phthalocyanine nanowire ink composition (12)).

(Example 13) <Production of phthalocyanine nanowire ink composition>
Polystyrene (manufactured by Aldrich: molecular weight 13000) was added to the phthalocyanine nanowire ink composition (1) of Example 1 so as to be 0.2% by mass with respect to the total ink composition, and the phthalocyanine nanowire ink composition (13 ) Was manufactured.

<Manufacture of organic transistors>
An organic transistor (13)) was produced in the same manner as in Example 1 except that the phthalocyanine nanowire ink composition (1) used for the production of the semiconductor film was changed to the phthalocyanine nanowire ink composition (13)).

(Example 14) <Production of phthalocyanine nanowire ink composition>
Polystyrene (manufactured by Aldrich: molecular weight 13000) was added to the phthalocyanine nanowire ink composition (1) of Example 1 so as to be 0.6% by mass with respect to the total ink composition, and the phthalocyanine nanowire ink composition (14 ) Was manufactured.

<Manufacture of organic transistors>
An organic transistor (14)) was produced in the same manner as in Example 1 except that the phthalocyanine nanowire ink composition (1) used for the production of the semiconductor film was changed to the phthalocyanine nanowire ink composition (14)).

(Example 15) <Production of phthalocyanine nanowire ink composition>
In the step (3) of Example 1 (dispersing step in an organic solvent), the procedure was carried out except that only 9.5 g of N-methylpyrrolidone was added to the water-containing micronized complex after centrifugation and stirred for 1 hour. In the same manner as in Example 1, a copper phthalocyanine nanowire ink composition (15) containing N-methylpyrrolidone as a dispersion and having a solid content of 2% was obtained.

<Manufacture of organic transistors>
An organic transistor (15)) was produced in the same manner as in Example 1 except that the phthalocyanine nanowire ink composition (1) used in the semiconductor film production was changed to the phthalocyanine nanowire ink composition (15) 3). .

(Example 16) <Production of phthalocyanine nanowire ink composition>
In the step (1) (crystallization step) of Example 1, N-methylpyrrolidone is used as a dispersion in the same manner as in Example 1 except that 1.2 g of the copper phthalocyanine derivative represented by [Chemical Formula 9] is used. A copper phthalocyanine nanowire ink composition (16) having a solid content of 2% was obtained.

<Manufacture of organic transistors>
An organic transistor (16)) was produced in the same manner as in Example 1 except that the phthalocyanine nanowire ink composition (1) used for the production of the semiconductor film was changed to the phthalocyanine nanowire ink composition (16)).

(Example 17) <Production of phthalocyanine nanowire ink composition>
In the process (1) (crystallization process) of Example 1, N-methylpyrrolidone was prepared in the same manner as in Example 1 except that 1.0 g of the copper phthalocyanine sulfamoyl compound represented by [Chemical Formula 20] was used. A copper phthalocyanine nanowire ink composition (17) having a solid content of 2% was obtained as a dispersion.

<Manufacture of organic transistors>
An organic transistor (17)) was produced in the same manner as in Example 1 except that the phthalocyanine nanowire ink composition (1) used for the production of the semiconductor film was changed to the phthalocyanine nanowire ink composition (17)).

(Example 18)
<Production of phthalocyanine nanowire ink composition>
Poly (2-methoxy-5- (2′-ethylhexyloxy) -1,4 was added to the phthalocyanine nanowire ink composition (5) of Example 5 at 0.6% by mass with respect to the total ink composition. -Phenylene vinylene (manufactured by Aldrich: molecular weight: 150,000 to 200,000) was added to produce a phthalocyanine nanowire ink composition (18).

<Manufacture of organic transistors>
An organic transistor (18)) was produced in the same manner as in Example 1 except that the phthalocyanine nanowire ink composition (1) used for the production of the semiconductor film was changed to the phthalocyanine nanowire ink composition (18)).

(Example 19) <Production of phthalocyanine nanowire ink composition>
In the phthalocyanine nanowire ink composition (5) of Example 5, regioregular poly (3-hexylthiophene-2,5-diyl) (manufactured by Merck: 0.5% by mass with respect to the total ink composition). Rishicone SP001) was added to produce a phthalocyanine nanowire ink composition (19).

