JP2009084555A - Method for producing substituent-eliminated compound, method for producing pigment fine particle, method for producing phthalocyanine compound, and method for producing thin film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a substituent-eliminated compound having high industrial applicability and exhibiting advantageous preservation stability relative to both a solvent-soluble precursor compound capable of preferably corresponding to a solution process and the objective compound obtained by applying an external stimulus to the precursor compound by using the precursor compound, and also to provide an efficient method for producing pigment fine particles, a phthalocyanine compound and a thin film each having excellent properties by using the above technique. <P>SOLUTION: This method for producing the substituent-eliminated compound comprises applying an external stimulus to a compound A-(B)<SB>m</SB>having a solvent-soluble group B to eliminate the solvent-soluble group B, and bonding a hydrogen atom instead of the eliminated solvent-soluble group B to produce a solvent-insoluble compound. In formula, A represents a solvent-insoluble compound residue, B represents a specified solvent-soluble group, and m represents a natural number, with proviso that the solvent-soluble group B is bonded to a carbon atom in the solvent-insoluble compound residue A. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a substituent-eliminating compound obtained by eliminating a specific substituent, and relates to a method for producing pigment fine particles, a method for producing a phthalocyanine compound, and a method for producing a thin film using this technique.

Colorants used in inks, paints, resins, etc. are roughly classified into dyes and pigments. For example, in a colorant for an inkjet recording liquid (ink) that requires high definition, an image formed by ink using a dye has characteristics such as high transparency, high definition, and excellent color rendering. In many cases, there is a problem in properties and water resistance.
Therefore, in recent years, in order to solve the problem of weather resistance and water resistance of an image, a shift to an ink using a pigment such as an organic pigment or carbon black instead of a dye has started. Conventionally, pigments have been researched mainly on physical properties as colorants, but in recent years, attention has been focused on the molecular physical properties of pigments (for example, see Non-Patent Document 1).

  Thus, one of the problems that hinders research in pigments is that pigments generally have poor solubility in solvents such as water and organic solvents. For example, the dispersion of the pigment becomes unstable due to the aggregation of the pigment generated in the ink, and there are many problems from the viewpoint of reliability such as ink ejection.

On the other hand, methods have been proposed in which a substituent is eliminated by applying an external stimulus to a precursor into which a reactive substituent that solubilizes an organic material is introduced (for example, Non-Patent Document 2 and Patent Document 1). See). In this method, for example, the Boc group is removed by heating the pigment precursor having a structure in which an amino group or alcoholic or phenolic hydroxy group in the pigment molecule is modified with a t-butoxycarbonyl group (Boc group). It is something to be released.
However, this method has limited compounds because the substituents need to be linked to nitrogen or oxygen atoms. Furthermore, the improvement was calculated | required also from the viewpoint of the preservability of a precursor.

In recent years, methods for converting from a highly solvent-soluble precursor to porphyrin or phthalocyanine by applying a retro Diels-Alder reaction to an external stimulus have been energetically studied (for example, Non-Patent Document 3 and Patents). See references 2-15.)
However, these examples needed improvement from the viewpoint of the preservability of the compound obtained after the precursor / treatment. In addition, all of them require complicated synthesis, so the application range is narrow, and the development of substituents that can be synthesized more simply is required.

JP-A-7-188234 JP 2006-165533 A JP 2006-131574 A JP 2005-93990 A JP 2004-256450 A JP 2004-6750 A JP 2003-304014 A JP 2006-182989 A JP 2006-249436 A JP 2004-320007 A JP 2004-319982 A JP 2005-79203 A JP-A-2005-294809 JP 2005-277029 A JP-A-2005-79204 "Technology of functional pigments and application development", CM Nature, 1997, Vol. 388, p. 131 Applied Physics Letters, 2004, Vol. 84, p. 2085

  The present invention uses a solvent-soluble precursor compound that can be suitably applied to a solution process, and exhibits good storage stability in both the precursor compound and the target compound obtained by applying external stimulation thereto. An object of the present invention is to provide a method for producing a substituent-eliminating compound having high utility. Another object of the present invention is to provide an efficient method for producing pigment fine particles, phthalocyanine compounds, and thin films having excellent characteristics by using this technique.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained solubility by using a compound having a specific substituent different from the conventionally used Boc group as a precursor. By adding an external stimulus such as heat to this, the elimination reaction of the substituent can proceed promptly, and the storage stability of the reactant and product is high, and if necessary, the crystal structure of the product can be changed. It has been found that it can be controlled, and the present invention has been completed.

（式中、Ｘは水素原子または置換基を表し、ｎは１又は２の整数を表す。）
（２）前記外部刺激が１５０〜５００℃に加熱することであることを特徴とする（１）記載の置換基脱離化合物の製造方法。
（３）前記溶媒不溶性化合物残基Ａが、２つ以上の芳香族炭化水素環または芳香族へテロ環が縮環され及び／又は共有結合で連結された構造のπ共役系化合物の残基であることを特徴とする（１）又は（２）に記載の置換基脱離化合物の製造方法。
（４）前記溶媒不溶性化合物残基Ａが色素骨格であることを特徴とする（１）〜（３）のいずれか１項に記載の置換基脱離化合物の製造方法。
（５）前記溶媒可溶性基Ｂが下記一般式（ＩＩ）で表される基であることを特徴とする（１）〜（４）のいずれか１項に記載の置換基脱離化合物の製造方法。

（式中、Ｘは水素原子または置換基を表す。）
（６）前記溶媒可溶性基Ｂが下記一般式（ＩＩＩ）で表される基であることを特徴とする（１）〜（５）のいずれか１項に記載の置換基脱離化合物の製造方法。

（式中、Ｒ^１〜Ｒ^３はそれぞれ独立に水素原子または置換基を表す。）
（７）前記化合物Ａ−（Ｂ）_ｍが下記一般式（ＩＶ）で表される化合物であることを特徴とする（１）〜（６）のいずれか１項に記載の置換基脱離化合物の製造方法。

（式中、Ｍは、金属原子または水素原子を表す。Ｍが水素原子を表す場合、２つの水素原子がＮ^１〜Ｎ^４のいずれか２つの窒素原子にそれぞれ結合する。Ｑは、芳香族炭化水素環または芳香族へテロ環を形成するのに必要な原子群を表す。複数のＱは同一でも異なっていてもよい。Ｒ^４〜Ｒ^６はそれぞれ独立に水素原子または置換基を表す。ｎは自然数である。ｎが２以上の場合、複数の−ＳＯ_２Ｃ（Ｒ^４）（Ｒ^５）（Ｒ^６）基は同一でも異なっていてもよい。）
（８）前記化合物Ａ−（Ｂ）_ｍがフタロシアニン化合物である、（７）記載の置換基脱離化合物の製造方法。
（９）顔料が溶媒可溶性基Ｂにより修飾された構造の顔料前駆体Ａ−（Ｂ）_ｍ（式中、Ａは顔料残基を表し、Ｂは下記一般式（Ｉ）で表される溶媒可溶性基を表す。ｍは自然数を表す。ただし、溶媒可溶性基Ｂは、顔料残基Ａ中の炭素原子に結合している。）に外部刺激を与えて前記溶媒可溶性基Ｂを脱離させ、代わりに水素原子が結合した顔料に転換することを特徴とする顔料微粒子の製造方法。

（式中、Ｘは水素原子または置換基を表し、ｎは１又は２の整数を表す。）
（１０）下記一般式（Ｉ）で表される置換基を有するフタロシアニン化合物（ただし、前記置換基は、フタロシアニン化合物残基中の炭素原子に結合している。）に外部刺激を与えて前記置換基を脱離させ、代わりに水素原子が結合したフタロシアニン化合物に転換することを特徴とするフタロシアニン化合物の製造方法。

（式中、Ｘは水素原子または置換基を表し、ｎは１又は２の整数を表す。）
（１１）溶媒可溶性基Ｂを有する化合物Ａ−（Ｂ）_ｍ（式中、Ａは溶媒不溶性化合物残基を表し、Ｂは下記一般式（Ｉ）で表される溶媒可溶性基を表す。ｍは自然数を表す。ただし、溶媒可溶性基Ｂは、溶媒不溶性化合物残基Ａ中の炭素原子に結合している。）を溶媒に溶解し、この溶解液を基材に塗布して塗付膜とし、該塗布膜中の前記化合物Ａ−（Ｂ）_ｍに外部刺激を与えて前記溶媒可溶性基Ｂを脱離させ、代わりに水素原子が結合した溶媒不溶性化合物とし、その薄膜を形成することを特徴とする薄膜の製造方法。

（式中、Ｘは水素原子または置換基を表し、ｎは１又は２の整数を表す。） The above-described problems of the present invention have been solved by the following means.
(1) Compound A- (B) _m having a solvent-soluble group B (wherein, A represents a solvent-insoluble compound residue, and B represents a solvent-soluble group represented by the following general formula (I). It represents a natural number, provided that the solvent-soluble group B is bonded to the carbon atom in the solvent-insoluble compound residue A.) to give an external stimulus to eliminate the solvent-soluble group B. A method for producing a substituent-eliminating compound, which is a bonded solvent-insoluble compound.

