JP5490386B2 - Phthalocyanine precursor and method for producing the same, method for producing phthalocyanine, and method for producing phthalocyanine film - Google Patents

Description

  The present invention relates to a novel phthalocyanine precursor and a method for producing the same, a method for producing phthalocyanine derived from the phthalocyanine precursor, and a method for producing a phthalocyanine film.

A compound having a phthalocyanine skeleton (hereinafter referred to as “phthalocyanine” as appropriate) exhibits strong absorption characteristic in the visible region, and has been used as a pigment for long time as a pigment for coating, color filters and the like.
In addition, as described in Patent Document 1, phthalocyanine is also known to exhibit good semiconductor characteristics by forming a film, such as an organic transistor such as an electroluminescence element or a field effect transistor, an organic solar cell, Applications to photoelectric conversion elements such as optical sensors and organic electronic elements such as sensors are also being studied.

  Phthalocyanine is a highly crystalline organic dye that is hardly soluble in ordinary solvents. As a method for producing phthalocyanine, for example, a method for obtaining phthalocyanine from a solvent-soluble precursor as disclosed in Non-Patent Document 1 and Non-Patent Document 2 is disclosed.

As a method for producing phthalocyanine, Patent Document 2 discloses a method for producing phthalocyanine by heating a phthalocyanine precursor. In Patent Document 2, a phthalocyanine precursor is produced by performing tetramer cyclization of a dicyano compound represented by the following formula (A).

JP 2003-304014 A JP 2003-327588 A Nature 388, 131 (1999) The Journal of the Imaging Society of Japan, 44, 347 (2005)

  When phthalocyanine is formed into a uniform film for use as a semiconductor, for example (ie, film formation), phthalocyanine is hardly soluble in ordinary solvents. It was. However, the vapor deposition method has a problem that the manufacturing cost is high and it is difficult to form a film with a large area.

  On the other hand, a method of coating a film by introducing a sterically bulky substituent such as a t-butyl group into phthalocyanine to weaken the intermolecular interaction and improving the solubility has been developed. However, such a compound has low crystallinity, and there is a problem that the durability of the dye is lowered and the semiconductor characteristics are lowered.

  Therefore, a phthalocyanine precursor that is soluble in a solvent is dissolved in an appropriate solvent to prepare a phthalocyanine precursor solution, and the phthalocyanine precursor solution is uniformly applied to form a film. A method of forming a film of phthalocyanine easily at low cost by converting it to phthalocyanine by a method such as heating has been proposed (Japanese Patent Laid-Open No. 2003-327588).

However, as a result of investigations by the present inventors, in the dicyano compound described in Patent Document 2, when the dicyano compound undergoes tetramer cyclization, the leaving group moiety in the molecule (specifically, mainly the above formula ( A) the upper bridge and the acetal group part in A) are easily thermally decomposed, and when the dicyano compound undergoes tetramer cyclization, a phthalocyanine pigment is produced, resulting in a phthalocyanine precursor. Has proved difficult to manufacture.
Such an inefficient method for synthesizing a phthalocyanine precursor has a problem in that the manufacturing cost increases.

  The present invention has been made in view of the above problems, and a novel phthalocyanine precursor that is less susceptible to thermal decomposition than the prior art and a method for producing the same, a method for producing phthalocyanine derived from the phthalocyanine precursor, and a phthalocyanine film It aims at providing the manufacturing method of.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have made a novel phthalocyanine precursor that is less thermally decomposed than before by making the above-mentioned bicyclo compound that is easily thermally decomposed to have high thermal stability. And the production method thereof, the production method of phthalocyanine derived from the phthalocyanine precursor, and the production method of the phthalocyanine film were found, and the present invention was completed.

（上記式中、Ｒ^ｍｎ（ｍ、ｎは１〜４の整数を表わす。）は水素原子又は１価の置換基を表わす。Ｍは２価の金属又は金属を含む２価の原子団を表わす。Ｑ^ｍを含むビシクロ部分の構造は、以下式（２）に表わすｓｙｎ体構造である。）

（上記式中、Ｐｏｒは式（１ａ）又は式（１ｂ）のポルフィリン環を表わしており、実線と破線はπ共役した一重結合または二重結合を表わす。Ｒ^ｍ１、Ｒ^ｍ２、Ｒ^ｍ３、及びＲ^ｍ４（ｍは１〜４の整数を表わす。）は、上記式（１ａ）又は式（１ｂ）に示される水素原子又は１価の置換基を表わす。Ｒ^ｍａ及びＲ^ｍｂは、水素原子又は１価の置換基を表わす。） That is, the gist of the present invention resides in a phthalocyanine precursor (hereinafter sometimes referred to as “the phthalocyanine precursor of the present invention”), which is represented by the following formula (1a) or formula (1b) ( Claim 1).

(In the above formula, R ^mn (m, n represents an integer of 1 to 4) represents a hydrogen atom or a monovalent substituent. M represents a divalent metal or a divalent atomic group containing a metal. (The structure of the bicyclo moiety containing Q ^m is a syn-body structure represented by the following formula (2).)

(In the above formula, Por represents the porphyrin ring of formula (1a) or formula (1b), and the solid and broken lines represent π-conjugated single bonds or double bonds. R ^m1 , R ^m2 , R ^m3 , and R ^m4 (m represents an integer of 1 to 4) represents a hydrogen atom or a monovalent substituent represented by the above formula (1a) or (1b), wherein R ^ma and R ^mb are a hydrogen atom or Represents a monovalent substituent.)

（上記式中、Ｒ^ｍｎ（ｍ、ｎは１〜４の整数を表わす。）は水素原子又は１価の置換基を表わす。Ｍは２価の金属又は金属を含む２価の原子団を表わす。Ｑ^ｍは２価の脱離基を表わす。） Another subject of the present invention is characterized by using di Shianobishikuro compound as a starting compound, a process for the preparation of the phthalocyanine precursor represented by the following formula (1c) or formula (1d), the dicyano bicyclo compound In the method for producing a phthalocyanine precursor, the ratio of the syn isomer to the total of the syn isomer and the anti isomer is greater than 0.8 (claim 2).

(In the above formula, R ^mn (m, n represents an integer of 1 to 4) represents a hydrogen atom or a monovalent substituent. M represents a divalent metal or a divalent atomic group containing a metal. Q ^m represents a divalent leaving group.)

（上記式中、Ｐｏｒは式（１ｃ）又は式（１ｄ）のポルフィリン環を表わしており、実線と破線はπ共役した一重結合または二重結合を表わす。Ｒ^ｍｎ（ｍ、ｎは１〜４の整数を表わす。）は、上記式（１ａ）又は式（１ｂ）に示される水素原子又は１価の置換基を表わす。Ｒ^ｍａ及びＲ^ｍｂは、水素原子又は１価の置換基を表わす。） At this time, it is preferable that the ratio of the syn isomer to the sum of the syn isomer and the anti isomer is 1 (claim 3).
Further, the formula (1c) or formula structure of bicyclo part of the phthalocyanine precursor represented by (1d) is preferably a syn body represented by the following formula (2) (claim 4)

(In the above formula, Por represents the porphyrin ring of formula (1c) or formula (1d), and the solid and broken lines represent π-conjugated single bonds or double bonds. R ^mn (m and n are 1 to 4) Represents a hydrogen atom or a monovalent substituent represented by the above formula (1a) or (1b), and R ^ma and R ^mb represent a hydrogen atom or a monovalent substituent. )

Another aspect of the present invention is a method for producing phthalocyanine (hereinafter referred to as phthalocyanine), characterized in that phthalocyanine is derived from the phthalocyanine precursor of the present invention or the phthalocyanine precursor produced by the method of producing the phthalocyanine precursor of the present invention. sometimes referred to as "production method of the phthalocyanine of the present invention".) to lie (claim 5).

Another gist of the present invention is characterized in that the phthalocyanine precursor of the present invention or the phthalocyanine precursor produced by the method of producing the phthalocyanine precursor of the present invention is applied to a substrate and converted into a phthalocyanine film, It exists in the manufacturing method of a phthalocyanine film | membrane (Hereafter, it may be called "the manufacturing method of the phthalocyanine film | membrane of this invention.") (Claim 6 ).

At this time, the phthalocyanine layer is preferably a electronic device (claim 7).

Further, the electronic device at this time is preferably a field effect transistor (claim 8).

Moreover, it is preferable that the said electronic device is a solar cell (Claim 9 ).

  ADVANTAGE OF THE INVENTION According to this invention, the novel phthalocyanine precursor which is hard to thermally decompose than before, its manufacturing method, the manufacturing method of the phthalocyanine induced | guided | derived from this phthalocyanine precursor, and the manufacturing method of a phthalocyanine film | membrane can be provided.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be arbitrarily modified and implemented without departing from the scope of the invention.

In this specification, “semiconductor” is defined by the magnitude of carrier mobility in a solid state. The carrier mobility is an index of how fast (or much) the charge can be moved. Specifically, the “semiconductor” in this specification has a carrier mobility at room temperature of usually 10 ⁻⁷ cm ² / V · s or more, preferably 10 ⁻⁶ cm ² / V · s or more, more preferably It represents 10 ⁻⁵ cm ² / V · s or more. The carrier mobility can be measured by, for example, IV characteristics of a field effect transistor, time-of-flight method, or the like.

（上記式中、Ｒ^ｍｎ（ｍ、ｎは１〜４の整数を表わす。）は水素原子又は１価の置換基を表わす。Ｍは２価の金属又は金属を含む２価の原子団を表わす。Ｑ^ｍを含むビシクロ部分の構造については後述する。） [1. Phthalocyanine precursor]
The phthalocyanine precursor of the present invention is a compound having a structure represented by the following formula (1a) or formula (1b).

