JP4590584B2 - Method for dissolving substituted metal phthalocyanines or subphthalocyanines and their analogs - Google Patents

Description

  The present invention relates to a method for dissolving certain substituted metal phthalocyanines or subphthalocyanines and their analogs.

  Phthalocyanine is often used as an organic pigment. To make this pigment fine, after dissolving the pigment in a specific acid such as sulfuric acid, trichloroacetic acid, trifluoroacetic acid, etc., this is dissolved in water or its poorly soluble organic pigment. A method of precipitation in addition to a solvent is well known.

  However, in this method, it is necessary to perform washing sufficiently so that no acid remains due to the acid treatment used for dissolving phthalocyanine, and the operation becomes complicated, and a large amount of inevitably discharged. There is a problem that environmental consideration is indispensable for acid waste liquid.

  By the way, as a method for dissolving the phthalocyanine pigment, supercritical water (see Patent Document 1), supercritical ketone solvent, alcohol solvent or water (see Patent Document 2) and the like are proposed in addition to the acid solvent.

JP 2002-285032 A (Claims and others) JP 2001-92165 A (Claims and others)

  Under such circumstances, it is an object of the present invention to provide another simple method for dissolving a phthalocyanine compound or a related compound without using these solvents.

  The inventors of the present invention have conducted various studies on the dissolution methods of phthalocyanine compounds, subphthalocyanine compounds, and their analogs. As a result, at least the substituents of the former two have been specified, and supercritical carbon dioxide as a solvent. Or it discovered that the said subject was achieved by using subcritical carbon dioxide, and came to make this invention based on this knowledge.

［式中、Ｍは金属であり、ＸはＮ又はＣＲ^５、ＹはＮ又はＣＲ^６、ＺはＮ又はＣＲ^７であって、しかもＸ及びＹ共にＮでないときＺもＮではなく、ＸがＮのときＹはＣＲ^６、ＹがＮのときＺはＣＲ^７であり、Ｒ^１ないしＲ^７は互いに同一或いは異なって、Ｈ、アルキル基、アルケニル基、アルキニル基、ハロアルキル基、アルコキシアルキル基、置換されていてもよいアルコキシル基、アルキルチオ基、アルキルスルフィニル基、アルキルスルホニル基、ハロゲン、水酸基、チオ基、シアノ基、アミノ基、アシルアミノ基、ニトロ基、ＣＯ_２Ｄ、ＳＯ_３Ｄ（以上のＤはＨ、ＮＨ_４又はアルキル基を示す）、ＣＯＮＲ^８Ｒ^９（ここでＲ^８、Ｒ^９は互いに同一或いは異なって、Ｈ又はアルキル基を示す）、アリール基、アラルキル基、アリールオキシ基、アリールチオ基、アリールスルフィニル基又はアリールスルホニル基であるか、或いは隣接するもの同士で一緒に、アルキレンジオキシ基、クラウンエーテル残基又は−ＣＯ−ＮＲ^１０−ＣＯ−（ここでＲ^１０はＨ、アルキル基、式

又は式

で表わされる基を示す）で表わされる酸イミド基を形成する。但し、Ｒ^１ないしＲ^７が全てＨである場合を除く。］
及び一般式

［式中、Ｂは金属であり、ＱはＮ又はＣＲ^１４、ＴはＮ又はＣＲ^１５、ＷはＮ又はＣＲ^１６であって、しかもＱ及びＴ共にＮでないときＷもＮではなく、ＱがＮのときＴはＣＲ^１５、ＴがＮのときＷはＣＲ^１６であり、Ｒ^１１ないしＲ^１６は互いに同一或いは異なって、Ｈ、アルキル基、アルケニル基、アルキニル基、ハロアルキル基、アルコキシアルキル基、置換されていてもよいアルコキシル基、アルキルチオ基、アルキルスルフィニル基、アルキルスルホニル基、ハロゲン、水酸基、チオ基、シアノ基、アミノ基、アシルアミノ基、ニトロ基、ＣＯ_２Ｇ、ＳＯ_３Ｇ（以上のＧはＨ、ＮＨ_４又はアルキル基を示す）、ＣＯＮＲ^１７Ｒ^１８（ここでＲ^１７、Ｒ^１８は互いに同一或いは異なって、Ｈ又はアルキル基を示す）、アリール基、アラルキル基、アリールオキシ基、アリールチオ基、アリールスルフィニル基又はアリールスルホニル基であるか、或いは隣接するもの同士で一緒に、アルキレンジオキシ基、クラウンエーテル残基又は−ＣＯ−ＮＲ^１９−ＣＯ−（ここでＲ^１９はＨ、アルキル基、式