(In the formula, X represents a hydrogen atom or a substituent, and n represents an integer of 1 or 2.)
(2) The method for producing a substituent-eliminating compound according to (1), wherein the external stimulus is heating to 150 to 500 ° C.
(3) The solvent-insoluble compound residue A is a residue of a π-conjugated compound having a structure in which two or more aromatic hydrocarbon rings or aromatic heterocycles are condensed and / or covalently linked. The method for producing a substituent-eliminating compound according to (1) or (2), wherein:
(4) The method for producing a substituent-eliminating compound according to any one of (1) to (3), wherein the solvent-insoluble compound residue A is a dye skeleton.
(5) The method for producing a substituent leaving compound according to any one of (1) to (4), wherein the solvent-soluble group B is a group represented by the following general formula (II): .

(In the formula, X represents a hydrogen atom or a substituent.)
(6) The method for producing a substituent-eliminating compound according to any one of (1) to (5), wherein the solvent-soluble group B is a group represented by the following general formula (III): .

(In the formula, R ^{1 to} R ³ each independently represents a hydrogen atom or a substituent.)
(7) The substituent elimination compound according to any one of (1) to (6), wherein the compound A- (B) _m is a compound represented by the following general formula (IV): Manufacturing method.

(In the formula, M represents a metal atom or a hydrogen atom. When M represents a hydrogen atom, two hydrogen atoms are each bonded to any two nitrogen atoms of N ^{1 to} N ^4. Q is aromatic. A group of atoms necessary for forming a hydrocarbon ring or an aromatic hetero ring, a plurality of Qs may be the same or different, and R ^{4 to} R ⁶ each independently represents a hydrogen atom or a substituent. n is a natural number, and when n is 2 or more, a plurality of —SO ₂ C (R ⁴ ) (R ⁵ ) (R ⁶ ) groups may be the same or different.
(8) The method for producing a substituent leaving compound according to (7), wherein the compound A- (B) _m is a phthalocyanine compound.
(9) Pigment precursor A- (B) _m having a structure in which the pigment is modified with a solvent-soluble group B (wherein A represents a pigment residue, and B is a solvent-soluble compound represented by the following general formula (I)) M represents a natural number, provided that the solvent-soluble group B is bonded to the carbon atom in the pigment residue A.) to give an external stimulus to the solvent-soluble group B, and A method for producing pigment fine particles, wherein the pigment is converted to a pigment having hydrogen atoms bonded thereto.

(In the formula, X represents a hydrogen atom or a substituent, and n represents an integer of 1 or 2.)
(10) A phthalocyanine compound having a substituent represented by the following general formula (I) (provided that the substituent is bonded to a carbon atom in the phthalocyanine compound residue) to give an external stimulus to the substitution A method for producing a phthalocyanine compound, characterized in that a group is eliminated and converted into a phthalocyanine compound to which a hydrogen atom is bonded instead.

(In the formula, X represents a hydrogen atom or a substituent, and n represents an integer of 1 or 2.)
(11) Compound A- (B) _m having a solvent-soluble group B (wherein A represents a solvent-insoluble compound residue, B represents a solvent-soluble group represented by the following general formula (I), and m represents Represents a natural number, provided that the solvent-soluble group B is bonded to the carbon atom in the solvent-insoluble compound residue A.) is dissolved in a solvent, and this solution is applied to a substrate to form a coated film. An external stimulus is applied to the compound A- (B) _m in the coating film to desorb the solvent-soluble group B, and a solvent-insoluble compound having a hydrogen atom bonded thereto is formed instead to form the thin film. A method for manufacturing a thin film.

(In the formula, X represents a hydrogen atom or a substituent, and n represents an integer of 1 or 2.)

  According to the method for producing a substituent-eliminating compound of the present invention, since a solvent-soluble precursor compound is used as a raw material, it can be suitably applied to a solution process, and the substitution is performed by applying an external stimulus to the precursor compound. The target compound can be obtained by promptly proceeding with the elimination reaction of the group. Furthermore, in the production method of the present invention, both the precursor compound and the target compound obtained by applying an external stimulus thereto have high storage stability such as light resistance, and can be stored as a raw material and a product. In addition, there is an excellent effect of increasing the degree of freedom of the manufacturing process and improving the efficiency and realizing high quality. In addition, this technique can be used to efficiently produce pigment fine particles, phthalocyanine compounds, and thin films thereof having high purity and excellent characteristics.

Hereinafter, the present invention will be described in detail.
The method for producing a substituent-eliminating compound of the present invention includes a step of dissolving a specific compound in a solvent and a step of eliminating the substituent from the compound. Here, the specific compound is represented by A- (B) _m . In the formula, A represents a solvent-insoluble compound residue, B represents a solvent-soluble group represented by the general formula (I), and m represents a natural number. Hereinafter, the compound A- (B) _m having the solvent-soluble group B is referred to as “solvent-soluble precursor compound”.
In the solvent-soluble precursor compound used in the production method of the present invention, the solvent-soluble group B is bonded to the carbon atom in the solvent-insoluble compound residue A. Then, in the step of removing the substituent, the solvent-soluble group B bonded to the carbon atom in the solvent-insoluble compound residue A is released, and instead a solvent-insoluble compound bonded with a hydrogen atom, preferably A- ( H) _m (wherein, A represents a solvent-insoluble compound residue, H represents a hydrogen atom, and m represents a natural number) is obtained.

  The solvent-soluble precursor compound used in the present invention has a structure in which a solvent-soluble group B is bonded to a solvent-insoluble compound residue A from which a hydrogen atom bonded to an arbitrary carbon atom in the solvent-insoluble compound is removed. Here, the solvent-soluble group B is represented by the following general formula (I).

  In the general formula (I), X represents a hydrogen atom or a substituent, and n represents an integer of 1 or 2.

  Examples of the substituent represented by X include halogen atoms, alkyl groups (including cyclic structures such as cycloalkyl groups and bicycloalkyl groups), and alkenyl groups (including cyclic structures such as cycloalkenyl groups and bicycloalkenyl groups). .), Alkynyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro group, carboxy group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy Group, aryloxycarbonyloxy group, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, Mercapto group, Alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group , Imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, and silyl group.

  More specifically, examples of the substituent represented by X include a halogen atom (for example, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group [a linear, branched, cyclic substituted or unsubstituted alkyl group. . These are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl). A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably having 5 to 30 carbon atoms). A substituted or unsubstituted bicycloalkyl group, that is, a monovalent group obtained by removing one hydrogen atom from a C 5-30 bicycloalkane, for example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl) and tricyclo structures with more ring structures It is intended to. In the substituents described below, unless otherwise specified, an alkyl group (for example, an alkyl group of an alkylthio group) represents an alkyl group of the above concept. ],

Alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or unsubstituted 3 to 30 carbon atoms). An unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), Bicycloalkenyl group (Substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. For example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2 2] is intended to encompass oct-2-en-4-yl). ],

Alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group, aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as Phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound A monovalent group in which one hydrogen atom is removed from a 5- to 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as 2-furyl, 2-thienyl, 2 -Pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxy group, nitro group, carboxy group,

An alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example, methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), an aryloxy group (preferably A substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy group (preferably Is a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy, a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, 1- Phenyltetrazol-5-oxy, 2-tetrahydropyranyl Ii) acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyl Oxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy),

A carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di- n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, t- Butoxycarbonyloxy, n-octylcarbonyloxy), aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms such as phenoxycarbonyloxy, p Methoxyphenoxy carbonyloxy, p-n-hexadecyloxycarbonyl phenoxycarbonyloxy),

An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms) Groups such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino groups (preferably substituted with 1 to 30 carbon atoms) Or unsubstituted aminocarbonylamino, eg , Carbamoylamino, N, N-dimethylaminocarbonyl amino, N, N-diethylamino carbonylamino, morpholinocarbonylamino),

An alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxy; Carbonylamino), aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m- (n-octyloxy) ) Phenoxycarbonylamino), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms such as sulfamoylamino, N, N-dimethylamino) Sulfonylamino, N-n-octylaminosulfonylamino),

Alkyl or arylsulfonylamino group (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, phenyl Sulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably Substituted or unsubstituted heterocyclic thio group prime 2-30, for example, 2-benzothiazolylthio, 1-phenyl-5-ylthio),

Sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N- Acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms) 6-30 substituted or unsubstituted arylsulfinyl groups such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), alkyl or arylsulfonyl groups (preferably substituted or unsubstituted having 1 to 30 carbon atoms) Substitutional alk Sulfonyl groups, 6-30 substituted or unsubstituted arylsulfonyl group, e.g., methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p- methylphenyl sulfonyl),

Acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, substituted or unsubstituted carbon group having 4 to 30 carbon atoms Heterocyclic carbonyl groups bonded to the carbonyl group by an atom, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl), aryl An oxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), alkoxy Carbonyl group ( Preferably, it is a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), carbamoyl group (preferably having 1 to 30 carbon atoms). Substituted or unsubstituted carbamoyl, such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl),

An aryl or heterocyclic azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, such as phenylazo, p-chlorophenylazo, 5- Ethylthio-1,3,4-thiadiazol-2-ylazo), an imide group (preferably N-succinimide, N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, For example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphini ), A phosphinyloxy group (preferably having 2 carbon atoms) 30 substituted or unsubstituted phosphinyloxy groups, for example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinylamino groups (preferably substituted or unsubstituted having 2 to 30 carbon atoms) Phosphinylamino group such as dimethoxyphosphinylamino, dimethylaminophosphinylamino), silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms such as trimethylsilyl, t-butyldimethyl Silyl, phenyldimethylsilyl).