(In the above formula, R ^mn (m, n represents an integer of 1 to 4) represents a hydrogen atom or a monovalent substituent. M represents a divalent metal or a divalent atomic group containing a metal. (The structure of the bicyclo moiety containing Q ^m will be described later.)

  The phthalocyanine precursor of the present invention has [2. It is preferable to synthesize | combine by the method similar to the manufacturing method of the phthalocyanine precursor of this invention mentioned later by the manufacturing method of a phthalocyanine precursor].

(About ^Rmn )
In the above formulas (1a) and (1b), R ^mn (m, n represents an integer of 1 to 4. That is, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ ) is a hydrogen atom or a monovalent substituent. Examples of monovalent substitution include halogen atoms such as fluorine, chlorine and bromine, and monovalent organic groups.

  The organic group may be linear or branched. Moreover, it may be a chain and may have a ring. Furthermore, the organic group may have a saturated bond and a double bond and / or a triple bond, but preferably has only a saturated bond.

Specific examples of the organic group include an alkyl group, a hydroxyl group, and an alkoxy group, and among them, an alkyl group is preferable.
Among the alkyl groups, an aliphatic alkyl group and an aromatic alkyl group can be mentioned, and among them, an aliphatic alkyl group is preferable. In addition, an organic group may be used individually by 1 type, and may be used 2 or more types by arbitrary ratios and combinations.
Specific examples of the aliphatic alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.

  The organic group may be substituted with a substituent. Specific examples of the substituent that can be substituted include the same substituents that can be substituted for the above-described leaving group. However, when the organic group is substituted with a substituent, it is preferable that the molecular weight and carbon number of the whole organic group including the substituent satisfy the ranges of the molecular weight and carbon number of the organic group. In addition, as for a substituent, 1 type may be substituted independently and 2 or more types may be substituted by arbitrary ratios and combinations. In addition, these substituents may be further substituted in multiple by one or more substituents. Examples of the substituent that can be substituted include the same substituents that can be substituted on the organic group.

(About M)
M in the above formula (1b) is a central metal, and M represents a divalent metal or a divalent atomic group containing a metal.
Specific examples of the divalent metal include Cu, Zn, Mg, Ni, Co (II), Fe (II), and Pt. Of these, Cu and Zn are preferable. This is because good semiconductor characteristics are known.
Further, even if M is not a divalent metal, it is divalent as a whole by combining a larger divalent metal such as trivalent or tetravalent with an atom or an atomic group (that is, 2 containing a metal). Valence atom group).
Specific examples of the divalent atomic group containing a metal include AlX, TiX ₂ , Sn (IV) X ₂ , TiO, SiX ₂ , and Fe (III) X (where X is a fluorine atom, a chlorine atom, a bromine atom, etc. A halogen atom or a hydroxyl group).

（上記式中、Ｐｏｒは式（１ａ）又は式（１ｂ）のポルフィリン環を表わしており、実線と破線はπ共役した一重結合または二重結合を表わす。Ｒ^ｍ１、Ｒ^ｍ２、Ｒ^ｍ３、及びＲ^ｍ４（ｍは１〜４の整数を表わす。）は、上記式（１ａ）又は式（１ｂ）に示される水素原子又は１価の置換基を表わす。Ｒ^ｍａ及びＲ^ｍｂは、水素原子又は１価の置換基を表わす。） (Structure of the bicyclo portion including a ^{Q m)}
Structure of bicyclo portion including a Q ^m are those having the following structure formula (2).

(In the above formula, Por represents the porphyrin ring of formula (1a) or formula (1b), and the solid and broken lines represent π-conjugated single bonds or double bonds. R ^m1 , R ^m2 , R ^m3 , and R ^m4 (m represents an integer of 1 to 4) represents a hydrogen atom or a monovalent substituent represented by the above formula (1a) or (1b), wherein R ^ma and R ^mb are a hydrogen atom or Represents a monovalent substituent.)

(About R ^m1 , R ^m2 , R ^m3 , and R ^m4 )
R ^m1 , R ^m2 , R ^m3 , and R ^m4 in the formula (2) are combinations of R ¹¹ , R ¹² , R ¹³ , and R ^{14 in} the formula (1a) or the formula (1b), R ²¹ , Represents any combination of R ²² , R ²³ , and R ²⁴ combinations, R ³¹ , R ³² , R ³³ , and R ³⁴ combinations, R ⁴¹ , R ⁴² , R ⁴³ , and R ⁴⁴ combinations. .
That is, the structure of the bicyclo moiety containing four Q ^m in the above formula (1a) or the above formula (1b) has the structure of the above formula (2).

R ^m1 , R ^m2 , R ^m3 , and R ^m4 represent the same groups as the specific examples of R ^mn described in the above formulas (1a) and (1b). The preferred group is the same as R ^mn . R ^m1 , R ^m2 , R ^m3 , and R ^m4 may be the same group, or may be another group in any combination and ratio.

(About R ^ma and R ^mb )
R ^ma and R ^mb represent the same groups as R ^mn described in the above formulas (1a) and (1b). The kind of the preferable group is the same as that of ^Rmn . R ^ma and R ^mb may be the same group or different groups.

However, [3. As described later in the production process on the phthalocyanine, Q ^m in the formula (1a) and the formula (1b) is a leaving group, the phthalocyanine precursor will phthalocyanine in that it is eliminated. Accordingly, under the environment of synthesizing the phthalocyanine precursor not desorbed, is leaving group Q ^m as desorbed in certain environments the other (e.g., higher temperatures than the synthesis of the phthalocyanine precursor) Preferably, R ^ma and R ^mb are selected such that such leaving group Q ^m is obtained.

(For stereoisomers of bicyclo portion including a Q ^m)
Bicyclo moiety containing a leaving group ^{Q m} is two stereoisomers of the syn body and anti body is present. In the environment for synthesizing the phthalocyanine precursor of the present invention, the anti-form tends to be easily broken, and the syn-form tends to be hard to break, so the syn-form is preferred. About this, [2. The method for producing a phthalocyanine precursor] will be described in detail.

（上記式中、Ｒ^ｍｎ（ｍ、ｎは１〜４の整数を表わす。）は水素原子又は１価の置換基を表わす。Ｍは２価の金属又は金属を含む２価の原子団を表わす。Ｑ^ｍは２価の脱離基を表わす。）

（上記式中、Ｒ^ｍｎ（ｍ、ｎは１〜４の整数を表わす。）は水素原子又は１価の置換基を表わす。Ｑ^ｍは２価の脱離基を表わす。） [2. Method for producing phthalocyanine precursor]
The method for producing a phthalocyanine precursor according to the present invention uses a thermally stable dicyanobicyclo compound, a phthalocyanine precursor represented by the following formula (1c) or the following formula (1d) (collectively referring to these phthalocyanine precursors). , “Sometimes referred to as a phthalocyanine precursor according to the present invention”).

(In the above formula, R ^mn (m, n represents an integer of 1 to 4) represents a hydrogen atom or a monovalent substituent. M represents a divalent metal or a divalent atomic group containing a metal. Q ^m represents a divalent leaving group.)

(In the above formula, R ^mn (m, n represents an integer of 1 to 4) represents a hydrogen atom or a monovalent substituent. Q ^m represents a divalent leaving group.)

The raw material compound for the above reaction is an example of a thermally stable dicyanobicyclo compound. Here, the thermally stable, the starting compound in the above reaction is at induced phthalocyanine precursor according to the present invention, elimination of Q ^m refers to 10% or less.

(About Q ^m )
Q ^m in (1c) and (1d) in the above formula is a leaving group, [3. In the method for producing phthalocyanine of the present invention, which will be described later in [Method for producing phthalocyanine], the type is not limited as long as it can be eliminated. However, the phthalocyanine precursor according to the present invention ((1c), (1d) ) in an environment in the preparation of, preferably one to Q ^m is difficult desorbed is more preferable that not eliminated.

The raw material compound leaving group Q ^m has a hard structure desorbed by thermal analysis at a heating rate of 10 ° C. / min, starting material compounds decomposition starting temperature of 170 ° C. or higher.
Examples of the dicyano compound, which is a raw material compound having a structure that does not desorb during the condensation reaction, include those having the following structure.

（上記式中、実線と破線はπ共役した一重結合または二重結合を表わす。Ｒ^ｍ１、Ｒ^ｍ２、Ｒ^ｍ３、及びＲ^ｍ４（ｍは１〜４の整数を表わす。）は、上記式（１ｃ）又は式（１ｄ）に示される水素原子又は１価の置換基を表わす。Ｒ^ｍａ及びＲ^ｍｂは、水素原子又は１価の置換基を表わす。） If this raw material compound becomes phthalocyanine precursor according to the present invention, the four, including structural bicyclo structure containing a leaving group Q ^m, such as below. That is, the structure of the bicyclo portion including the leaving group Q ^m of the phthalocyanine precursor according to the present invention, the following structures are preferred.

(In the above formula, a solid line and a broken line represent a π-conjugated single bond or double bond. R ^m1 , R ^m2 , R ^m3 , and R ^m4 (m represents an integer of 1 to 4) 1c) represents a hydrogen atom or a monovalent substituent represented by formula (1d), and R ^ma and R ^mb represent a hydrogen atom or a monovalent substituent.