又は式

で表わされる基を示す）で表わされる酸イミド基を形成する。但し、Ｑ、Ｔ及びＷがいずれもＮでないとき、Ｒ^１１ないしＲ^１６が全てＨである場合を除く。］
で表わされる、置換金属フタロシアニン、置換金属サブフタロシアニン及びそれらの類縁体の中から選ばれた少なくとも１種を超臨界二酸化炭素又は亜臨界二酸化炭素と加圧混合して溶解させることを特徴とする、置換金属フタロシアニン、置換金属サブフタロシアニン及びそれらの類縁体の溶解方法。
（２）置換金属フタロシアニン又はサブフタロシアニンが、その中心金属にＣｕ、Ｆｅ、Ａｌ、Ｎｉ、Ｃｏ、Ｚｎ、Ｔｉ、Ｃｒ、Ｖ、Ｒｈ、Ｒｕ、Ｓｉ及びＭｏの群から選ばれるものを有する前記（１）記載の方法。
（３）さらに、炭化水素系溶媒、ハロゲン化炭化水素系溶媒、アルコール系溶媒、エーテル系溶媒、アセタール系溶媒、ケトン系溶媒、エステル系溶媒、窒素化合物系溶媒及び硫黄化合物系溶媒の中から選ばれた少なくとも１種の準溶媒を、それと超臨界二酸化炭素又は亜臨界二酸化炭素との合計量／超臨界二酸化炭素又は亜臨界二酸化炭素に対し、体積比で５０％を超えない割合で併用する前記（１）又は（２）記載の方法。
（４）準溶媒の使用割合を、０．１〜１０％の範囲とする前記（３）記載の方法。
（５）準溶媒がピリジン、イミダゾール、メタノール又はエタノールである前記（１）ないし（４）のいずれかに記載の方法。
（６）溶解するのを、超臨界二酸化炭素下とする、温度が３１．１℃の臨界温度以上５００℃以下、圧力が７．３８ＭＰａの臨界圧以上５０ＭＰａ以下の操作条件下で行う前記（１）ないし（５）のいずれかに記載の方法。
（７）前記（１）ないし（６）のいずれかに記載の方法で得られる置換金属フタロシアニン、置換金属サブフタロシアニン又はそれらの類縁体の溶液。 That is, the present invention is as follows.
(1) General formula

[Wherein M is a metal, X is N or CR ⁵ , Y is N or CR ⁶ , Z is N or CR ⁷ , and when X and Y are not N, Z is not N, and X is Y is CR ⁶ when N, Z is CR ⁷ when Y is N, and R ¹ to R ⁷ are the same or different from each other, and H, alkyl group, alkenyl group, alkynyl group, haloalkyl group, alkoxyalkyl group, Optionally substituted alkoxyl group, alkylthio group, alkylsulfinyl group, alkylsulfonyl group, halogen, hydroxyl group, thio group, cyano group, amino group, acylamino group, nitro group, CO ₂ D, SO ₃ D (above D Represents H, NH ₄ or an alkyl group), CONR ⁸ R ⁹ (wherein R ⁸ and R ⁹ are the same or different from each other and represent H or an alkyl group), an aryl group, an aralkyl group Group, aryloxy group, arylthio group, arylsulfinyl group, arylsulfonyl group, or adjacent groups together, an alkylenedioxy group, a crown ether residue or —CO—NR ¹⁰ —CO— (where R ¹⁰ is H, an alkyl group, a formula

Or expression

An acid imide group represented by (1) is formed. However, the case where R ¹ to R ⁷ are all H is excluded. ]
And general formula

[Wherein B is a metal, Q is N or CR ¹⁴ , T is N or CR ¹⁵ , W is N or CR ¹⁶ and W is not N when Q and T are not N, and Q is When N is N, T is CR ¹⁵ , and when T is N, W is CR ¹⁶ and R ¹¹ to R ¹⁶ are the same as or different from each other, and H, an alkyl group, an alkenyl group, an alkynyl group, a haloalkyl group, an alkoxyalkyl group, Optionally substituted alkoxyl group, alkylthio group, alkylsulfinyl group, alkylsulfonyl group, halogen, hydroxyl group, thio group, cyano group, amino group, acylamino group, nitro group, CO ₂ G, SO ₃ G (above G Represents H, NH ₄ or an alkyl group), CONR ¹⁷ R ¹⁸ (wherein R ¹⁷ and R ¹⁸ are the same as or different from each other, and represent H or an alkyl group), An aryl group, an aralkyl group, an aryloxy group, an arylthio group, an arylsulfinyl group, an arylsulfonyl group, or adjacent groups together, an alkylenedioxy group, a crown ether residue, or —CO—NR ¹⁹ —CO -Where R ¹⁹ is H, an alkyl group, a formula