  Among the above substituents, those having a hydrogen atom may be substituted with the above groups after removing this. Examples of such a substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups. X may be further substituted with a substituent.

  In the general formula (I), n is preferably 2, and the substituent represented by the general formula (I) is preferably a substituent represented by the following general formula (II).

In said general formula (II), X is synonymous with X in the said general formula (I), and its preferable range is also the same.
Furthermore, the substituent represented by the general formula (II) is preferably a substituent represented by the following general formula (III).

In the general formula (III), R ^{1 to} R ³ each independently represent a hydrogen atom or a substituent. Of R ^{1 to} R ³ , two or more are preferably substituents other than hydrogen atoms, and more preferably all three are substituents other than hydrogen atoms.

Examples of the substituent represented by R ^{1 to} R ³ are the same as those exemplified as the examples of the substituent represented by X above. R ¹ , R ² and R ³ may be connected to each other to form a ring.
The substituents represented by R ^{1 to} R ³ are preferably each independently a halogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, 5- or 6-membered substituted or unsubstituted heterocyclic group, cyano group, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, 7 to 7 carbon atoms A substituted or unsubstituted arylcarbonyl group having 30 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, and a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms. More preferred are a halogen atom, an alkyl group having 1 to 30 carbon atoms, a cyano group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, and a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms. Most preferably, R ^{1 to} R ³ are all methyl groups.

  There is no restriction | limiting in particular in the number of the substituents represented with the said general formula (I) which it has in a compound molecule | numerator. From the viewpoint of solvent solubility and film formability, the larger the number of substituents, the more advantageous. On the other hand, from the viewpoint of thin film uniformity, it is preferable that the volume change before and after elimination of substituents is smaller. preferable. Therefore, the number of substituents represented by the general formula (I) in the molecule is preferably 1 to 4. When there are a plurality of substituents represented by the general formula (I) in the molecule, they may be the same or different.

The solvent-soluble precursor compound used in the production method of the present invention has a solvent-soluble group as described above, and the solvent-insoluble compound residue from which any hydrogen atom or the like in the solvent-insoluble compound is removed has a solvent-soluble group. It has a combined structure. And in the manufacturing method of the substituent elimination compound of this invention, the solvent soluble group of the said precursor compound is eliminated, and it is set as a solvent insoluble compound.
In the present invention, “solvent soluble” means that the solvent has a solubility of 0.1% by mass or more in a state where the solvent is heated to reflux and then cooled to room temperature. Preferably it is 0.5 mass% or more, More preferably, it is 1 mass% or more. Further, “solvent insolubilization” refers to lowering the solubility by one digit or more than the solvent-soluble state. Specifically, it is preferable to lower the solubility from 0.1% by mass or more (solvent solubility) to 0.01% by mass or less in a state where the solvent is heated to reflux and then cooled to room temperature. More preferably, the solubility is decreased from 0.5% by mass or more (solvent soluble) to 0.05% by mass or less, and from 1% by mass or more (solvent soluble) to less than 0.1% by mass. It is particularly preferable to reduce it. “Solvent insolubility” means that the solvent has a solubility of less than 0.1% by mass in a state where the solvent is heated to reflux and then cooled to room temperature, and is 0.05% by mass or less. Preferably, it is 0.01 mass% or less.
The kind of the solvent for defining the degree of “solvent solubility” and “solvent insolubility” is not particularly limited, and may be determined depending on the actually used solvent and temperature. For example, solubility in water (distilled water) (25 ° C. ) Can be specified. However, the solvent used in the present invention is not limited thereto.

A π-conjugated compound can be obtained by the production method of the present invention, and the π-conjugated compound may be any compound as long as it has a wide π-conjugated plane, but a benzene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, Triazine ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, furan ring, thiophene ring, more preferably benzene ring, pyridine ring, pyrazine ring, pyrrole ring, pyrrole ring, pyrazole ring, imidazole ring , An oxazole ring, a thiazole ring, a thiophene ring, etc., two or more aromatic hydrocarbon rings or aromatic heterocycles, condensed and / or covalently linked, and these aromatic hydrocarbon rings Alternatively, the π electrons of each aromatic heterocycle may interact with each other through condensed ring and / or linking interactions. It is preferable condensed and / or the entire coupling ring is delocalized structure. The number of condensed aromatic rings and / or covalently linked aromatic hydrocarbon rings or aromatic heterocycles is preferably 2-20, more preferably 3-12.
Specific examples of the π-conjugated compound include condensed polycyclic compounds such as tetracene, pentacene, triphenylene, and hexabenzocoronene, heterocyclic oligomers such as quarterthiophene and sexithiophene, phthalocyanines, and porphyrins.

  The solvent-insoluble compound obtained by the production method of the present invention can be a compound used as a UV absorber, and examples thereof include triazine compounds, benzotriazole compounds, and benzophenone compounds. Further, it can be any compound used as an organic pigment, and any compound can be used. For example, an azo pigment (for example, an insoluble azo pigment is roughly classified into an insoluble monoazo pigment and an insoluble disazo pigment, Are acetoacetate arylides, β-naphthols, naphthol ASs, and benzimidazolones, and insoluble disazo pigments include acetoacetate arylides, pyrazolones, and condensed azos, and azo lake pigments. ), Condensed polycyclic pigments (for example, anthraquinone, isoindolinone, isoindoline, quinacridone, perylene, perinone, dioxazine, diketopyrrolopyrrole, indigo, and quinophthalone). Metal complex pigments (eg phthalocyanine-based, azo Chin system. Nitroso the like), other pigments (e.g. azine, daylight fluorescent pigments, carbon black) can be mentioned.

  In the present invention, from the viewpoint of chemical stability of the compound, tetracene, pentacene, triphenylene, hexabenzocoronene, porphyrins and the like are preferable as the π-conjugated compound, and triazine compound and benzotriazole compound are preferable as the UV absorber. The organic pigment is preferably a condensed polycyclic pigment or a metal complex pigment. More preferred are tetracene, pentacene, triphenylene, hexabenzocoronene, triazine compounds, condensed polycyclic pigments or metal complex pigments.

  From the viewpoint of obtaining the target compound described above, the solvent-insoluble compound residue A from which a hydrogen atom bonded to any carbon atom in the solvent-insoluble compound is removed includes two or more aromatic hydrocarbon rings or aromatic heterocycles. It is preferably a residue of a π-conjugated compound having a structure which is condensed and / or linked by a covalent bond. Further, a dye skeleton is preferable. Furthermore, the solvent-insoluble compound residue A is preferably a pigment residue, and more preferably a phthalocyanine compound residue.

  The solvent-soluble precursor compound used in the present invention is more preferably a compound represented by the following general formula (IV) from the viewpoint of chemical stability of the compound, and is represented by the following general formula (IV). It is particularly preferred that the compound is a phthalocyanine compound. Here, the phthalocyanine compound refers to a compound having a phthalocyanine skeleton, and is a derivative in which a substituent is bonded to phthalocyanine.

In the general formula (IV), Q represents an atomic group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocycle. A plurality of Q may be the same or different. Here, the aromatic hydrocarbon ring or aromatic hetero ring is preferably a 4- to 10-membered ring, more preferably a 5- to 7-membered ring, further preferably a 5- or 6-membered ring, and particularly preferably a 6-membered ring.
Although the hetero atom contained in the aromatic heterocycle formed by Q is not particularly limited, nitrogen, oxygen, sulfur, selenium, silicon, germanium or phosphorus is preferable, nitrogen, oxygen or sulfur is more preferable, and nitrogen is particularly preferable. The number of heteroatoms contained in one aromatic heterocycle formed by Q is not particularly limited, but is preferably 1 to 3.

Specific examples of the aromatic hydrocarbon ring or aromatic heterocycle formed by Q include benzene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring. Oxadiazole ring, thiazole ring, thiadiazole ring, furan ring, thiophene ring, selenophene ring, silole ring, germol ring, phosphole ring and the like.
The aromatic hydrocarbon ring or aromatic heterocycle formed by Q may have a substituent, and as the substituent, those mentioned above for R ^{1 to} R ³ can be applied.

The aromatic hydrocarbon ring or aromatic heterocycle formed by Q may further form a condensed ring with another ring. Examples of the condensed ring include a benzene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, and a pyridazine ring. , Pyrrole ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, oxadiazole ring, thiazole ring, thiadiazole ring, furan ring, thiophene ring, selenophene ring, silole ring, gelmol ring, phosphole ring and the like. The above substituent and condensed ring may further have a substituent and may be further condensed with another ring. As the substituent, those described above as R ^{1 to} R ³ can be applied.

  The aromatic hydrocarbon ring or aromatic heterocycle formed by Q is preferably a benzene ring, pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole. Ring, furan ring, thiophene ring, more preferably benzene ring, pyridine ring, pyrazine ring, pyrrole ring, pyrazole ring, imidazole ring, oxazole ring, thiazole ring, thiophene ring, more preferably benzene ring, A pyridine ring, a pyrazine ring, a pyrazole ring, an imidazole ring, and a thiophene ring are preferable, and a benzene ring, a pyridine ring, and a pyrazine ring are particularly preferable.