Phthalocyanine precursors of the present invention (1a) and (1b), the structure of the bicyclo portion including the leaving group Q ^m is one when having the above structure. That is, when the structure of the bicyclo portion including the leaving group Q ^m in the formula (1c) has the above structure, the phthalocyanine precursor of the present invention (1a), and the leaving group Q ^m in the formula (1d) When the structure of the bicyclo part to contain has said structure, it becomes the phthalocyanine (1b) of this invention.

The molecular weight of the leaving group ^{Q m} is usually 18 g / mol or more, and generally 200 g / mol or less, preferably 150 g / mol or less, more preferably 100 g / mol or less. When the molecular weight is too large, it tends to be difficult to remove the leaving group out of the system.

(Method for producing raw material compound)
A method for producing a thermally stable dicyanobicyclo compound, which is a raw material compound, will be described. Here, R ^mn = H and R ^ma = methyl group will be described, but in the case of other groups, corresponding raw material compounds may be used.

First, a bicyclo compound is synthesized by the following Diels-Alder reaction. For this reaction, for example, a method described in JP-A-2006-131574 can be used.

  Two types of isomers (anti isomer and syn isomer) are produced. Here, the syn body and the anti body are separated. Examples of the separation method include a separation and purification method using a column chromatography method, a fractional recrystallization method, and the like, and a column chromatography method is preferable. The following phthalocyanine precursor is synthesized using only the syn isomer thus obtained.

(Method for producing phthalocyanine precursor)
Hereafter, the specific example of the manufacturing method of the phthalocyanine precursor based on this invention which used said raw material compound (syn body) as a raw material is demonstrated.

Method for synthesizing phthalocyanine precursor (1d) in which central metal M is magnesium When the central metal M of the phthalocyanine precursor according to the present invention represented by the above formula (1d) is magnesium, that is, in the following formula A case where 'becomes Mg will be described.

  As shown in the above formula, a raw material compound (syn body) and a catalyst containing magnesium such as dibutoxymagnesium are heated in a solvent such as butanol, whereby a phthalocyanine precursor compound (1d) whose central metal is Mg. ) Is obtained.

  At this time, the catalyst may be any catalyst containing magnesium, for example, a catalyst containing dibutoxymagnesium is preferable.

  Although there is no restriction | limiting in the kind of solvent, For example, a butanol is preferable.

  The heating temperature is usually 80 ° C. or higher, preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and usually 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 180 ° C. or lower.

  The reaction time is usually 3 hours or longer, preferably 6 hours or longer, more preferably 12 hours or longer, and usually 72 hours or shorter, preferably 48 hours or shorter, more preferably 36 hours or shorter.

-Method for synthesizing phthalocyanine precursor (1d) in which central metal M is other than magnesium It is also possible to introduce another central metal instead of Mg as the central metal of phthalocyanine precursor (1d) according to the present invention. In this case, the central metal Mg is desorbed from the phthalocyanine precursor (1d) having Mg in the central metal obtained above, and a metal-free phthalocyanine precursor (1c) having no central metal is synthesized, and another center is obtained. Examples thereof include a method of introducing a metal, or a method of previously synthesizing a metal-free phthalocyanine precursor (1c) having no central metal and introducing the central metal therein. Hereinafter, it demonstrates in this order.

First, a method for desorbing Mg as a central metal will be described.
A metal-free phthalocyanine precursor (1c) can be obtained by reacting the phthalocyanine precursor (1d) having Mg with the central metal obtained above with an acid such as trifluoroacetic acid.

  At this time, although there is no restriction | limiting in the kind of acid, For example, a trifluoroacetic acid is preferable.

  In this case, the reaction temperature in the case of reacting with an acid is usually 0 ° C. or higher, preferably 10 ° C. or higher, more preferably 20 ° C. or higher, and usually 150 ° C. or lower, preferably 120 ° C. or lower, more preferably 100 ° C. It is as follows.

  The amount of the acid used is usually 1 mol or more, preferably 2 mol or more, and usually 100 mol or less, preferably 50 mol or less, more preferably 30 mol or less.

  The reaction time is usually 1 hour or longer, preferably 2 hours or longer, and usually 48 hours or shorter, preferably 24 hours or shorter. Furthermore, as a solvent used for the reaction, a chlorinated solvent is preferable, and chloroform is particularly preferable.

Next, a method for directly synthesizing the metal-free phthalocyanine precursor (1c) will be described.
In order to directly synthesize the metal-free phthalocyanine precursor (1c), instead of using a magnesium-containing catalyst such as dibutoxymagnesium in the step of obtaining the phthalocyanine precursor compound (1d) in which the central metal is Mg, By reacting in the same manner except that a catalyst such as lithium (Li) alkoxide is used, the raw material compound can be tetramerized.

  At this time, as the catalyst, for example, lithium (Li) alkoxide is preferable. It is also possible to synthesize using lithium alkoxide as a base.

Next, a method for introducing a metal other than Mg into the metal-free phthalocyanine precursor (1c) will be described. Examples of the metal to be introduced include copper and nickel.
By reacting the metal-free phthalocyanine precursor (1c) obtained by the above-described method with the metal salt of the metal to be introduced, the phthalocyanine precursor (1d) into which the central metal is introduced can be obtained.

At this time, examples of the metal salt include copper acetate and nickel chloride.
The amount of the metal salt used is usually 1 times mol or more, preferably 1.5 times mol or more, and usually 20 times mol or less, preferably 10 times mol or less, more preferably 5 times mol or less with respect to the raw material compound. It is.

  The solvent is not particularly limited as long as it can dissolve both the metal-free phthalocyanine precursor (1c) and the phthalocyanine precursor (1d) having a central metal, and a polar solvent is preferable, for example, dimethylformamide.

  The reaction temperature is usually 20 ° C. or higher, preferably 30 ° C. or higher, and usually 150 ° C. or lower, preferably 100 ° C. or lower, more preferably 80 ° C. or lower.

  The reaction time is usually 3 hours or longer, preferably 5 hours or longer, more preferably 10 hours or longer, and usually 72 hours or shorter, preferably 48 hours or shorter, more preferably 36 hours or shorter.

-Method for synthesizing metal-free (no central metal) phthalocyanine precursor (1c) Among the phthalocyanine precursors according to the present invention, the metal-free phthalocyanine precursor (1c) is a phthalocyanine precursor whose central metal M is magnesium. After synthesizing (1d), any of a method of removing the central metal and a method of synthesizing directly by excluding the element as the central metal can be used for tetramerization of the raw material compound. The specific method is as described above.

[3. Method for producing phthalocyanine]
The phthalocyanine production method of the present invention is produced by the phthalocyanine precursor of the present invention (that is, the phthalocyanine precursor represented by the above formula (1a) or (1b)) or the phthalocyanine precursor production method of the present invention. Further, phthalocyanine (hereinafter sometimes referred to as “phthalocyanine according to the present invention”) is derived from a phthalocyanine precursor (that is, a phthalocyanine precursor represented by the above formula (1c) or (1d)).

  Hereinafter, although it demonstrates using the phthalocyanine precursor (1a) of this invention, another phthalocyanine precursor ((1b), (1c), and (1d)) can be performed similarly.

（上記式中、Ｒ^ｍｎ（ｍ、ｎは１〜４の整数を表わす。）は水素原子又は１価の置換基を表わす。Ｑ^ｍは脱離基である。） The following formula represents a reaction for deriving phthalocyanine represented by the following formula (3) from the phthalocyanine precursor (1a) of the present invention.

(In the above formula, R ^mn (m, n represents an integer of 1 to 4) represents a hydrogen atom or a monovalent substituent. Q ^m is a leaving group.)

  In the above reaction, the phthalocyanine (3) can be obtained by heating the phthalocyanine precursor (1a) of the present invention. Here, various conditions such as heating means, heating temperature, and heating time can be arbitrarily determined as long as the phthalocyanine according to the present invention can be induced.

(Heating means)
The heating means is optional as long as the phthalocyanine according to the present invention is obtained. Specific examples of the heating means include: hot plate; oven; heat roller; light such as laser light and infrared light; microwave; contact with one or more kinds selected from heated gas, liquid and solid; Can be mentioned. A heating means may be used individually by 1 type, and may be used in combination of 2 or more types. When two or more methods are used, the order, the ratio used for heating, and the like are arbitrary.

(Heating conditions)
The heating temperature is usually 100 ° C or higher, preferably 120 ° C or higher, more preferably 140 ° C or higher, and usually 400 ° C or lower, preferably 350 ° C or lower, more preferably 300 ° C or lower. If the reaction temperature is too low, it may take too long to obtain the phthalocyanine according to the present invention. Moreover, when too high, the various materials used in the production of the phthalocyanine according to the present invention may be affected by heat.

  The heating temperature may be constant as long as the phthalocyanine according to the present invention is obtained, or may be heated a plurality of times at different temperatures. Moreover, after heating, it may be cooled and further heated at a desired temperature.

  The heating time depends on the heating temperature, the heating device, etc., but cannot be generally specified, but is usually 1 nanosecond or more and usually 1 day or less.

  More specifically, for example, when heating with laser light, it is usually 1 nanosecond or more, preferably 10 nanoseconds or more, more preferably 100 nanoseconds or more, and usually 1 second or less, preferably 0.5 seconds or less. More preferably, it is 0.1 second or less.

  In addition, for example, when a hot plate, oven, or the like is used as a heating means, it is usually 0.1 seconds or longer, preferably 10 seconds or longer, more preferably 30 seconds or longer, and usually 10 hours or shorter, preferably 3 hours or shorter, more Preferably it is 1 hour or less.