Or expression

An acid imide group represented by (1) is formed. However, when all of Q, T, and W are not N, the case where R ¹¹ to R ¹⁶ are all H is excluded. ]
Wherein at least one selected from a substituted metal phthalocyanine, a substituted metal subphthalocyanine and an analog thereof represented by the formula (1) is mixed under pressure with supercritical carbon dioxide or subcritical carbon dioxide and dissolved. A method for dissolving substituted metal phthalocyanines, substituted metal subphthalocyanines and analogs thereof.
(2) The substituted metal phthalocyanine or subphthalocyanine having a metal selected from the group consisting of Cu, Fe, Al, Ni, Co, Zn, Ti, Cr, V, Rh, Ru, Si, and Mo as the central metal ( 1) The method described.
(3) Further, selected from hydrocarbon solvents, halogenated hydrocarbon solvents, alcohol solvents, ether solvents, acetal solvents, ketone solvents, ester solvents, nitrogen compound solvents and sulfur compound solvents. The total amount of supercritical carbon dioxide or subcritical carbon dioxide / supercritical carbon dioxide or subcritical carbon dioxide is used in combination at a ratio not exceeding 50% by volume ratio The method according to (1) or (2).
(4) The method according to (3) above, wherein the ratio of the quasi-solvent used is in the range of 0.1 to 10%.
(5) The method according to any one of (1) to (4), wherein the quasi-solvent is pyridine, imidazole, methanol or ethanol.
(6) Dissolving is performed under supercritical carbon dioxide, under the operating conditions of a temperature of 31.1 ° C. to 500 ° C. and a pressure of 7.38 MPa to 50 MPa. ) To (5).
(7) A solution of a substituted metal phthalocyanine, a substituted metal subphthalocyanine or an analog thereof obtained by the method according to any one of (1) to (6).

  In the method of the present invention, the compound subjected to dissolution is a specific substitute of metal phthalocyanine or metal subphthalocyanine, an analog in which a specific position of the benzene ring is replaced with nitrogen at one position or two positions, and a corresponding non-substituted Which are represented by the following general formulas.

［式中、Ｍは金属であり、ＸはＮ又はＣＲ⁵、ＹはＮ又はＣＲ⁶、ＺはＮ又はＣＲ⁷であって、しかもＸ及びＹ共にＮでないときＺもＮではなく、ＸがＮのときＹはＣＲ⁶、ＹがＮのときＺはＣＲ⁷であり、Ｒ¹ないしＲ⁷は互いに同一或いは異なって、Ｈ、アルキル基、アルケニル基、アルキニル基、ハロアルキル基、アルコキシアルキル基、置換されていてもよいアルコキシル基、アルキルチオ基、アルキルスルフィニル基、アルキルスルホニル基、ハロゲン、水酸基、チオ基、シアノ基、アミノ基、アシルアミノ基、ニトロ基、ＣＯ₂Ｄ、ＳＯ₃Ｄ（以上のＤはＨ、ＮＨ₄又はアルキル基を示す）、ＣＯＮＲ⁸Ｒ⁹（ここでＲ⁸、Ｒ⁹は互いに同一或いは異なって、Ｈ又はアルキル基を示す）、アリール基、アラルキル基、アリールオキシ基、アリールチオ基、アリールスルフィニル基又はアリールスルホニル基であるか、或いは隣接するもの同士で一緒に、アルキレンジオキシ基、クラウンエーテル残基又は−ＣＯ−ＮＲ¹⁰−ＣＯ−（ここでＲ¹⁰はＨ、アルキル基、式

又は式

で表わされる基を示す）で表わされる酸イミド基を形成する。但し、Ｒ¹ないしＲ⁷が全てＨである場合を除く。］
で表わされる置換金属フタロシアニン又はその類縁体。 Formula (I)