In the general formula (IV), the —SO ₂ C (R ⁴ ) (R ⁵ ) (R ⁶ ) group bonded to the phthalocyanine skeleton may be bonded anywhere in the molecule, but preferably by Q Substitution with the aromatic hydrocarbon ring or aromatic heterocycle formed. R < ⁴ > -R < ⁶ > is synonymous with R < ¹ > -R < ³ > in the said general formula (III), and its preferable range is also the same. n is a natural number. When n is 2 or more, a plurality of —SO ₂ C (R ⁴ ) (R ⁵ ) (R ⁶ ) groups may be the same or different.

In the general formula (IV), M represents a metal atom or a hydrogen atom. When M represents a hydrogen atom, two hydrogen atoms are each bonded to any two nitrogen atoms of N ^{1 to} N ⁴ .
When M represents a metal atom, any metal may be used as long as it forms a stable complex, and Li, Na, K, Be, Mg, Ca, Ba, Al, Si, Hg, Cr, Fe, Co Ni, Cu, Zn, Ge, Pd, Cd, Sn, Pt, Pb, Sr, V, Mn, Ti, In, or Ga can be used. A substituent may be bonded to the metal atom, and as the substituent, those mentioned above for R ^{1 to} R ³ can be used.
The preferred _{M Mg, Ca, AlCl, SiCl} 2, Fe, Co, Ni, Cu, Zn, Pd, Sn, SnCl 2, Pt, Pb, V = O, is Mn or Ti = O is used, more preferably Fe, Co, Ni, Cu or Zn is used, and Cu or Zn is particularly preferably used. M is preferably a hydrogen atom. When M is a hydrogen atom, the general formula (IV) is represented by the following general formula (IV ′).

In Formula (IV ^'), Q, R ^4, R 5, ^{R 6} and n are ^Q in each formula (IV), and R ^4, R 5, ^{R 6} and n synonymous with the preferred range Is the same.

  Generally, in a phthalocyanine compound having a plurality of substituents, there may exist positional isomers having different positions to which the substituents are bonded. In the present invention, there is no exception, and in some cases, several kinds of positional isomers can be considered. In the present invention, the phthalocyanine compound may be used as a single compound or as a mixture of positional isomers. When used as a mixture of regioisomers, the number of regioisomers mixed, the substitution position of the substituent in each regioisomer, and the mixing ratio of regioisomers may be arbitrary.

Although the preferable specific example of the phthalocyanine compound used for this invention is given to the following, this invention is not limited to these illustrated compounds.
In the following Tables 1 to 4, for example, the notation “R ^α1 / R ^α2 ” represents the meaning of “one of R ^α1 and R ^α2 ”. Therefore, a compound having this notation is a mixture of substitutional isomers. is there. Further, when R ^{α1 to} R ^α8 or R ^{β1 to} R ^β8 are unsubstituted, that is, when a hydrogen atom is substituted, the notation is omitted. The * mark of the substituent indicates a binding site to the phthalocyanine derivative represented by the following general formula (V). Bu represents a butyl group, and Me represents a methyl group.

  The phthalocyanine ring-forming reaction of the phthalocyanine compound in the present invention is described by Shigeyoshi Shirai and Kobayashi Nagao, "Phthalocyanine-Chemistry and Function" (IPC, 1997), pages 1 to 62, Takahashi Ryo and Sakamoto Keiichi. This can be carried out according to pages 29 to 77 of “Phthalocyanine as a functional pigment” edited by Eiko Okumura (IPC, published in 2004).

  Typical methods for synthesizing phthalocyanine compounds include the Weiler method, phthalonitrile method, lithium method, subphthalocyanine method, and chlorinated phthalocyanine method described in these documents. In the present invention, the phthalonitrile method can be preferably used. Specifically, it is preferable to perform a phthalocyanine ring formation reaction using a compound having a substituent represented by the general formula (I) such as t-butylsulfonylphthalonitrile as a raw material. Any reaction conditions may be used in the phthalocyanine ring formation reaction. In the ring formation reaction, it is preferable to add various metals to be the central metal of phthalocyanine, but a desired metal may be introduced after the synthesis of a phthalocyanine compound having no central metal. Any solvent may be used as the reaction solvent, but a solvent having a high boiling point is preferable. Further, an acid or a base may be used for promoting the ring formation reaction. Optimum reaction conditions vary depending on the structure of the target phthalocyanine compound, but can be set with reference to specific reaction conditions described in the above-mentioned documents.

  As raw materials used for the synthesis of the phthalocyanine compound, derivatives such as phthalic anhydride, phthalimide, phthalic acid and salts thereof, phthalic acid diamide, phthalonitrile, 1,3-diiminoisoindoline can be used. These raw materials may be synthesized by any ordinary method.

  Further, the compound used in the present invention can be prepared by introducing the substituent represented by the general formula (I) into the solvent-insoluble compound with reference to the description in JP-A-2005-119165 and the like. it can.

In the method for producing a substituent-eliminating compound of the present invention, it is preferable to first dissolve the solvent-soluble precursor compound A- (B) _m used in the present invention in a solvent.
As the solvent, water and / or an organic solvent can be used. Examples of the organic solvent include hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, ethylbenzene, 1-methylnaphthalene, and 1,2-dichlorobenzene; for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ketone solvents; for example, halogenated hydrocarbon solvents such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, and chlorotoluene; for example, esters such as ethyl acetate, butyl acetate, and amyl acetate System solvents; for example, alcohols such as methanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol Solvents; for example, ether solvents such as dibutyl ether, tetrahydrofuran, dioxane, anisole, etc .; for example, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1-methyl-2-imidazolid Polar solvents such as non- and dimethyl sulfoxide can be used.
The concentration of the solvent-soluble precursor compound in the solution is not particularly limited and varies depending on the application, but can be dissolved in the concentration range defined as “solvent-soluble” described above.

In the method for producing a substituent-eliminating compound of the present invention, the solvent-soluble group is formed by applying an external stimulus such as heating after application using a solution in which the solvent-soluble precursor compound is dissolved in a solvent. It can be desorbed and converted to a solvent insoluble compound.
The external stimulus is typically heat treatment using a heater. The heating temperature is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and further preferably 250 ° C. or higher. Further, the upper limit is preferably 550 ° C. or lower, more preferably 500 ° C. or lower, and further preferably 400 ° C. or lower. The higher the temperature, the shorter the reaction time, and the lower the temperature, the longer the time required for the elimination reaction. Such heating is preferably performed in an inert atmosphere such as nitrogen or argon.
Depending on the application, by changing the heating temperature and the heating time, it is possible to remove only a part of the substituents represented by the general formula (I) and adjust the properties of the resulting compound. For example, when used as an organic semiconductor film, the mobility can be adjusted.
In addition to heating by heat transfer using a heater, heating is performed by providing a layer that absorbs light in the vicinity of the layer containing the solvent-soluble precursor compound used in the present invention, and absorbing the light in this layer. May be.

In addition, as the external stimulus, any treatment for decomposing the substituent represented by the general formula (I) can be performed. In addition to the heat treatment as described above, photolysis treatment or chemical decomposition can be performed. (Using organic or inorganic acids or bases). These conversion methods can also be combined.
In the case of the photolysis treatment, an infrared lamp, irradiation with light having a wavelength absorbed by the compound (for example, exposure to a wavelength of 405 nm or less), and the like may be used. At that time, a semiconductor laser may be used. For example, near-infrared laser light (usually laser light having a wavelength of around 780 nm), visible laser light (usually laser light having a wavelength in the range of 630 nm to 680 nm), and laser light having a wavelength of 390 to 440 nm can be mentioned.
Laser light having a wavelength of 390 to 440 nm is particularly preferable, and semiconductor laser light having an oscillation wavelength in the range of 440 nm or less is preferably used. Among them, as a preferable light source, a blue-violet semiconductor laser light having an oscillation wavelength in the range of 390 to 440 (more preferably 390 to 415 nm) and an infrared semiconductor laser light having a central oscillation wavelength of 850 nm are half wavelength using an optical waveguide device. And blue-violet SHG laser light having a central oscillation wavelength of 425 nm.
Examples of organic or inorganic acids or bases that can be preferably used in the case of chemical decomposition include acids, mineral acids (for example, sulfuric acid, hydrochloric acid, hydrobromic acid, nitric acid, phosphoric acid, etc.), organic carboxylic acids ( For example, acetic acid, succinic acid, formic acid, propionic acid, benzoic acid, etc.) or sulfonic acids (for example, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.) are preferably used, more preferably sulfuric acid, Hydrochloric acid, hydrobromic acid or acetic acid, particularly preferably sulfuric acid or hydrochloric acid. In addition, you may use these acids individually or in mixture of 2 or more types. The base is preferably an organic base, alkyl metal, metal hydride (for example, sodium hydride) and the like. More preferred is triethylamine, pyridine or sodium hydride. Particularly preferred is triethylamine or pyridine.

In an embodiment in which a phthalocyanine compound is obtained as the solvent-insoluble compound, a phthalocyanine compound having a solvent-soluble group (however, the substituent is bonded to a carbon atom in the phthalocyanine compound residue) is dissolved in a solvent. Thereafter, the substituent can be eliminated by applying an external stimulus such as heating to obtain an unsubstituted phthalocyanine compound.
Phthalocyanine compounds have been attracting attention for their molecular properties, but their insolubility in solvent has been a hindrance to research. According to the present invention, thin film formation or the like is performed using a solution in which a phthalocyanine compound having a structure substituted with a specific solvent-soluble group is dissolved in a general solvent, regardless of introduction of a special substituent or molecular modification. Can do. Thereafter, by removing the substituent, a thin film of an unsubstituted phthalocyanine compound can be obtained, and a semiconductor thin film or a finely processed film can be efficiently produced without requiring a complicated process.