  Further, for example, when the phthalocyanine precursor according to the present invention is heated by contacting a heated gas, liquid, or solid, it is usually 1 millisecond or more, preferably 10 milliseconds or more, more preferably 100 milliseconds or more, It is usually 1 day or less, preferably 3 hours or less, more preferably 1 hour or less.

  When the heating time is too short, when the phthalocyanine precursor according to the present invention is used as a film, the manufactured phthalocyanine film according to the present invention may not have good crystallinity. Moreover, when too long, productivity of a film | membrane may fall.

  From the viewpoint of productivity of the phthalocyanine according to the present invention, it is preferable that the heating time is short, but the reaction is sufficiently advanced, the semiconductor characteristics of the phthalocyanine according to the present invention, crystal growth for the development of color tone, etc. are desired. When it is assumed that the heating time is, the heating time is usually 1 second or longer, preferably 10 seconds or longer, more preferably 30 seconds or longer, and usually 3 hours or shorter, preferably 2 hours or shorter, more preferably 1 hour or shorter. It is. When the heating time is too short, crystallization does not proceed sufficiently, and there is a possibility that the characteristics as a pigment or a semiconductor are not sufficiently exhibited. Moreover, when too long, productivity may deteriorate or degradation of the other material to combine may be caused.

(Atmosphere during heating)
The atmosphere during heating is arbitrary as long as the phthalocyanine according to the present invention is obtained. However, since oxygen, water, or the like may become an obstacle in producing the phthalocyanine according to the present invention, an atmosphere of an inert gas such as nitrogen is preferable. An inert gas may be used individually by 1 type and may be used 2 or more types by arbitrary ratios and combinations.

  Further, from the viewpoint of improving the properties of the phthalocyanine according to the present invention, it is preferable that the formed phthalocyanine crystal grows. Specifically, a crystal with few amorphous parts and few defects is preferable. As a method for growing phthalocyanine crystals according to the present invention, for example, once formed crystals are further subjected to heat treatment at an appropriate temperature and time, contacted with a solvent, or exposed to solvent vapor to be subjected to solvent treatment. Things can be mentioned.

Furthermore, it is preferable to heat the phthalocyanine precursor while monitoring the degree of conversion to phthalocyanine. By this operation, phthalocyanine having desired physical properties can be obtained by determining optimum conversion conditions. As the method of monitoring, any known method can be used. For example, observation of changes in appearance with a microscope, observation of changes in color (that is, absorption spectrum), infrared spectroscopy, ultraviolet spectroscopy, Examples include measurement of vibrational spectra such as mass spectrum and Raman spectrum, measurement of X-ray diffraction, measurement of ¹ H-NMR and ¹³ C-NMR, measurement of simultaneous thermogravimetric differential thermal analysis (TG-DTA), and the like.

(Other conditions)
When heating the phthalocyanine precursor according to the present invention, the state of the phthalocyanine precursor according to the present invention is not particularly limited as long as the phthalocyanine according to the present invention is obtained. The phthalocyanine precursor according to the present invention may be, for example, a liquid or a gel. Further, for example, a film-like phthalocyanine precursor obtained by applying the phthalocyanine precursor according to the present invention may be heated, or the phthalocyanine precursor may be directly heated. Especially, in the manufacturing method of the phthalocyanine of this invention, it is preferable to apply | coat the phthalocyanine precursor which concerns on this invention, to form into a film, and to heat the film-like phthalocyanine precursor which concerns on this invention.

  Moreover, in the manufacturing method of the phthalocyanine of this invention, as long as the phthalocyanine which concerns on this invention is obtained, arbitrary processes other than a heating can be performed. Specific examples of treatment include drying and washing. For example, after the phthalocyanine precursor according to the present invention is washed with a solvent such as water before heating, the phthalocyanine precursor is heated after drying, or the phthalocyanine precursor is heated and then washed with a solvent such as water. It can also be dried. Arbitrary processing may be performed only 1 type and may be performed combining 2 or more types arbitrarily.

(Mode of preferred steps in the method for producing phthalocyanine of the present invention)
In the method for producing phthalocyanine of the present invention, as long as the phthalocyanine precursor according to the present invention is heated to obtain the phthalocyanine according to the present invention, other steps, conditions and the like can be arbitrarily determined. As described above, as long as the phthalocyanine precursor according to the present invention is heated to obtain the phthalocyanine according to the present invention, other steps, conditions, and the like are arbitrary.

[4. Method for producing phthalocyanine film]
The method for producing a phthalocyanine film of the present invention is produced by the method for producing a phthalocyanine precursor of the present invention (that is, the phthalocyanine precursor represented by the above formula (1a) or (1b)) or the phthalocyanine precursor of the present invention. The prepared phthalocyanine precursor (that is, the phthalocyanine precursor represented by the above formula (1c) or (1d)) is applied to a substrate, and may be referred to as a phthalocyanine film (hereinafter referred to as “the phthalocyanine film according to the present invention”). .)).

  As a more specific example of the production method, a step of coating the phthalocyanine precursor according to the present invention to form a film, and heating the film to convert the phthalocyanine precursor according to the present invention into the phthalocyanine according to the present invention The manufacturing method which has a process to do is mentioned. Hereinafter, this method will be specifically described. However, the method for producing the phthalocyanine film of the present invention is not limited to the following contents.

<The process of apply | coating the phthalocyanine precursor which concerns on this invention, and forming a film>
In the step of applying the phthalocyanine precursor according to the present invention to form a film, the film forming method, conditions, and the like are arbitrary as long as the phthalocyanine precursor according to the present invention is applied to form a film.

(Film formation method)
As a film forming method, any method can be used as long as the phthalocyanine film according to the present invention is obtained. For example, as a film forming method, a solution in which the phthalocyanine precursor according to the present invention is dissolved in a solvent (hereinafter sometimes referred to as “phthalocyanine precursor solution”) may be applied on a substrate by an arbitrary application method. And a printing method in which a film of a phthalocyanine precursor is patterned on a substrate using an arbitrary printing method.
Among these, from the viewpoint that the phthalocyanine precursor of the present invention is usually soluble in a solvent, the film formation is preferably performed by a coating method and / or a printing method. In addition, the film-forming method may be used individually by 1 type, and may be used combining 2 or more types arbitrarily.

  Any known method can be used as the coating method. Specific examples of the application method include coating methods such as casting, spin coating, dip coating, blade coating, wire bar coating, and spray coating. As the coating method, one type may be used alone, or two or more types may be used in arbitrary combination.

  Examples of the printing method include inkjet lithography, screen printing, offset printing, relief printing, flexographic printing, gravure printing, and soft lithography techniques such as microcontact printing. One printing method may be used alone, or two or more printing methods may be used in any combination.

(solvent)
The solvent for dissolving the phthalocyanine precursor according to the present invention is arbitrary as long as the phthalocyanine film according to the present invention is obtained. For example, aliphatic hydrocarbons such as hexane, heptane, octane, isooctane, nonane and decane; aromatic hydrocarbons such as toluene, benzene, xylene and chlorobenzene; lower alcohols such as methanol, ethanol, propanol and butanol; acetone Ketones such as methyl ethyl ketone, cyclopentanone and cyclohexanone; esters such as ethyl acetate, butyl acetate and methyl lactate; nitrogen-containing organic solvents such as pyridine and quinoline; halogens such as chloroform, methylene chloride, dichloroethane, trichloroethane and trichloroethylene Hydrocarbons; ethers such as ethyl ether, tetrahydrofuran and dioxane; amides such as dimethylformamide and dimethylacetamide; These can be selected according to the purpose. A solvent may be used individually by 1 type and may be used 2 or more types by arbitrary ratios and combinations.

(Concentration in solution)
The concentration of the phthalocyanine precursor according to the present invention in the phthalocyanine precursor solution is arbitrary as long as the phthalocyanine film according to the present invention is obtained, but is usually 0.01% by weight or more, preferably 0.1% by weight or more. It is preferably 0.5% by weight or more, and usually 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less. If the concentration is too low, the coating film thickness may be reduced. If it is too high, a solute may precipitate or it may be difficult to produce a thin film.

(Amount of solution used)
Although the usage-amount of a phthalocyanine precursor solution is arbitrary as long as the phthalocyanine film | membrane concerning this invention is obtained, what is necessary is just to determine so that it may become a desired film thickness.

(Other ingredients)
The phthalocyanine precursor solution may contain components other than the above-mentioned solvent and the phthalocyanine precursor according to the present invention (hereinafter sometimes referred to as “other components”). Any other component can be used as long as the phthalocyanine according to the present invention is obtained. In addition, another component may contain 1 type independently, and may contain 2 or more types by arbitrary ratios and combinations.

  For example, when the phthalocyanine according to the present invention is used as a semiconductor, other components include semiconductor materials of the same kind and / or different types of semiconductor materials as the phthalocyanine according to the present invention; precursors of these semiconductor materials; electrons for controlling semiconductor characteristics Examples include dopants such as an acceptor and / or a donor; additives for controlling film-forming properties; antioxidants; and the like. In particular, when phthalocyanine is used as an organic electronic device such as a solar cell in which holes and electrons are involved in the reaction, a p-type semiconductor component and an n-type semiconductor component coexist in the phthalocyanine precursor solution. Can also be used.

  Examples of the p-type semiconductor component include conjugated molecules such as polythiophene linked with a thiophene ring, pentacene, phthalocyanine, benzoporphyrin, and precursors thereof.