<Manufacture of organic transistors>
An organic transistor (19)) was produced in the same manner as in Example 1 except that the phthalocyanine nanowire ink composition (1) used in the production of the semiconductor film was changed to the phthalocyanine nanowire ink composition (19)).

(Comparative Example 1)
In Example 1, a treatment and dispersion liquid were obtained in the same manner as in Example 1 using only copper phthalocyanine without using a phthalocyanine derivative. When the solid content of the dispersion obtained here was observed using a transmission electron microscope, the ratio of the length to the width was 5 with the needle-like crystal coarsened to a length of several tens of μm and the width of about 100 nm. Nanowires were not obtained with a mixture of less plate-like particles, and the dispersion was unstable and settled in a few minutes after shaking (see FIGS. 24 and 25).

(Comparative example 2) <Manufacture of a copper phthalocyanine dispersion ink composition>
A copper phthalocyanine-dispersed ink composition (2) was prepared by mixing 1.2 g of copper phthalocyanine, 0.6 g of a copper phthalocyanine sulfamoyl compound represented by [Chemical Formula 20], 0.2 g of PMMA, and 98 g of N-methylpyrrolidone. ) 'Manufactured.

<Manufacture of organic transistors>
An organic transistor (2) ′ was produced in the same manner as in Example 1 except that the phthalocyanine nanowire ink composition (1) used for the production of the semiconductor film was changed to the copper phthalocyanine-dispersed ink composition (2) ′.

(Comparative Example 3) <Production of phthalocyanine rod-dispersed ink composition>
In the step (1) (crystallization step) of Example 1, the solid content was 2% in the same manner as in Example 1 except that only 2.0 g of copper phthalocyanine (DIC Corporation, Fastogen Blue 5380E) was used. N-methylpyrrolidone dispersion was prepared. When the solid content of the phthalocyanine rod-dispersed ink composition (3) ′ obtained here was observed using a transmission electron microscope, the plate had a width of 100 nm or more and a ratio of the length to the width of less than 20 Copper phthalocyanine that is in the shape was confirmed. The stability of the N-methylpyrrolidone dispersion was low and the copper phthalocyanine settled in a few minutes after shaking.

<Manufacture of organic transistors>
An organic transistor (3) ′ was produced in the same manner as in Example 1 except that the phthalocyanine nanowire ink composition (1) used for the semiconductor film production was changed to the phthalocyanine rod-dispersed ink composition (3) ′.

<FET evaluation>
The transistor characteristics of each of the organic transistors (1), (2), (5), (12) to (19), (2) ′, and (3) ′ were measured (see FIGS. 2 and 26). The transistor characteristic is measured by using a digital multimeter (237, manufactured by Keithley), sweeping 0 to -80V voltage (Vg) to the gate electrode, and applying -80V applied current (Id) between the source and drain electrodes. This was done by measuring. The mobility was determined by a known method from the slope of √Id−Vg. The unit is cm ² / V · s. The ON / OFF ratio (hereinafter referred to as ON / OFF) was obtained by (maximum value of absolute value of Id) / (minimum value of absolute value of Id). These results are shown in Table 1.

The organic transistor of the embodiment shown in Table 1, the ^{mobility: 10 -5 ~10 -3, ON /} OFF: it can be seen that the 10 3 to 10 ⁵ of the transistor characteristics.
On the other hand, in the organic transistors of Comparative Examples 2 and 3, Id was not modulated by the gate voltage, and did not exhibit transistor characteristics.

According to the present invention, by using phthalocyanine nanowires, it is possible to produce a semiconductor film-forming ink having excellent dispersibility, and by applying this to an OFET by a wet process, it is an electronic element that is hard to break and is light and inexpensive. Can be provided.

A molecular assembly having a nano-sized fine-line crystal structure, containing 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 Since the ink composition to be formed can be formed into a film by printing or coating (wet process), it is possible to provide a lightweight and inexpensive electronic device that is hard to break on a flexible plastic substrate.