  In an embodiment in which a pigment is obtained as the solvent-insoluble compound, after the pigment precursor having a structure in which the pigment is modified with a solvent-soluble group is dissolved in the solvent, the pigment is converted to the pigment by applying an external stimulus such as heating. A pigment dispersion in which pigment fine particles are dispersed can be obtained. The particle size of the pigment fine particles is not particularly limited, but when it is obtained as a nanometer size, the average particle size is preferably 1 to 1000 nm, more preferably 10 to 500 nm. The obtained pigment particles can be preferably used for applications such as paints, printing inks, electrophotographic toners, inkjet inks, and color filters.

In an embodiment of obtaining a dye compound by the method for producing a substituent-eliminating compound of the present invention, the use of the obtained dye includes an image recording material for forming an image, particularly a color image, specifically, Examples include inkjet recording materials described in detail below, thermal recording materials, pressure-sensitive recording materials, recording materials using electrophotographic methods, transfer type silver halide photosensitive materials, printing inks, recording pens, etc., preferably inkjet A recording material using a method recording material, a heat-sensitive recording material, or an electrophotographic method, and more preferably an ink jet recording material.
Further, the present invention can also be applied to a solid-state image pickup device such as a CCD, a color filter for recording / reproducing a color image used in a display such as an LCD or PDP, and a dyeing solution for dyeing various fibers.
The coloring matter obtained by the present invention is used by adjusting the physical properties such as solvent solubility, dispersibility, heat transferability, etc. suitable for its use with a substituent. Moreover, the pigment | dye obtained by this invention can be used also in a dissolved state, an emulsified dispersion state, and also a solid dispersion state according to the system to be used.

In the embodiment of producing pigment fine particles in the present invention, ink can be produced using the pigment fine particles obtained there. Therefore, the ink means an ink containing at least one kind of pigment fine particles obtained by the present invention as a coloring matter.
The ink can contain a medium, but when a solvent is used as the medium, it is particularly suitable as an ink for inkjet recording. The ink can be prepared by using a lipophilic medium or an aqueous medium as a medium and dissolving and / or dispersing the pigment obtained by the present invention in the medium. Preferably, an aqueous medium is used. The ink includes an ink composition excluding a medium.
The ink may contain other additives as necessary. Other additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, Known additives (described in JP-A No. 2003-306623) such as a foaming agent, a viscosity modifier, a dispersant, a dispersion stabilizer, a rust inhibitor, and a chelating agent can be used. These various additives are directly added to the ink liquid in the case of water-soluble ink. When an oil-soluble dye is used in the form of a dispersion, it is generally added to the dispersion after the preparation of the dye dispersion, but it may be added to the oil phase or the aqueous phase at the time of preparation.

  When the pigment obtained by the present invention is dispersed in an aqueous medium, it is described in JP-A-11-286637, JP-A-2001-240763, JP-A-2001-262039, JP-A-2001-247788, and the like. As described above, coloring fine particles containing a dye and an oil-soluble polymer are dispersed in an aqueous medium, or described in JP-A-2001-262018, JP-A-2001-240763, JP-A-2001-335734, etc. As described above, it is preferable to disperse the dye obtained by the present invention dissolved in a high-boiling organic solvent in an aqueous medium. The specific method for dispersing the pigment obtained by the present invention in an aqueous medium, the oil-soluble polymer to be used, the high-boiling organic solvent, the additive and the amount used thereof are preferably those described in the above-mentioned patent documents. can do. Or you may disperse | distribute the said pigment | dye to a fine particle state with a solid. At the time of dispersion, a dispersant or a surfactant can be used.

  Dispersing devices include simple stirrer, impeller stirring method, in-line stirring method, mill method (for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.), ultrasonic method, high-pressure emulsification dispersion method (high-pressure homogenizer) Specific examples of commercially available devices include gorin homogenizers, microfluidizers, DeBEE2000 (trade name), and the like. Regarding the method for preparing the ink for ink jet recording, in addition to the above-mentioned patent documents, JP-A Nos. 5-148436, 5-295212, 7-97541, 7-82515, 7-118584, The details are described in JP-A-11-286637 and JP-A-2001-271003, and can also be used for the preparation of inks for ink jet recording using the dyes obtained by the present invention.

  As the aqueous medium, a mixture containing water as a main component and optionally adding a water-miscible organic solvent can be used. Examples of the water miscible organic solvent include those described in JP-A No. 2003-306623. In addition, the said water miscible organic solvent may use 2 or more types together.

  Preferably, the pigment obtained by the present invention is contained in an amount of 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.2 parts by mass or more and 10 parts by mass or less, in 100 parts by mass of the ink for inkjet recording. It is more preferable to contain 0.5-9 mass parts. Moreover, you may use another pigment | dye together with the pigment | dye obtained by this invention for the inkjet ink. When two or more kinds of dyes are used in combination, the total content of the dyes is preferably within the above range.

  The ink can be used not only for forming a single color image but also for forming a full color image. In order to form a full color image, a magenta color ink, a cyan color ink, and a yellow color ink can be used, and a black color ink may be further used to adjust the color tone.

  Furthermore, the ink for inkjet recording can use another cyan dye simultaneously with the pigment | dye obtained by this invention. As the applicable yellow dye, applicable magenta dye, and applicable cyan dye, any of them can be used, but each dye described in paragraph Nos. 0090 to 0092 of JP-A-2003-306623 can be used. . Applicable black materials include disazo, trisazo, tetraazo dyes, and carbon black dispersions.

  In the ink jet recording method, energy is supplied to the ink for ink jet recording, and a known image receiving material, that is, plain paper, resin-coated paper, such as JP-A-8-169172, JP-A-8-27693, and JP-A-2-276670. Gazettes, 7-276789, 9-323475, JP-A-62-238783, JP-A-10-153898, 10-217473, 10-235995, 10 -337947, 10-217597, 10-337947, etc. An image is formed on an inkjet exclusive paper, film, electrophotographic co-paper, fabric, glass, metal, ceramics, and the like. In addition, the description of Paragraph Nos. 0093 to 0105 of JP-A No. 2003-306623 can be applied as an ink jet recording method.

  When forming an image, a polymer latex compound may be used in combination for the purpose of giving glossiness or water resistance or improving weather resistance. The timing of applying the latex compound to the image receiving material may be before, after, or simultaneously with the application of the colorant, and therefore the addition location may be in the image receiving paper. It may be in ink or may be used as a liquid material of polymer latex alone. Specifically, JP 2002-166638 A, JP 2002-121440 A, JP 2002-154201 A, JP 2002-144696 A, JP 2002-080759 A, Japanese Patent Application 2000-299465. And the method described in Japanese Patent Application No. 2000-297365 and the like can be preferably used.

Although there is no restriction | limiting in particular in content of the pigment | dye obtained by this invention in 100 mass parts of color toners, it is preferable to contain 0.1 mass part or more, 1-20 mass parts is more preferable, 2-10 mass parts containing Most preferably.
As the binder resin for a color toner into which the pigment obtained by the present invention is introduced, all commonly used binders can be used. Examples thereof include styrene resin, acrylic resin, styrene / acrylic resin, and polyester resin.
Inorganic fine powders and organic fine particles may be externally added to the toner for the purpose of improving fluidity and controlling charging. Silica fine particles and titania fine particles whose surface is treated with an alkyl group-containing coupling agent or the like are preferably used. These have a number average primary particle diameter of preferably 10 to 500 nm, and more preferably 0.1 to 20% by mass in the toner.

  As the release agent, all conventionally used release agents can be used. Specific examples include olefins such as low molecular weight polypropylene, low molecular weight polyethylene, and ethylene-propylene copolymer, microcrystalline wax, carnauba wax, sazol wax, and paraffin wax. These addition amounts are preferably 1 to 5% by mass in the toner.

  The charge control agent may be added as necessary, but is preferably colorless from the viewpoint of color development. Examples thereof include those having a quaternary ammonium salt structure and those having a calixarene structure.

  As the carrier, either an uncoated carrier composed only of magnetic material particles such as iron and ferrite, or a resin-coated carrier whose magnetic material particle surface is coated with a resin or the like may be used. The average particle size of the carrier is preferably 30 to 150 μm in terms of volume average particle size.

  The image forming method to which the toner is applied is not particularly limited. For example, a method of forming a color image by repeatedly forming a color image on a photoconductor and transferring the image, or an image formed on the photoconductor And the like, and a color image is formed on the intermediate transfer member and then transferred to an image forming member such as paper to form a color image.

The heat-sensitive recording material includes an ink sheet in which the dye obtained by the present invention is coated on a support together with a binder, and an image-receiving sheet that fixes the dye transferred in accordance with the thermal energy applied from the thermal head according to the image recording signal Consists of The ink sheet is prepared by dissolving the compound obtained by the present invention in a solvent together with a binder or by dispersing the compound in a fine particle form in a solvent, and applying the ink on a support. It can be formed by drying. The amount of ink applied on the support is not particularly limited, but is preferably 30 to 1000 mg / m ² . As the preferred binder resin, ink solvent, support, and image receiving sheet, those described in JP-A-7-137466 can be preferably used.