  Examples of the semiconductor component exhibiting n-type include n-type semiconductors soluble in solvents such as PCBM ([6,6] -phenyl C61-butyric acid methyl ester), inorganic or organic semiconductor fine particles, and precursors of n-type semiconductors. Examples include the body.

Specific examples of the dopant include acids such as hydrochloric acid, sulfuric acid and sulfonic acid, Lewis acids such as PF ₆ , AsF ₅ , FeCl ₃ and SbF ₅ , halogens such as chlorine, bromine and iodine, ICl, ICl ₃ , IBr and IF _3. Alkali metal atoms such as lithium, potassium, sodium and cesium, and alkaline earths such as barium, calcium and magnesium.

  Examples of the additive for controlling the film forming property include a surfactant.

  Specific examples of the antioxidant include hindered phenol.

  For example, when the phthalocyanine according to the present invention is used as a pigment, a binder or the like can be used as the other component. By including the binder in the phthalocyanine precursor solution, the advantages such as the improvement of the mechanical strength of the film, the provision of environmental resistance such as water repellency, light resistance and weather resistance, and the improvement of the optical properties such as reflectance are recorded. It can be applied to the phthalocyanine film according to the invention.

  Specific examples of the binder include polymers usually used for paints, acrylic resins, epoxy resins, urethane resins, silicone resins, fluororesins, and the like.

(substrate)
Any substrate can be used. Specific examples of the substrate include glass substrates such as glass and sapphire, polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyimide, nylon, polystyrene, polyvinyl alcohol, ethylene vinyl alcohol copolymer, fluororesin film, vinyl chloride, and polyethylene. , Cellulose, polyvinylidene chloride, aramid, polyphenylene sulfide, polyurethane, polycarbonate, polyarylate, polynorbornene, epoxy resin, phenol resin, novolac resin, acrylic resin, siloxane resin, polynorbornene and other plastic substrates, paper, synthetic paper, aluminum And metals such as stainless steel and iron. A board | substrate may be used individually by 1 type and may use 2 or more types by arbitrary ratios and combinations.

The thickness of the substrate is also arbitrary as long as the strength as the substrate can be maintained. However, the thickness of the substrate is usually 5 μm or more, preferably 10 μm or more, more preferably 20 μm or more, and usually 1 cm or less, preferably 5 mm or less, more preferably 2 mm or less. When the thickness of the substrate is too thin, the strength as the substrate may not be maintained. Moreover, when the thickness of a board | substrate is too thick, the manufacturing cost of the phthalocyanine precursor which concerns on this invention may become high.
In the case where the phthalocyanine precursor according to the present invention is directly formed on another structure such as a window glass, a roof tile, or a car body, the substrate to be coated is used. In this case, the thickness of the substrate is not limited.

(Film thickness)
There is no limitation on the thickness of the film obtained by forming the phthalocyanine precursor solution, and it may be determined as appropriate according to the purpose of the film. For example, when the film after being converted into phthalocyanine according to the present invention is used for a horizontal field effect transistor (FET), various characteristics of the organic electronic element are usually not affected as long as the film thickness is a certain value or more. However, from the viewpoint that the leakage current may increase if the film thickness is too thick, the film thickness is usually 1 nm or more, preferably 10 nm or more, and usually 10 μm or less, preferably 500 nm or less.

  In addition, when the phthalocyanine film is used for a coating film using the optical characteristics of phthalocyanine, the film thickness is from the viewpoint that the color tone is sufficiently developed and / or the effect of protecting the surface to be painted by coating can be obtained. Is usually 0.1 μm or more, preferably 1 μm or more, and usually 1 mm or less.

  As the shape of the film, a film having a uniform film thickness is preferable. However, even if the film thickness is not constant, it is preferable that the film thickness falls within the above range in all parts of the film. For example, when the phthalocyanine precursor solution adheres to the film surface as droplets, it is preferable that the thickness of the attached portion be within the above range.

<Step of converting the phthalocyanine precursor according to the present invention to the phthalocyanine according to the present invention by heating the phthalocyanine film>
In this step, as long as the phthalocyanine precursor according to the present invention can be converted into the phthalocyanine according to the present invention by heating the film formed as described above, the heating method, conditions, and the like are arbitrary. However, [3. It is preferable to apply the heating method described in (Heating means) in [Method for producing phthalocyanine] also in this step.

  As described above, the method for producing a phthalocyanine film according to the present invention includes the steps of coating and forming the phthalocyanine precursor according to the present invention, and heating the film to the phthalocyanine precursor according to the present invention. And a step of converting to phthalocyanine according to the invention. In this case, each of these two steps may be performed only once, or may be performed twice or more. For example, after film formation, the film may be heated to convert the phthalocyanine precursor to phthalocyanine, and then the phthalocyanine precursor may be applied onto the film to form a film, and then heated again to convert to phthalocyanine. Moreover, you may carry out combining arbitrarily with the other process mentioned later.

(Other processes)
The method for producing a phthalocyanine film of the present invention includes a step of applying a phthalocyanine precursor according to the present invention to form a film, and heating the film to convert the phthalocyanine precursor according to the present invention into the phthalocyanine according to the present invention. However, as long as the phthalocyanine film according to the present invention is obtained, other steps may be included.

As other steps, for example, [3. Arbitrary treatments other than the heating method described in (Heating means) of [Production method of phthalocyanine].
Moreover, another process may be performed individually by 1 type, and may be performed combining 2 or more types arbitrarily. For example, after washing twice, it may be dried once.

[5. Applications of phthalocyanine film]
Since the phthalocyanine according to the present invention has strong light absorption in the visible region, it is suitably used for coating application as a pigment. Furthermore, the phthalocyanine according to the present invention preferably has semiconductor characteristics. That is, the phthalocyanine according to the present invention is preferably a semiconductor. Thereby, the phthalocyanine film | membrane which concerns on this invention can be used suitably as a material of semiconductor members, such as organic electronic elements, such as a field effect transistor, a solar cell, and an electroluminescent element.

However, in order to use the phthalocyanine according to the present invention as a semiconductor, the electrical characteristics of the film when the phthalocyanine according to the present invention is formed into a film are important. Specifically, the carrier mobility at room temperature in the film is usually 1 × 10 ⁻⁵ cm ² / Vs or higher, preferably 1 × 10 ⁻⁴ cm ² / Vs or higher, more preferably 1 × 10 ⁻³ cm ² / Vs. Vs or higher. When the carrier mobility is too small, the semiconductor characteristics are low, and the function may not be sufficiently exhibited.

  A semiconductor is capable of transporting charges in its material. By controlling the carrier density according to various conditions such as impurity doping, applied electric field, and light irradiation, the function as a rectifier, transistor function, and light Various functions such as a current generation function and an electromotive force generation function by light can be developed.

[6. Advantages obtained by the phthalocyanine precursor of the present invention]
Since phthalocyanine usually shows poor solubility in many solvents, for example, by using a phthalocyanine precursor that is soluble in the solvent, a purification method in a solution state such as column chromatography or recrystallization is used. Thus, a highly pure phthalocyanine can be produced, or a film of phthalocyanine precursor can be applied to form a film, and the film can be heated to produce a hardly soluble phthalocyanine film.

[7. Organic electronic device]
The phthalocyanine according to the present invention is preferably used as a semiconductor, and particularly preferably used as an organic electronic device. Hereinafter, the organic electronic device using the phthalocyanine according to the present invention may be referred to as “the organic electronic device of the present invention”.

  An organic electronic device has two or more electrodes. As the organic electronic device of the present invention, for example, an element that controls the current flowing between electrodes, the voltage generated, etc. by electricity, light, magnetism, chemical substances, etc .; light, electric field, magnetic field, etc. are controlled by applied voltage or current. Examples include an element for generating; an element for controlling current or voltage by applying a voltage or current; an element for controlling voltage or current by applying a magnetic field; an element for controlling a voltage or current by applying a chemical substance. Examples of these control methods include rectification, switching, amplification, and oscillation.

  Specific examples of the organic electronic element of the present invention include: a resistor; a rectifier such as a diode; a switching element such as a switching element transistor and a thyristor; an amplifying element such as a transistor; a memory element, a chemical sensor, or a combination of these elements. Examples include integrated devices.

  Moreover, the phthalocyanine according to the present invention usually has strong light absorption in the near ultraviolet to visible to near infrared region. By utilizing this, the phthalocyanine according to the present invention can also be used as an optical functional material. In this case, specific examples of the organic electronic device of the present invention include devices that function by causing charge separation by absorbed light.

  Examples of such an element include a solar cell that generates electromotive force by light, a photoelectric conversion element such as a photodiode that generates photocurrent, and a phototransistor. Here, the solar cell uses an internal electric field generated at a junction between a semiconductor and a metal or another semiconductor to cause charge separation by light and take it out to the outside. In addition, such an element can generate photo radicals by sensitizing a radical generator using an excited state generated by light absorption or generating radicals directly from the excited state. Can also be applied.

  Especially, it is preferable that the organic electronic element of this invention is a field effect transistor, a solar cell, or an electroluminescent element.

  As a manufacturing method of the organic electronic device of this invention, it has the process of manufacturing a phthalocyanine with the manufacturing method of said phthalocyanine of this invention. Therefore, as long as the phthalocyanine according to the present invention is produced by the above-described method for producing phthalocyanine of the present invention, other steps, methods, conditions and the like are arbitrary.

  Examples of other electronic elements include S.I. M.M. Those described in Sze, Physics of Semiconductor Devices, 2nd Edition (Wiley-Interscience 1981) and the like can be used.