1 Film (phthalocyanine nanowire film)
2 Phthalocyanine nanowire 3 Binder resin 4 Transistor 5 Source electrode 6 Drain electrode 7 Substrate 8 Gate electrode 9 Gate insulating film 10 Sealing layer 11 Light shielding film 12 Interlayer insulating film 13 Pixel electrode

Claims (22)

A phthalocyanine nanowire containing phthalocyanine and a phthalocyanine derivative,
A phthalocyanine nanowire having a minor axis of 100 nm or less and a ratio of length to minor axis (length / minor axis) of 10 or more. The phthalocyanine nanowire according to claim 1, wherein the phthalocyanine is copper phthalocyanine, zinc phthalocyanine or iron phthalocyanine. The phthalocyanine nanowire according to claim 1 or 2, wherein the phthalocyanine derivative is represented by the general formula (1) or (2).

(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 represent an integer of 0 to 2, of which at least one is 1. ) 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) A phenylene group or a (oligo) naphthylene group which may have a substituent, a (oligo) heteroaryl group which may have a substituent may have a (oligo) pyrrole group, a substituent The (oligo) thiophene group which may have a group, the (oligo) benzopyrrole group which may have a substituent or the (oligo) benzothiophene group which may have a substituent. Phthalocyanine nanowire. The phthalocyanine nanowire according to claim 1 or 2, wherein the phthalocyanine derivative is represented by the general formula (3).

(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), a, b, c and d each independently represent an integer of 0 to 2, of which at least one is 1.

(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.) An ink composition comprising the phthalocyanine nanowire according to any one of claims 1 to 5 and an organic solvent as essential components. The ink composition according to claim 6, wherein the content of the phthalocyanine nanowire is in the range of 0.05 to 20% by mass. The ink composition according to claim 6, wherein the organic solvent is an amide organic solvent, an aromatic organic solvent, or a halogen organic solvent. The ink composition according to claim 8, wherein the amide organic solvent is N-methylpyrrolidone, N, N-dimethylformamide, N, N-diethylformamide, or N, N-dimethylacetamide. The ink composition according to claim 8, wherein the aromatic organic solvent is toluene, xylene, ethylbenzene, chlorobenzene, or dichlorobenzene. The ink composition according to claim 8, wherein the halogen-based organic solvent is chloroform, methylene chloride, or dichloroethane. The ink composition according to claim 6, further comprising a film-forming material. The ink composition according to claim 12, wherein the film-forming material is polymethyl methacrylate, polythiophene, polyphenylene vinylene, polystyrene, polycarbonate, or polyvinyl carbazole. A film comprising the phthalocyanine nanowire according to any one of claims 1 to 5. The film according to claim 14, further comprising a film-forming material. The film according to claim 15, wherein the film-forming material is polymethyl methacrylate, polythiophene, polyphenylene vinylene, polystyrene, polycarbonate, or polyvinyl carbazole. An electronic device comprising the film according to claim 14. In the manufacturing method of the phthalocyanine nanowire in any one of Claims 1-5,
(1) Step (a) of obtaining a composite by dissolving phthalocyanine and a phthalocyanine derivative in an acid, and then precipitating them in a poor solvent.
(2) Step (b) of micronizing the complex to obtain a micronized complex
(3) Step (c) of obtaining a dispersion by dispersing the finely divided composite in an organic solvent,
(4) Step (d) of forming the dispersion into a nanowire
A method for producing phthalocyanine nanowires, comprising: The method for producing a phthalocyanine nanowire according to claim 18, 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 18 or 19, wherein the organic solvent in the step (c) is an amide organic solvent or an aromatic organic solvent. The method for producing a phthalocyanine nanowire according to claim 20, wherein the amide organic solvent is N-methylpyrrolidone, dimethylformamide, diethylformamide, or N, N-dimethylacetamide. The method for producing a phthalocyanine nanowire according to claim 20, wherein the aromatic organic solvent is toluene, xylene, ethylbenzene, chlorobenzene, or dichlorobenzene.

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