  In order to apply the heat-sensitive recording material to a heat-sensitive recording material capable of full-color image recording, a cyan ink sheet containing a heat-diffusible cyan dye capable of forming a cyan image, and heat diffusion capable of forming a magenta image. It is preferable to form a magenta ink sheet containing a reactive magenta dye and a yellow ink sheet containing a heat-diffusible yellow dye capable of forming a yellow image by sequentially coating on a support. In addition, an ink sheet containing a black image forming substance may be further formed as necessary.

  As a method for forming a color filter, a pattern is first formed with a photoresist and then dyed, or disclosed in JP-A-4-163552, JP-A-4-128703, JP-A-4-17553, and the like. As described above, there is a method of forming a pattern with a photoresist added with a dye. Any of these methods may be used as a method used for introducing the dye obtained by the present invention into a color filter, and preferred methods include JP-A-4-175533 and JP-A-6-35182. A positive resist composition comprising a thermosetting resin, a quinonediazide compound, a cross-linking agent, a dye and a solvent, as described in the publication, and after being coated on a substrate, it is exposed through a mask. Examples of the color filter forming method include developing a portion to form a positive resist pattern, exposing the entire surface of the positive resist pattern, and then curing the exposed positive resist pattern. In addition, a black matrix can be formed according to a conventional method to obtain an RGB primary color system or Y, M, C complementary color system color filter. In the case of a color filter, although there is no restriction | limiting of the usage-amount of a pigment | dye, 0.1-50 mass% is preferable.

  Regarding the thermosetting resin, quinonediazide compound, crosslinking agent, and solvent used in this case, and those used, those described in the above-mentioned patent documents can be preferably used.

  When the solvent-insoluble compound exhibits crystallinity, the crystal system of the solvent-insoluble compound can be controlled as necessary by using the production method of the present invention. When the solvent-soluble precursor compound having a substituent represented by the general formula (I) used in the present invention exhibits an amorphous crystal structure, the substituent is eliminated by the method of the present invention to form a solvent-insoluble compound. Can be converted, resulting in a crystal transition. For example, copper phthalocyanine shows homogeneous heterocrystals, and crystals such as α, β, ε, γ, δ, π, χ, and R have been reported (for example, “Basic and Applied Phthalocyanine as Functional Dye”). (See IPC).) The crystal system that can be controlled in the embodiment for obtaining the phthalocyanine compound according to the present invention is preferably α, β or ε, more preferably α or β. In particular, the metastable α-type crystal has been produced by the acid paste method in the past, so the crystallite is small and the peak of the X-ray diffraction measurement result is broad. Therefore, a sharp peak with a small half width can be obtained, and an α-type crystal with a large crystallite can be produced.

  In the present invention, the solvent-soluble precursor compound is dissolved in a solvent, applied onto a substrate, dried, and then subjected to an external stimulus such as heating to desorb the solvent-soluble group, thereby making the solvent insoluble Compound thin films can be produced. Examples of the base material include a substrate, but may be the upper surface or wall surface of other members.

As the substrate used in this embodiment, various materials such as polyester films such as polyethylene naphthalate (PEN) and polyethylene terephthalate (PET), polyimide films, ceramics, silicon, quartz, and glass can be used. Preferred is ceramic, silicon, quartz or glass, and more preferred is silicon, quartz or glass. Any substrate may be selected depending on the application. For example, a flexible substrate can be used in the case of use of a flexible element.
The thickness of the substrate is not particularly limited, but is preferably 1 to 1000 μm, and more preferably 10 to 800 μm.

  In the present invention, when the solution of the solvent-soluble precursor compound is applied on a substrate to form a film, the method may be any method, but it is particularly preferable to form the film by a solution process. Here, film formation by a solution process refers to a method in which an organic compound is dissolved in a solvent capable of dissolving, and the solution is applied onto a substrate and dried to form a film. Specifically, casting method, blade coating method, wire bar coating method, spray coating method, dipping (dipping) coating method, bead coating method, air knife coating method, curtain coating method, ink jet method, spin coating method, Langmuir- An ordinary method such as a Langmuir-Blodgett (LB) method can be used. In the present invention, it is more preferable to use a casting method, a spin coating method, and an ink jet method. By such a solution process, a thin film having a smooth surface and a large area can be produced at a low cost.

When a film is formed on a substrate by a solution process, carbonization of a material for forming the layer with an appropriate organic solvent (for example, hexane, octane, decane, toluene, xylene, ethylbenzene, 1-methylnaphthalene, 1,2-dichlorobenzene, etc.) Hydrogen solvents; for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; halogenated carbonization such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, chlorotoluene Hydrogen solvents; for example, ester solvents such as ethyl acetate, butyl acetate, and amyl acetate; for example, methanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl celloso Alcohol solvents such as butyl, ethyl cellosolve and ethylene glycol; for example, ether solvents such as dibutyl ether, tetrahydrofuran, dioxane and anisole; for example, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2 A polar solvent such as -pyrrolidone, 1-methyl-2-imidazolidinone, dimethyl sulfoxide, etc.) and / or water to form a coating solution, and a thin film can be formed by various coating methods. .
The concentration of the compound used in the present invention in the coating solution is preferably 0.1 to 80% by mass, more preferably 0.1 to 10% by mass, whereby a film with an arbitrary thickness can be formed.

It is also possible to use a resin binder during film formation. In this case, the material for forming the layer and the binder resin can be dissolved or dispersed in the above-mentioned appropriate solvent to form a coating solution, and a thin film can be formed by various coating methods. Resin binders include polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose, polyethylene, polypropylene, and other insulating polymers, and their co-polymers. Examples thereof include photoconductive polymers such as coalescence, polyvinyl carbazole and polysilane, and conductive polymers such as polythiophene, polypyrrole, polyaniline and polyparaphenylene vinylene. The resin binder may be used alone or in combination. Considering the mechanical strength of the thin film, a resin binder having a high glass transition temperature is preferable.
It is preferable not to use a resin binder in terms of the characteristics of the organic semiconductor, but it may be used depending on the purpose. The amount of the resin binder used in this case is not particularly limited, but is preferably 0.1 to 30% by mass in the thin film.

  In the film formation, the substrate may be heated or cooled, and the film quality and packing of molecules in the film can be controlled by changing the temperature of the substrate. Although there is no restriction | limiting in particular as temperature of a board | substrate, It is preferable that it is between 0 degreeC-200 degreeC.

  The solvent-soluble precursor compound used in the present invention is particularly suitable for film formation by a solution process. The film may also be formed by a vacuum process such as a physical vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, a molecular beam epitaxy (MBE) method, or a chemical vapor deposition (CVD) method such as plasma polymerization. Although possible, these are not preferred because of high production costs and poor film surface smoothness. In addition, in order to form a film by a solution process, it is necessary that the material is dissolved in the above-described solvent or the like, but it is not sufficient to simply dissolve the material. Usually, even a material for forming a film by a vacuum process can be dissolved in a solvent to some extent. However, in the solution process, there is a process in which after the material is dissolved in a solvent and applied, the solvent evaporates to form a thin film. Here, since many materials not suitable for the solution process have high crystallinity, they are crystallized in this process, and it is difficult to form a good thin film. On the other hand, the solvent-soluble precursor compound used in the present invention is excellent in that crystallization hardly occurs.

  The coating amount of the solution containing the compound varies depending on the type of solvent and the concentration of the solution, but is appropriately determined so that the thickness of the thin film to be formed is preferably 5 nm to 50 μm, more preferably 20 nm to 500 nm. The The film thickness is not limited to this range and varies depending on the application.

  The produced film can be adjusted by post-treatment. For example, characteristics can be improved by changing the film morphology and molecular packing in the film by heat treatment or exposure to solvent vapor. In addition, exposure to an oxidizing or reducing gas, solvent, substance, or the like, or mixing of these causes an oxidation or reduction reaction, and the association state in the film can be adjusted.

  In the production method of the present invention, as described above, a precursor compound having solvent solubility suitable for a solution process is used. Then, external stimuli are given to this, but storage stability such as light resistance before and after that, that is, the above-mentioned solvent-soluble precursor compound and the target compound obtained by giving external stimuli thereto are decomposed even if stored for a predetermined period. It has the property that it will not change or change. This is different from a conventionally used precursor compound into which a Boc group is introduced. By using a compound having the above specific substituent as a precursor, it can be easily dissolved in various solvents, and the substituent can be efficiently eliminated by applying external stimulus such as heat to the solution or coating film. And useful compounds can be obtained in high yield. In addition, this technique can efficiently form fine pigment particles, phthalocyanine compounds, and thin films thereof.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these.

<Example 1>
Exemplified compound (1) (compound of M = Cu) was prepared according to the synthesis of dye compound (I-1) described in JP-A-2005-119165. This exemplary compound (1) was dissolved in a solvent such as chloroform.
The prepared exemplary compound (1) was heated to a predetermined temperature as described below, and changes in molecular weight and crystal structure before and after heating were measured.

(TG / DTA measurement)
The prepared exemplary compound (1) was subjected to thermal analysis (TG / DTA measurement). TG / DTA measurement was performed by Seiko Instruments Inc. Using EXSTAR6000 (trade name), the temperature was increased at a rate of 10 ° C./min in the range of 30 ° C. to 550 ° C. under an N ₂ air flow (flow rate 200 ml / min) to obtain the mass reduction rate. The measurement results are shown in FIG. FIG. 1 is a graph showing the TG / DTA measurement results of Example Compound (1). In each of the following examples and comparative examples, TG was measured using the above-described apparatus and conditions.