  Among them, for example, when the organic electronic element of the present invention is a field effect transistor, Japanese Patent Application Laid-Open No. 2004-6750, and when it is a solar cell, Japanese Patent Application Laid-Open No. 2007-324587, and further, an electroluminescent element such as an organic EL In this case, a method described in JP 2004-327166 A can also be used.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to a following example, unless it deviates from the summary.

[Synthesis Example of Raw Material Compound A]
Hereinafter, the raw material compound A which can be used for the manufacturing method of the phthalocyanine precursor of this invention was manufactured. Hereinafter, the reaction steps will be described.

Hexane (300.0 ml) and 1.4-cyclohexadiene (21.5 ml, 0.22 mol) were placed in a three-necked reaction vessel (1 L) and cooled to −45 ° C. or lower. Hexane (100.0 ml) and Br ₂ (11.0 ml, 0.21 mol) were placed in the dropping funnel and slowly dropped into a three-necked reaction vessel cooled to −60 ° C. After returning to room temperature, suction filtration was performed, and the filtrate was concentrated under reduced pressure to obtain a target product (4.5-dibromocyclohexane) as white crystals.

When the obtained target product was analyzed, the following results were obtained.
Yield: 49.7g
Yield: 99%
Molecular formula: C ₆ H ₈ Br ₂ (239.9357)
¹ H-NMR (CDCl ₃ , 400 MHz): 5.66 (m, 2H), 4.52 (m, 2H), 3.14-3.26 (m, 2H), 2.55-2.67 (m, 2H).

In a reaction vessel (50 ml), 4.5-dibromocyclohexane (1.61 g, 6.71 mmol), NMO (N-methylmorpholine N-oxide: 0.906 g, 7.74 mmol), acetone (5.0 ml), pure water ( 10.0 ml) was added and stirred. The t-BuOH solution of OsO ₄ 4.0ml (OsO ₄ to about 20mg, 0.0787mmol) was added and stirred at room temperature for 1 day. After confirming the completion of the reaction, sodium dithionite (1 g, 5.74 mmol) suspended in water (5 ml) was added and stirred overnight at room temperature. Celite filtration was performed, and the filtrate was adjusted to pH 3 with 3M HCl, then concentrated under reduced pressure, and filtered again through celite. The filtrate was extracted with AcOEt (ethyl acetate), washed with water and saturated brine, dried over anhydrous sodium sulfate, and then dried under reduced pressure to give the desired product (trans-4) as white crystals. .5-dibromocyclohexane-1.2-diol) was obtained.

When the obtained target product was analyzed, the following results were obtained.
Yield: 1.59g
Yield: 98%
Molecular formula: C ₆ H ₁₀ Br ₂ O ₂ (2733.9504)
Shape: white powder
¹ H-NMR (CDCl ₃ , 400 MHz): 4.42 (m, 1H), 4.11 (m, 1H), 4.01 (m, 1H), 3.82 (m, 1H), 2.66 (m, 1H), 2.54 (m , 1H), 2.40 (m, 1H), 2.03 (m, 1H).

Raw materials (trans-4.5-dibromocyclohexane-1.2-diol: 21.8 g, 90.3 mmol) and TsOH.H ₂ O (1.07 g, 5.60 mmol) were placed in a reaction vessel (500 ml), and Ar substitution was performed. did. dry-CH ₂ Cl ₂ (300.0 ml) was added and stirred, followed by addition of 2.2-dimethylpropane (15.5 ml, 120 mmol), and the mixture was stirred at room temperature for 6 hours. The reaction solution was passed through a Buchner funnel packed with alumina, and the filtrate was concentrated under reduced pressure to obtain the desired product (a).

When the obtained target product was analyzed, the following results were obtained.
Yield: 25.8g
Yield: 91%
Chemical formula: C ₉ H ₁₄ Br ₂ O ₂ (314.0143)
Shape: colorless oil
¹ H-NMR (CDCl ₃ , 400 MHz): 4.41-4.46 (m, 1H), 4.29-4.32 (m, 1H), 4.16-4.23 (m, 2H), 2.73-2.79 (m, 2H), 2.34-2.42 (m, 1H), 2.20-2.27 (m, 1H), 1.54 (s, 3H), 1.34 (s, 3H).

A reaction vessel (1 L) was charged with the raw material ((a): 17.5 g, 55.8 mmol), and Ar was substituted with a reflux tube, and dry-toluene (300.0 ml) and dry-DBU (anhydrous-diazabicyclo [5. 4.0] undec-7-ene: 25.5 ml, 171 mmol) was added and heated to reflux for 6 hours. The completion of the reaction was confirmed by NMR, washed with saturated aqueous sodium hydrogen carbonate, and dried over anhydrous sodium sulfate to obtain the desired product (b).

A three-necked reaction vessel (50 ml) containing dicyanoacetylene (1.10 g, 14.5 mmol) was cooled in an ice bath, degassed CHCl ₃ (15.0 ml) was added and dissolved, and then the raw Et ₂ O solution (2.11 g, 13.8 mmol: where Et represents an ethyl group) was added slowly.
The mixture was stirred overnight at room temperature and concentrated under reduced pressure to obtain the desired product. Purification by alumina column chromatography (CHCl ₃ ) and recrystallization (CHCl ₃ / Hexane) were carried out to obtain the starting compound A.

When the obtained raw material compound A was analyzed, the following results were obtained.
Yield: 1.80 g
Yield: 54%

Further purification was performed by silica gel column chromatography (Hexane: AcOEt = 1: 2) to separate isomers.
When the separated isomers were analyzed by NMR, it was found from the integrated values that anti-isomers: syn-isomers were present at a ratio of 1: 4.

  Moreover, when each isomer (anti body, syn body) of the obtained raw material compound A was analyzed, the following results were obtained.

・ Anti Rf value = 0.8 (Hexane: AcOEt = 1: 2)
Shape: colorless crystal Melting point: 181-182 ° C
¹ H-NMR (CDCl ₃ , 400 MHz): 6.39 (m, 2H), 4.38 (m, 2H), 4.24 (m, 2H), 1.33 (s, 3H), 1.28 (s, 3H).
¹³ C-NMR (CDCl ₃ , 100 MHz): 131.17, 129.96, 114.85, 113.37, 77.31, 46.39, 25.61, 25.56.
IR (KBr) max / cm < ^-1 >: 2223 (CN).
Mass spectrometry (FAB) m / z (%): 229 (10) [M ⁺ ], 154 (100).
Elemental analysis Calcd: (+ 1 / 6H ₂ O): C, 67.52; H, 5.38; N, 12.11.
Found: C, 67.66; H, 5.07; N, 12.12.
Construction:

Syn field Rf value = 0.5 (Hexane: AcOEt = 1: 2)
Shape: colorless crystalline Melting point: 201-202 ° C
¹ H-NMR (CDCl ₃ , 400 MHz): 6.33 (m, 2H), 4.34 (m, 2H), 4.25 (m, 2H), 1.41 (s, 3H), 1.28 (s, 3H).
¹³ C-NMR (CDCl ₃ , 100 MHz): 131.13, 130.11, 114.41, 114.21, 77.44, 46.28, 25.97, 25.17.
IR (KBr) max / cm ^-1 : 2224 (CN).
Mass spectrometry (FAB) m / z (%): 229 (8) [M ⁺ ], 154 (100).
Elemental analysis Calcd: C, 68.41; H, 5.30; N, 12.27.
Found: C, 68.53; H, 5.23; N, 12.34.
Construction:

[Reference Example 1]
Thermal analysis of the syn and anti isomers of the raw material compound A was performed. As a result, it was observed that weight loss due to the reverse Diels-Alder reaction occurred from about 180 ° C. for the syn isomer and from about 160 ° C. for the anti isomer. The results for the syn isomer are shown in FIG. 1, and the results for the anti isomer are shown in FIG.

  Further, when the melting point was measured using a melting point meter, it was observed that the reverse Diels-Alder reaction occurred from around 181 ° C. for the syn isomer and around 161 ° C. for the anti isomer. This result is consistent with the result of thermal analysis.

[Example 1]
Of the raw material compound A produced in the synthesis example of the raw material compound A, the following phthalocyanine precursor A, which is one of the phthalocyanine precursors of the present invention, was produced using only the syn isomer.

  Lithium wire (26.07 mg, 3.76 mmol in a 5 ml reaction vessel; 33.29 mg, 4.80 mmol in a 10 ml reaction vessel) was placed in a two-necked reaction vessel (5 ml, 10 ml) equipped with a reflux tube, and replaced with Ar. did. 3.80 ml and 4.80 ml of dry-BuOH were added to each and heated to reflux until Li was dissolved.

After cooling to room temperature, raw material compound A (0.1864 g, 0.816 mmol for a 5 ml reaction vessel; 0.2308 g, 1.01 mmol for a 10 ml reaction vessel) was added and heated at 110 ° C. for 1 day.
Methanol: H ₂ O = 1: 1 solution (20 ml) was added, the two reaction solutions were combined and extracted with CHCl ₃ , washed with water, saturated brine, dried over anhydrous sodium sulfate, and reduced pressure The solvent was removed. Purification was performed by silica gel chromatography (CHCl ₃ ), followed by alumina column chromatography (CHCl ₃ ), and further purification was performed by GPC (gel permeation chromatography) to obtain phthalocyanine precursor A.