In FIG. 1, the top curve shows mass change (TG) with respect to temperature, the bottom curve shows heat input / output (enthalpy change) (DTA) with respect to temperature, and the middle curve shows TG. The amount of change per hour (differential value) (DTG) is shown.
From the uppermost curve in FIG. 1, it was found that the mass decreased gradually from around 200 ° C., and the mass decreased by about 50% up to about 340 ° C. This mass reduction corresponds to the mass of the substituent (—SO ₂ C (CH ₃ ) ₃ group) in the exemplary compound (1). Further, from the lowest curve in FIG. 1, it was found that the heat absorption started from around 240 ° C. and the heat absorption occurred up to about 340 ° C. From these results, it can be seen that the substituent was eliminated from the exemplified compound (1) by heating.

(MALDI-TOF-MS measurement)
About the exemplary compound (1) before and after heating to 400 degreeC, the matrix assistance ionization-time-of-flight mass spectrometry (MALDI-TOF-MS) measurement was performed, respectively. MALDI-TOF-MS measurement was performed using Voyager-DE PRO (trade name) manufactured by Applied Biosystems and using α-cyano-4-hydroxycinnamic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) as a matrix. The spectrum measurement results are shown in FIG. FIG. 2 (a) is a graph showing the MALDI-TOF-MS spectrum measurement result before heat treatment of the exemplary compound (1), and FIG. 2 (b) is MALDI-TOF- after heat treatment of the exemplary compound (1). It is a graph which shows a MS spectrum measurement result.
In FIG. 2A showing the state before the heat treatment, a peak of 1056 ([M ⁺ ] +1) corresponding to the molecular weight of the exemplary compound (1) was observed, but FIG. In b), this peak disappeared, and it was found that a peak of 575 ([M ⁺ ]) corresponding to the molecular weight of unsubstituted copper phthalocyanine (CuPc: C ₃₂ H ₁₆ CuN ₈ ) appears. The same results were obtained when heated to 350 ° C. and 550 ° C., respectively. From this result, it can be seen that Exemplified Compound (1) was converted to unsubstituted copper phthalocyanine by heating.

(X-ray diffraction measurement)
X-ray diffraction measurement was performed on the exemplified compound (1) heated to 350 ° C., 400 ° C. or 550 ° C., respectively. For X-ray diffraction measurement, X-RAY DIFFRACTOMETER RINT-2500 (trade name) manufactured by Rigaku was used. The measurement results are shown in FIG.
As is clear from the results of FIG. 3, it was found that the exemplary compound (1) which was an amorphous solid before heating was crystallized after heating. It was also found that the crystal system changed as the temperature was raised. The crystal system at 350 ° C. and 400 ° C. was α-type, and when it was heated to 550 ° C., a β-type phthalocyanine compound pigment was formed. I understand that.

(Measurement of heat change)
About exemplary compound (1), DSC apparatus: Seiko Instruments Inc. Using DSC6200R (trade name) manufactured by sealing a sample in a closed cell made of SUS, raising the temperature at 10 ° C./min in the range of 30 ° C. to 550 ° C., and the amount of heat in the decomposition temperature region determined by the above TG-DTA measurement Changes were measured. The measurement results are shown in FIG.
As is clear from the results of FIG. 4, an endothermic peak due to dye decomposition was observed at around 350 ° C., and an exothermic peak was observed at a region near 430 ° C. where there was no mass loss. Also from this result, it can be seen that the heated exemplary compound (1) changes its crystal system from α-type to β-type at around 430 ° C.

From the above measurement results, Exemplified Compound (1) [Solvent-Soluble Precursor Compound] is an amorphous solid, and the substituent (—SO ₂ C (CH ₃ ) ₃ group) is eliminated by heating, and the crystalline compound It was converted to unsubstituted copper phthalocyanine (α-type), and it was further found that the crystal system changed to β-type at around 430 ° C.

<Example 2>
6.21 g of α-t-butylsulfonylphthalonitrile was added to 10.5 ml of hexamethyldisilazane and 6.4 ml of dimethylformamide, and 1.40 g of zinc bromide was further added. Thereafter, the mixture was stirred at 100 ° C. for 8 hours, and then filtered through methanol to obtain 4.00 g of Exemplified Compound (51). Its MS spectrum was 1057 (= [M ⁺ ] +1: polar positive). This exemplified compound (51) was dissolved in a solvent such as chloroform.
The measurement result of TG of exemplary compound (51) is shown in FIG.
The exemplified compound (51) obtained above was heated at 400 ° C., and the MS spectrum of the residue was measured. The peak of the MS spectrum was changed to 576 (= [M ⁺ ]: polar positive). From these results, it can be seen that the substituent was eliminated from the exemplified compound (51) at around 300 ° C. and changed to a zinc phthalocyanine pigment.

<Example 3>
20.0 g of α-t-butylsulfonylphthalonitrile was added to 2.2 g of N, N′-dimethylethylenediamine and 25 ml of N-methylpyrrolidone, and the mixture was stirred at 160 ° C. for 8 hours. Thereafter, the mixture was filtered with methanol to obtain 3.50 g of Exemplified Compound (52), and the MS spectrum thereof was 996 (= [M ⁺ ] +1: polar positive). This exemplified compound (52) was dissolved in a solvent such as chloroform.
FIG. 6 shows a TG measurement result of the exemplary compound (52).
The exemplified compound (52) obtained above was heated at 400 ° C., and the MS spectrum of the residue was measured. The peak of the MS spectrum was changed to 514 (= [M ⁺ ]: polar positive). From these results, it can be seen that the substituent was eliminated from the exemplified compound (52) and changed to a metal-free (hydrogen type) phthalocyanine pigment.

<Example 4>
Commercially available 4-substituted zinc sulfonate phthalocyanine (Exemplary Compound (53), Frontier Science Co., Ltd.) had an MS spectrum of 895 (= [M ⁺ ]: polar negative). This exemplified compound (53) was water-soluble.
The result of measuring the TG of this compound is shown in FIG.
Even when 4-substituted zinc sulfonate phthalocyanine was heated at 250 ° C., it showed water solubility. The initial weight loss in TG is believed to be due to solvent or water. Thereafter, the mixture was heated to 400 ° C., and the MS spectrum of the residue was measured. As a result, the peak of the MS spectrum was changed to 576 (= [M ⁺ ]: polar positive). From these results, it can be seen that the substituent was eliminated from the exemplified compound (53) and changed to a zinc phthalocyanine pigment.

<Example 5>
The MS spectrum of a commercially available 4-substituted sulfonic acid metal-free phthalocyanine (Exemplary Compound (54), manufactured by Frontier Science Co., Ltd.) was 832 (= [M ⁺ ] -1: polar negative). This exemplified compound (54) was water-soluble.
The result of measuring the TG of this compound is shown in FIG.
The exemplified compound (54) was water-soluble even when heated at 250 ° C. The initial weight loss in TG is believed to be due to solvent or water. Thereafter, the mixture was heated to 400 ° C., and the MS spectrum of the residue was measured. As a result, the peak of the MS spectrum was changed to 514 (= [M ⁺ ]: polar positive). From these results, it can be seen that the substituent was eliminated from the exemplified compound (54) and changed to an unsubstituted metal-free (hydrogen type) phthalocyanine pigment.

<Example 7>
(Preparation of thin film 1)
Illustrative compound (1) [solvent-soluble precursor compound] 2 g was added and dissolved in 100 ml of chloroform to prepare a dye precursor-containing coating solution. A dye film (thin film 1) is produced by coating the prepared dye-containing solution on a glass plate having a thickness of 1.0 mm under the conditions of 23 ° C. and 50% RH while changing the rotational speed from 500 to 1000 rpm by a spin coating method. did. When the organic film at this time was observed with a polarizing optical microscope and an electron microscope, a uniform amorphous film was formed.

Moreover, the absorption spectrum was measured about the produced film | membrane. The absorption spectrum was measured using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, trade name, MPC-2200 / UV-2400). The measurement results are shown in FIG. The absorption spectrum is as shown in the figure, and since the spectrum shape is similar to the absorption spectrum (not shown) of the coating solution containing the dye precursor, the solvent-soluble precursor compound does not change in the film, and the molecule It was found that there was almost no intermolecular interaction (λ _max = 673 nm).

(Preparation of thin film 2)
Next, the thin film 1 was heat-treated at 350 ° C. for 3 minutes in the air, and then the absorption spectrum of the film was measured in the same manner as described above. The measurement results are shown in FIG. The absorption spectrum is as shown in the figure, and it was found that the substituent was eliminated by the heat treatment, and the intermolecular interaction between the molecules in the film was increased (λ _max = 709 nm). Moreover, when it combines with the result of the said Example 1, it turns out that the thin film obtained by the said heat processing is a thin film which consists of a target solvent insoluble phthalocyanine compound (copper phthalocyanine ((alpha) type)).

<Comparative Example 1>
(Preparation of thin film 3)
In Example 2, Example 1 was used except that the compound described in “Nature, 1997, Vol. 388, p. 131” (Comparative Compound 1 below) was used instead of Exemplified Compound (1). Similarly, a thin film 3 was produced.
The absorption spectrum of the produced film was measured in the same manner as in Example 2. The measurement results are shown in FIG. The absorption spectrum is as shown in the figure, and since the spectrum shape is similar to the absorption spectrum of the solution in which the following Comparative Compound 1 is dissolved, the Comparative Compound 1 does not change, and the molecules in the film are almost intermolecular. It was found that it was not working (λ _max = 435 nm).