When the obtained phthalocyanine precursor A was analyzed, the following results were obtained.
Yield: 3.8mg
Yield: 2.0%
Molecular formula: C ₅₂ H ₅₀ N ₈ O ₈ (914.3752)
Shape: purple powder
¹ H-NMR (CDCl ₃ , 400 MHz): 7.02 (m, 8H), 5.97 (m, 8H), 5.05 (m, 8H), 0.89-1.26 (m, 16H), -0.76- -0.51 (m, 8H ), -3.09 (br, 2H).
¹³ C-NMR (CDCl ₃ , 100 MHz): 135.42, 112.80, 80.09, 80.03, 79.84, 76.60, 41.72, 41.65, 24.92, 24.89, 24.81.
Mass spectrometry (HRMS): calcd for 914.3752
: Found 915.3830 [M + H] ⁺

[Example 2]
From the phthalocyanine precursor A synthesized in Example 1, phthalocyanine was derived according to the following synthesis route.

As a result of thermal analysis of the phthalocyanine precursor A produced in Example 1, the reverse Diels-Alder reaction occurred from 180 ° C to around 250 ° C.
Therefore, phthalocyanine precursor A (0.65 mg) was placed in an Al disk and heated to 250 ° C. under a nitrogen atmosphere to obtain phthalocyanine.

When the obtained phthalocyanine was analyzed, the following results were obtained.
Yield: 0.36mg
Yield: 98.6%
Molecular formula: C ₃₂ H ₁₈ N ₈ (514.5389)
Melting point:> 300 ° C
Shape: Blue powder mass spectrometry (MALDI-TOF) m / z: 514 [M ⁺ ].

  FIG. 3 shows the results of mass analysis (MALDI-TOF) of phthalocyanine precursor A, and FIG. 4 shows the results of phthalocyanine mass analysis (MALDI-TOF). From the results of mass spectrometry (MALDI-TOF), it can be seen that the phthalocyanine precursor A is converted to phthalocyanine by heating.

  Further, FIG. 5 shows the result of the absorption spectrum measurement of the phthalocyanine precursor A, and FIG. 6 shows the result of the absorption spectrum measurement obtained by heat conversion. This absorption spectrum measurement result also shows that phthalocyanine is obtained.

[Example 3]
A phthalocyanine field effect transistor (FET) was produced from the phthalocyanine precursor A obtained in Example 1 by inducing phthalocyanine in the same manner as in Example 2, and the FET characteristics were measured.

  First, on an N-type silicon substrate (Sb-doped, resistivity 0.02 Ωcm or less, manufactured by Sumitomo Metal Industries, Ltd.) on which an oxide film having a thickness of 300 nm is formed, a length (L) of 10 μm and a width (W) are obtained by photolithography. Gold electrodes (source electrode, drain electrode) having a gap of 500 μm were formed. A part of the oxide film was removed and a voltage was applied to the silicon substrate (gate electrode).

  A 0.7% by weight chloroform precursor solution of the phthalocyanine precursor A obtained in Example 1 was prepared. The film formation of the phthalocyanine precursor A and the evaluation of electric characteristics were all performed in a nitrogen atmosphere.

  Next, the precursor solution was spin-coated at 1000 rpm on the substrate on which the electrode was formed to obtain a good film.

  This substrate was placed on a hot plate heated to 320 ° C. and heated for 20 minutes to produce a phthalocyanine FET.

  The characteristics of the FET thus obtained were measured using a semiconductor parameter analyzer 4155C manufactured by Agilent Technologies. When a voltage Vd was applied between the source electrode and the drain electrode and a voltage Vg was applied between the source electrode and the gate electrode, a current Id flowing through the semiconductor film (phthalocyanine film) was measured.

When the threshold voltage is Vt, the capacitance per unit area of the insulating film is Ci, the distance between the source electrode and the drain electrode is L, the width is W, and the mobility of the semiconductor film is μ, the operation is as follows. Can be expressed as:

The mobility μ can be obtained from the current-voltage characteristics of the element. Although the equation (1) or (2) is used to obtain the mobility μ, a method of obtaining from the slope of Id ^1/2 −Vg of the saturation current portion of the equation (2) was adopted. From the intercept of Id = 0 in this plot, the threshold voltage Vt, and the ratio of Id between Vg = 30V and −50V when Vd = −30V was applied was defined as the on / off ratio.

In the above phthalocyanine FET, the mobility was 6.0 × 10 ⁻² cm ² / Vs, and the _on / off ratio (I _on / I _off ) was 1.8 × 10 ⁴ .

（上記式中、Ｍｅはメチル基を表わす。） [Synthesis Example of Raw Material Compound B]
Hereinafter, the raw material compound B which can be used for the manufacturing method of a phthalocyanine precursor was manufactured. Hereinafter, the reaction steps will be described.

(In the above formula, Me represents a methyl group.)

  The reaction vessel (100 ml) was brought to −40 ° C. with acetonitrile and liquid nitrogen, and cooled with stirring with 28% aqueous ammonia (20 ml). Dimethyl acetylenedicarboxylate (1.25 ml, 10 mmol) was slowly added dropwise thereto, and after completion of the addition, the temperature was slowly returned to room temperature. After stirring at room temperature for 3 hours and filtering, the solid was washed with pure water to obtain the target product (Acetylene dicarboxamide).

When the obtained target product was analyzed, the following results were obtained.
Yield: 0.93g
Yield: 83% (crude)
Molecular formula: C ₄ H ₄ N ₂ O ₄ (112.0273)
Shape: White solid mass spectrometry (EI) m / z (%): 113 (9) [M ⁺ +1], 112 (100) [M ⁺ ].

  A rotor was placed in a three-necked reaction vessel and a dropping funnel was attached. In order to trap the target product (Dicyanoacetylene), another three-necked reaction vessel cooled to −78 ° C. was connected, and the target product was used as it is for the next reaction, and a rotor was added.

The instrument was completely replaced with Ar, and P ₂ O ₅ (7.63 g, 0.054 mmol) was dissolved in Sulfolane (70 ml) in a three-necked reaction vessel, and then the raw material (Acetylene dicarbonate): 2.25 g, 20.0 mmol ) Was suspended in Sulfolane (25 ml) from a dropping funnel at 12 torr (16 hPa) at 110 ° C. for 30 minutes or more and added dropwise with vigorous stirring.

  After the dripping was completed, the temperature was raised to 120 ° C., and the mixture was further stirred for 1 hour, whereby colorless crystals were aggregated in another three-necked reaction vessel to obtain the desired product (Dicianoacetylene).

When the obtained target product was analyzed, the following results were obtained.
Yield: 1.3g
Yield: 86%
¹³ C-NMR (CDCl ₃ ): 103.1, 55.1.

CHCl ₃ (20 ml) was added to and dissolved in a three-necked reaction vessel containing raw materials (Dicyanoacetylene: 1.74 g, 22.9 mmol), and then 1,3-cyclohexadiene (2.5 ml, 26 mmol) was added in an ice bath. Slowly added.
The mixture was stirred overnight at room temperature and concentrated under reduced pressure to obtain starting compound B (Bicyclo [2.2.2] octa-2,5-diene-2,3-dicarbonitile). Finally, it was purified by silica gel column chromatography (CHCl ₃ ).

When the obtained raw material compound B was analyzed, the following results were obtained.
Yield: 2.95 g
Yield: 83%
Molecular formula: C ₁₀ H ₈ N ₂ (156.1839)
Melting point: 101-102 ° C
Shape: White powder 1H-NMR (CDCl ₃ , 270 MHz) δ = 6.38-6.41 (dd, 2H, J = 3.4, 4.4 Hz), 4.04 (m, 2H), 1.54-1.58 (m, 4H)
¹³ C-NMR (CDCl ₃ , 67.5 MHz): = 132.31, 131.86, 113.94, 41.13, 24.06.
IR (KBr) max / cm ⁻¹ : 2221 (CN), 1585, 1342, 736, 686.
Mass spectrometry (DI-EI) m / z (%): 156 (8) [M ⁺ ], 128 (100), 101 (10), 69 (14), 57 (13).
Elemental analysis Calcd: C, 76.90; H, 5.16; N, 17.94.
Found: C, 78.85; H, 5.16; N, 17.61.

[Comparative Examples 1-6]
Using raw material compound B of the following formula as a raw material, synthesis of phthalocyanine precursor B was attempted according to the conditions of the following Table 1 as in the synthesis route of the following formula. However, none of the methods could obtain the phthalocyanine precursor B.

・ Comparative Examples 1-3
A three-necked reaction vessel equipped with a reflux tube was charged with Mg and a small amount of I ₂ and replaced with Ar. The solvent was added and heated to reflux until Mg was dissolved. After cooling to room temperature, the raw material compound B was added and heated.
When analyzed by mass spectrometry (MALDI-TOF), the phthalocyanine precursor B was not produced.

Comparative example 4
A reflux tube was attached to the _two- necked reaction vessel, and CuCl ₂ (17.57 mg, 0.13 mmol) and the raw material compound B (77.71 mg, 0.50 mmol) were added thereto, and Ar substitution was performed. Dry-EtOH (2.5 ml) was added and stirred for 15 minutes, then dry-DBU (0.08 ml, 0.537 mmol) was added and heated to reflux for 2 days. Dry-DBU (0.08 ml, 0.537 mmol) was added, and the mixture was further heated under reflux for 1 day, washed with NaHCO ₃ water, water and saturated brine, and concentrated under reduced pressure.
When analyzed by mass spectrometry (MALDI-TOF), phthalocyanine precursor B was not produced.

Comparative example 5
The raw material compound B (25.97 mg, 0.166 mmol) was placed in a one-necked reaction vessel, substituted with Ar, added with a LiOPr (0.5 ml) base solution, and stirred at room temperature for 25 days. After quenching with methanol: H ₂ O = 1: 1 aqueous solution (10 ml), the mixture was extracted with CHCl ₃ , washed with water and saturated brine, and concentrated under reduced pressure.
When analyzed by mass spectrometry (MALDI-TOF), the phthalocyanine precursor B was not produced.

Comparative Example 6
Raw material compound B (157.00 mg, 1.01 mmol) was placed in a one-necked reaction vessel, substituted with Ar, added with dry-MeOH (1.5 ml), stirred, and further Zn powder (143.83 mg, 2.20 mmol). ) And stirred at room temperature for 25 days. After quenching with methanol: H ₂ O = 1: 1 aqueous solution (50 ml), the mixture was extracted with CHCl ₃ , washed with water and saturated brine, and concentrated under reduced pressure.
When analyzed by mass spectrometry (MALDI-TOF), raw material compound B was detected, and phthalocyanine precursor B was not produced.

[Reference Example 2]
Thermal analysis of the dicyano compound of raw material compound B was performed.
The reverse Diels-Alder reaction occurred at about 100 degrees in the crystalline state. In the solution state, it is expected that the reverse Diels-Alder reaction occurs at a temperature lower than this temperature, and it is considered that when the temperature is higher than this temperature, it is converted to phthalonitrile from which ethylene molecules are eliminated.

[Summary of Comparative Examples 1 to 8, Reference Example 1]
As explained in Reference Example 1, the generation of phthalonitrile from the raw material compound B is considered to be one of the reasons why the reactions of Comparative Examples 1 to 6 do not proceed. However, Comparative Examples 7 to 8 were carried out according to the literature (Journal of Porphyrins and Phthalocyanines Vol. 4, p103-111 (2000)) conducted at room temperature, but Comparative Example phthalocyanine precursor B was not produced. It was.

[Comparative Examples 7 to 27]
The raw material compound A obtained in the synthesis example of the raw material compound A was used as a raw material without separating the isomers in the column, and the conditions of the following formula were used in the same manner as in Example 1 except for the conditions shown in Table 2 below. Then, the raw material compound A was tetramerized and an attempt was made to synthesize the phthalocyanine precursor A.
However, phthalocyanine precursor A could not be obtained by any method.

Comparative examples 7-12
Comparative Examples 7-12 used lithium wire. Only in the case of Comparative Example 11, a peak of phthalocyanine was observed by mass spectrometry (MALDI-TOF), and it was confirmed that tetramer cyclization occurred, but a peak where an acetal protecting group was not eliminated could not be confirmed. . Comparative Example 10 and Comparative Example 11 have different alkoxide adjustment times, which are 3 hours and 24 hours, respectively.

  Although the production | generation of the soluble precursor was able to be confirmed in the comparative example 15 and the comparative example 16, the yield in the comparative example 15 was a trace amount. In Comparative Example 16, a complex mixture is obtained, and in both cases, the yield is estimated to be 0.1% or less. Under the conditions of Comparative Example 15, one or two acetal protecting groups were not eliminated, but a peak could be confirmed by mass spectrometry (MALDI-TOF).

The compound obtained in Comparative Example 21 was analyzed by NMR. As a result, the following phthalocyanine precursor C from which two acetal protecting groups were eliminated had a yield of 24%, and the following phthalocyanine precursor D from which three had been eliminated had a yield of 11 % Was synthesized.

  In other conditions (Comparative Examples 13, 14, 17-20, 22-27), the raw materials or phthalonitrile produced by the reverse Diels-Alder reaction were recovered, or unidentifiable products such as polymers were recovered. . In Comparative Example 24, since a reaction using a microwave oven was attempted, the temperature was not measured.

  When the experiment was performed a plurality of times under the conditions of Comparative Example 17, not only the soluble precursor but also the raw material was recovered. Since the recovered raw material was only the syn-form raw material compound A, it is presumed that there is a difference in reactivity between the anti-form raw material compound A and the syn-form raw material compound A.

  From the above results, the synthesis process of the soluble precursor is the case where the phthalonitrile produced as a result of the reverse Diels-Alder reaction and the raw material compound A are tetramerized, and the tetramerized material is the reverse Diels-Alder reaction. However, the reaction may be complicated because the protecting group may be eliminated.

[Comparative Examples 28-31]
The raw material compound A-48 was used as a raw material, and the raw material compound A was tetramerized in the same manner as in Example 1 except for the conditions shown in Table 3 below, and synthesis of the phthalocyanine precursor A was attempted. .

Comparative Example 28
Under the conditions of Comparative Example 28, a peak of phthalocyanine could be confirmed by mass spectrometry (MALDI-TOF), but a peak where an acetal protecting group was not eliminated was not observed.
Comparative Example 29
In Comparative Example 29, a trace amount of 1.7% of the following phthalocyanine precursor C from which two acetal protecting groups were eliminated and the following phthalocyanine precursor D from which three acetal protecting groups were eliminated was obtained.
Comparative Example 30
In Comparative Example 30, the peak of copper phthalocyanine was confirmed by mass spectrometry (MALDI-TOF), but the peak of the precursor was not observed.
Comparative Example 31
The conditions of Comparative Example 31 were those obtained by tetramerization of the syn-form material compound A, but could not be synthesized with the anti-form material compound A.

[Comparison rate 32]
An FET was produced in the same manner as in Example 3 except that a vapor-deposited film was produced by vapor deposition using metal-free phthalocyanine represented by the following formula. The FET characteristics of this FET were 2 × 10 ⁻⁶ cm ² / Vs, and the on / off ratio was 83.

The present invention provides a novel phthalocyanine precursor that is less susceptible to thermal decomposition than the conventional one, a method for producing the same, a method for producing phthalocyanine derived from the phthalocyanine precursor, and a method for producing a phthalocyanine film.
There is no limit to the field to be applied unless it is contrary to the gist of the present invention, for example, an electrophotographic photosensitive member, an organic transistor, an organic solar cell, an organic electronic device such as an organic EL, a paint or ink as a pigment, optical recording, It can be applied to fields such as color filters and light therapy.

In Reference Example 1, it is a graph showing the result of thermal analysis for the syn isomer of the raw material compound A. In Reference example 1, it is a graph showing the result of the thermal analysis with respect to the anti body of the raw material compound A. In Example 2, it is a graph showing the result of the mass spectrometry (MALDI-TOF) of the phthalocyanine precursor A. In Example 2, it is a graph showing the result of the mass spectrometry (MALDI-TOF) of phthalocyanine. In Example 2, it is a graph showing the result of the absorption spectrum measurement of the phthalocyanine precursor A. In Example 2, it is a graph showing the result of the absorption spectrum measurement of a phthalocyanine.

Claims (9)

A phthalocyanine precursor represented by the following formula (1a) or (1b):

(In the above formula, R ^mn (m, n represents an integer of 1 to 4) represents a hydrogen atom or a monovalent substituent. M represents a divalent metal or a divalent atomic group containing a metal. (The structure of the bicyclo moiety containing Q ^m is a syn-body structure represented by the following formula (2).)

(In the above formula, Por represents the porphyrin ring of formula (1a) or formula (1b), and the solid and broken lines represent π-conjugated single bonds or double bonds. R ^m1 , R ^m2 , R ^m3 , and R ^m4 (m represents an integer of 1 to 4) represents a hydrogen atom or a monovalent substituent represented by the above formula (1a) or (1b), wherein R ^ma and R ^mb are a hydrogen atom or Represents a monovalent substituent.) Characterized by using the di Shianobishikuro compound as a starting compound, a process for the preparation of the phthalocyanine precursor represented by the following formula (1c) or formula (1d),
The method for producing a phthalocyanine precursor, wherein the ratio of the syn isomer to the total of the syn isomer and the anti isomer in the dicyanobicyclo compound is greater than 0.8 .

(In the above formula, R ^mn (m, n represents an integer of 1 to 4) represents a hydrogen atom or a monovalent substituent. M represents a divalent metal or a divalent atomic group containing a metal. Q ^m represents a divalent leaving group.)   The ratio of the syn body to the total of the syn body and the anti body is 1.
The method for producing a phthalocyanine precursor according to claim 2. Structure of bicyclo portion of the formula (1c) or phthalocyanine precursor represented by Formula (1d), characterized in that a syn body represented by the following formula (2), according to claim 2 or claim 3 A method for producing a phthalocyanine precursor.

(In the above formula, Por represents the porphyrin ring of formula (1c) or formula (1d), and the solid and broken lines represent π-conjugated single bonds or double bonds. R ^mn (m and n are 1 to 4) Represents a hydrogen atom or a monovalent substituent represented by the above formula (1a) or (1b), and R ^ma and R ^mb represent a hydrogen atom or a monovalent substituent. ) Phthalocyanine precursor of claim 1, or wherein the inducing phthalocyanine phthalocyanine precursor produced by the production method of the phthalocyanine precursor according to any one of claims 2 to 4, A method for producing phthalocyanine. Phthalocyanine precursor of claim 1, or claim 2 or by applying a phthalocyanine precursor produced in the substrate by the production method of the phthalocyanine precursor according to any one of claims 4, converted into a phthalocyanine film A method for producing a phthalocyanine film, comprising: The method for producing a phthalocyanine film according to claim 6 , wherein the phthalocyanine film is for an electronic device. The method of manufacturing a phthalocyanine film according to claim 7 , wherein the electronic device is a field effect transistor. The method for producing a phthalocyanine film according to claim 7 , wherein the electronic device is a solar cell.

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