(Preparation of thin film 4)
Next, the thin film 3 was heat-treated at 180 ° C. for 3 minutes in air, and then the absorption spectrum of the film was measured in the same manner as described above. The measurement results are shown in FIG. The absorption spectrum is as shown in the figure, the substituent (Boc group) is eliminated by heat treatment, a diketopyrrolopyrrole compound pigment is formed, and the intermolecular interaction between the pigment molecules in the film increases. (Λ _max = 546 nm).

Light fastness evaluation <Light resistance evaluation of dye film>
After each of the above thin films 1 to 4 is stored at 23 ° C. and 50% RH for 24 hours, a merry-go-round type light resistance tester (manufactured by Eagle Engineering, Cell Tester Type III, with Schott WG320 filter, all are trade names) is used. The light resistance test was conducted. With respect to the dye film immediately before the light resistance test and the dye film after 48 hours of the light resistance test, an absorption spectrum was measured using UV-1600PC (trade name, manufactured by SHIMADZU), and a change in absorbance at the maximum absorption wavelength was read. The results are shown in Table 6.

  As is clear from the results in Table 6, in Exemplified Compound (1) and Comparative Compound 1, both the substituents were eliminated by heat treatment, and a dye film with high fastness was obtained. However, the comparative compound 1 having a Boc group before the heat treatment was inferior in light fastness. In contrast, the exemplary compound (1) used in the present invention was excellent in light fastness even before heat treatment. From this result, it can be seen that according to the present invention, the storage stability is extremely high before and after the elimination of the substituent, that is, both the solvent-soluble precursor compound and the solvent-insoluble compound obtained therefrom.

<Comparative example 2>
Fine α-type copper phthalocyanine crystals were obtained by the acid pasting method using copper phthalocyanine (β-type manufactured by Tokyo Chemical Industry Co., Ltd.) instead of the exemplified compound (1). Specifically, 2.5 g of copper phthalocyanine (Tokyo Chemical Industry β-type) was dissolved in 25 ml of concentrated sulfuric acid and then poured into 500 ml of water at 0 ° C. to obtain the fine α-type crystals.

  The obtained fine α-type crystals were each subjected to X-ray diffraction measurement. For X-ray diffraction measurement, X-RAY DIFFRACTOMETER RINT-2500 (trade name) manufactured by Rigaku was used. The results are shown in FIG. Further, among the X-ray diffraction measurement results in Example 1, data of the α-type crystal in FIG. 3 (heated at 350 ° C. or 400 ° C.) and the chart in FIG. 11 showing the X-ray diffraction measurement results in Comparative Example 2 FIG. 12 shows a comparison with the above.

  As is clear from the results in the figure, both of those obtained in Example 1 and Comparative Example 2 showed a peak of the α-type copper phthalocyanine crystal structure. However, the half-width was smaller in the crystal obtained in Reference Example 1 than in the crystal obtained in Comparative Example 2. From this, it can be seen that in the case of a metastable α-type crystal, it is difficult to produce a large crystallite, but according to the present invention, an α-type crystal having a large crystallite can be produced.

<Comparative Example 3>
The results of measuring TG / DTA of commercially available 4-substituted sodium sulfonate copper phthalocyanine (manufactured by Aldrich) are shown below. This comparative compound (2) was dissolved in water. The result of measuring the TG of this compound is shown in FIG. The initial weight loss in TG is due to solvent or water. Subsequent heating to 400 ° C does not cause weight loss. From this result, it is understood that a high temperature exceeding 400 ° C. is required for the elimination of the substituent (sodium sulfonate) from the 4-substituted sodium sulfonate copper phthalocyanine.

It is a figure which shows the TG / DTA measurement result of exemplary compound (1). It is a figure which shows the MALDI-TOF-MS spectrum measurement result of exemplary compound (1), (a) is a thing before heat processing, (b) is a thing after heat processing. It is a figure which shows the X-ray-diffraction measurement result of exemplary compound (1), (a) is before heat processing and after 350 degreeC heating, (b) is before heat processing and after 400 degreeC heating, (c) Is before heat treatment and after heat treatment at 550 ° C. It is a figure which shows the SC / DSC measurement result of exemplary compound (1). It is a figure which shows the measurement result of TG of exemplary compound (51). It is a figure which shows the measurement result of TG of exemplary compound (52). It is a figure which shows the measurement result of TG of exemplary compound (53). It is a figure which shows the measurement result of TG of exemplary compound (54). It is a figure which shows the absorption spectrum of the film | membrane which consists of exemplary compound (1), (a) is a thing before heat processing, (b) is a thing after heat processing. It is a figure which shows the absorption spectrum of the film | membrane which consists of the comparative compound 1, (a) is a thing before heat processing, (b) is a thing after heat processing. It is a figure which shows the X-ray-diffraction measurement result of the crystal | crystallization obtained in the comparative example 2. 3 is a graph comparing the X-ray diffraction measurement result of the α-type crystal of Example 1 and the X-ray diffraction measurement result of the α-type crystal of Comparative Example 2. FIG. It is a figure which shows the measurement result of TG / DTA of commercially available 4-substituted sodium sulfonate copper phthalocyanine.

Claims (11)

Compound A- (B) _m having a solvent-soluble group B (wherein, A represents a solvent-insoluble compound residue, B represents a solvent-soluble group represented by the following general formula (I), and m represents a natural number). However, the solvent-soluble group B is bonded to the carbon atom in the solvent-insoluble compound residue A.) The solvent-soluble group B is eliminated by applying an external stimulus to the solvent-insoluble compound residue A. A method for producing a substituent-eliminating compound, which is an insoluble compound.

(In the formula, X represents a hydrogen atom or a substituent, and n represents an integer of 1 or 2.)   The method for producing a substituent-eliminating compound according to claim 1, wherein the external stimulus is heating to 150 to 500 ° C.   The solvent-insoluble compound residue A is a residue of a π-conjugated compound having a structure in which two or more aromatic hydrocarbon rings or aromatic heterocycles are condensed and / or covalently linked. The method for producing a substituent-eliminating compound according to claim 1 or 2.   The method for producing a substituent-eliminating compound according to any one of claims 1 to 3, wherein the solvent-insoluble compound residue A is a dye skeleton. The method for producing a substituent-eliminating compound according to any one of claims 1 to 4, wherein the solvent-soluble group B is a group represented by the following general formula (II).

(In the formula, X represents a hydrogen atom or a substituent.) The method for producing a substituent-eliminating compound according to any one of claims 1 to 5, wherein the solvent-soluble group B is a group represented by the following general formula (III).

(In the formula, R ^{1 to} R ³ each independently represents a hydrogen atom or a substituent.) The said compound A- (B) _m is a compound represented by the following general formula (IV), The manufacturing method of the substituent elimination compound of any one of Claims 1-6 characterized by the above-mentioned.

(In the formula, M represents a metal atom or a hydrogen atom. When M represents a hydrogen atom, two hydrogen atoms are each bonded to any two nitrogen atoms of N ^{1 to} N ^4. Q is aromatic. A group of atoms necessary for forming a hydrocarbon ring or an aromatic hetero ring, a plurality of Qs may be the same or different, and R ^{4 to} R ⁶ each independently represents a hydrogen atom or a substituent. n is a natural number, and when n is 2 or more, a plurality of —SO ₂ C (R ⁴ ) (R ⁵ ) (R ⁶ ) groups may be the same or different. The method for producing a substituent-eliminating compound according to claim 7, wherein the compound A- (B) _m is a phthalocyanine compound. Pigment precursor A- (B) _m having a structure in which the pigment is modified with a solvent-soluble group B (wherein A represents a pigment residue and B represents a solvent-soluble group represented by the following general formula (I)) M represents a natural number, provided that the solvent-soluble group B is bonded to the carbon atom in the pigment residue A.) to give an external stimulus to remove the solvent-soluble group B, and instead a hydrogen atom A method for producing pigment fine particles, wherein the pigment is converted to a pigment having a bound thereto.

(In the formula, X represents a hydrogen atom or a substituent, and n represents an integer of 1 or 2.) The phthalocyanine compound having a substituent represented by the following general formula (I) (wherein the substituent is bonded to a carbon atom in the phthalocyanine compound residue) is applied to external stimuli to remove the substituent. A method for producing a phthalocyanine compound, characterized in that the phthalocyanine compound is converted to a phthalocyanine compound having a hydrogen atom bonded thereto.

(In the formula, X represents a hydrogen atom or a substituent, and n represents an integer of 1 or 2.) Compound A- (B) _m having a solvent-soluble group B (wherein, A represents a solvent-insoluble compound residue, B represents a solvent-soluble group represented by the following general formula (I), and m represents a natural number). However, the solvent-soluble group B is bonded to the carbon atom in the solvent-insoluble compound residue A.) is dissolved in a solvent, and this solution is applied to a substrate to form a coating film. The thin film is formed by applying an external stimulus to the compound A- (B) _m in which the solvent-soluble group B is eliminated and a hydrogen-bonded solvent-insoluble compound is formed instead. Method.

(In the formula, X represents a hydrogen atom or a substituent, and n represents an integer of 1 or 2.)

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