[Wherein M is a metal, X is N or CR ⁵ , Y is N or CR ⁶ , Z is N or CR ⁷ , and when X and Y are not N, Z is not N, and X is Y is CR ⁶ when N, Z is CR ⁷ when Y is N, and R ¹ to R ⁷ are the same or different from each other, and H, alkyl group, alkenyl group, alkynyl group, haloalkyl group, alkoxyalkyl group, Optionally substituted alkoxyl group, alkylthio group, alkylsulfinyl group, alkylsulfonyl group, halogen, hydroxyl group, thio group, cyano group, amino group, acylamino group, nitro group, CO ₂ D, SO ₃ D (above D is H, shows the NH ₄ or an alkyl group), CONR ⁸ R ⁹ (wherein R ^8, R ⁹ are the same or different from each other, represent H or an alkyl group), an aryl group, an aralkyl group, an aryloxy , Arylthio group, or an aryl sulfinyl group or an arylsulfonyl group, or together with each other adjacent ones, alkylenedioxy groups, crown ether residue or -CO-NR ¹⁰ -CO- (wherein R ¹⁰ is H, Alkyl group, formula

Or expression

An acid imide group represented by (1) is formed. However, the case where R ¹ to R ⁷ are all H is excluded. ]
A substituted metal phthalocyanine represented by the formula:

［式中、Ｂは金属であり、ＱはＮ又はＣＲ¹⁴、ＴはＮ又はＣＲ¹⁵、ＷはＮ又はＣＲ¹⁶であって、しかもＱ及びＴ共にＮでないときＷもＮではなく、ＱがＮのときＴはＣＲ¹⁵、ＴがＮのときＷはＣＲ¹⁶であり、Ｒ¹¹ないしＲ¹⁶は互いに同一或いは異なって、Ｈ、アルキル基、アルケニル基、アルキニル基、ハロアルキル基、アルコキシアルキル基、置換されていてもよいアルコキシル基、アルキルチオ基、アルキルスルフィニル基、アルキルスルホニル基、ハロゲン、水酸基、チオ基、シアノ基、アミノ基、アシルアミノ基、ニトロ基、ＣＯ₂Ｇ、ＳＯ₃Ｇ（以上のＧはＨ、ＮＨ₄又はアルキル基を示す）、ＣＯＮＲ¹⁷Ｒ¹⁸（ここでＲ¹⁷、Ｒ¹⁸は互いに同一或いは異なって、Ｈ又はアルキル基を示す）、アリール基、アラルキル基、アリールオキシ基、アリールチオ基、アリールスルフィニル基又はアリールスルホニル基であるか、或いは隣接するもの同士で一緒に、アルキレンジオキシ基、クラウンエーテル残基又は−ＣＯ−ＮＲ¹⁹−ＣＯ−（ここでＲ¹⁹はＨ、アルキル基、式

又は式

で表わされる基を示す）で表わされる酸イミド基を形成する。但し、Ｑ、Ｔ及びＷがいずれもＮでないとき、Ｒ¹¹ないしＲ¹⁶が全てＨである場合を除く。］
で表わされる置換金属サブフタロシアニン及びその類縁体。 Formula (II)

[Wherein B is a metal, Q is N or CR ¹⁴ , T is N or CR ¹⁵ , W is N or CR ¹⁶ , and W is not N when Q and T are not N, and Q is When N is N, T is CR ¹⁵ , and when T is N, W is CR ¹⁶ and R ¹¹ to R ¹⁶ are the same or different from each other, and H, alkyl group, alkenyl group, alkynyl group, haloalkyl group, alkoxyalkyl group, Optionally substituted alkoxyl group, alkylthio group, alkylsulfinyl group, alkylsulfonyl group, halogen, hydroxyl group, thio group, cyano group, amino group, acylamino group, nitro group, CO ₂ G, SO ₃ G (above G is H, shows the NH ₄ or an alkyl group), CONR ¹⁷ R ¹⁸ (wherein R ^17, R ¹⁸ are the same or different from each other, represent H or an alkyl group), an aryl group, an aralkyl group, aryl Or oxy group, arylthio group, aryl sulfinyl group or an arylsulfonyl group, or together with each other adjacent ones, alkylenedioxy groups, crown ether residue or -CO-NR ¹⁹ -CO- (wherein R ¹⁹ is H, alkyl group, formula

Or expression

An acid imide group represented by (1) is formed. However, when Q, T and W are not all N, the case where R ¹¹ to R ¹⁶ are all H is excluded. ]
A substituted metal subphthalocyanine represented by the formula:

The substituents in the compounds represented by the general formula (I) and the general formula (II) (hereinafter also referred to as target compounds) will be described below.
The alkyl group may be a methyl group, a propyl group or the like, and preferably a branched alkyl group such as an isopropyl group or a t-butyl group, an ethyl group, or the like.
Alkenyl groups include aryl groups, 3,3- dimethylbutenyl groups, alkynyl groups include 3,3-dimethylbutynyl groups, haloalkyl groups include fluoromethyl groups, trifluoroethyl groups, etc., alkoxyalkyl groups Methoxymethyl group, ethoxymethyl group, methoxyethyl group, etc., optionally substituted alkoxyl groups include methoxy group, ethoxy group, trifluoroethoxy group, etc., and alkylthio groups include methylthio group, ethylthio group, etc. A methylsulfinyl group, an ethylsulfinyl group and the like as an alkylsulfinyl group, a methylsulfonyl group and an ethylsulfonyl group as an alkylsulfonyl group, Cl, Br, F and the like as a halogen, an acetylamino group as an acylamino group, and the like to but, CO ₂ G or SO ₃ G In the case where G is an alkyl group, the group is a methyl group, an ethyl group, a butyl group, a decyl group, the aryl group is a phenyl group, the aralkyl group is a benzyl group, a phenethyl group, or the like. As an arylthio group, a phenylthio group as an arylthio group, a phenylsulfinyl group as an arylsulfinyl group, a phenylsulfonyl group as an arylsulfonyl group, and a methylenedioxy group as an alkylenedioxy group. F, methoxy group, ethoxy group, propoxy group, butoxy group, 2,2,2-trifluoroethoxy group, t-butyl group, ethyl group, trifluoromethyl group, 2,2,2-trimethyl group Fluoroethyl group, perfluoroethyl group, etc., especially butoxy group, 2,2,2-trif Oroechiru group, perfluoroethyl group, t- butyl group, 2,2,2-trifluoroethoxy group and the like are preferable.

  The target compound is preferably selected from the group 3A to group 8 and the group 1B to group 6B in the short periodic table, more preferably Cu, Fe, Al, Ni, Co, Zn, Ti. , Cr, V, Rh, Ru, Si and Mo are preferred.

  In the method of the present invention, in order to dissolve, a hydrocarbon solvent, a halogenated hydrocarbon solvent, an alcohol solvent, an ether solvent, an acetal solvent, a ketone solvent, an ester solvent, a carboxylic acid solvent, nitrogen It is preferable to use at least one quasi-solvent selected from a compound solvent and a sulfur compound solvent in order to facilitate dissolution of the target compound.

  For these quasi-solvents, examples of hydrocarbon solvents include hexane, kerosene, benzene, toluene, and halogenated hydrocarbon solvents such as methyl chloride, chloroform, dichloromethane, dichloroethane, chlorobenzene, and the like as alcohol solvents. For example, methanol, ethanol, propanol, butanol, etc., ether solvents such as diethyl ether, tetrahydrofuran, etc., acetal solvents such as acetaldehyde diethyl acetal, etc., ketone solvents such as acetone, methyl ethyl ketone, etc. However, examples of the ester solvent include ethyl acetate and butyl acetate, and examples of the nitrogen compound solvent include acetonitrile, pyridine, N, N-dimethylformamide, imidazole, and the like. The sulfur compound-based solvents such as dimethyl sulfoxide and the like, respectively, among others pyridine, methanol, ethanol, chloroform, hexane, imidazole and the like are preferably used.

  These quasi-solvents may be used alone or in combination of two or more. When a quasi-solvent is used in combination, the ratio of use is a total amount of supercritical carbon dioxide or subcritical carbon dioxide / a range not exceeding 50% by volume with respect to supercritical carbon dioxide or subcritical carbon dioxide. , Preferably 0 to 20%, more preferably 0.1 to 10%.

  Regarding the dissolution operation, if the temperature is too low, the solubility in a predetermined solvent may be poor, and if the temperature is too high, the substituted metal phthalocyanine or subphthalocyanine may be decomposed, preferably supercritical carbon dioxide. The temperature is below the critical temperature of 31.1 ° C., the pressure is above the critical pressure of 7.38 MPa, the temperature is above the critical temperature of 31.1 ° C. and below 500 ° C., and the pressure is above the critical pressure of 7.38 MPa and above 50 MPa. It is good to carry out under the following operating conditions.

In this way, a solution of substituted metal phthalocyanine, substituted metal subphthalocyanine or an analog thereof is prepared.
This solution is useful as a raw material liquid, a coating solution or a catalyst for obtaining a fine pigment.

Moreover, this solution shows a peculiar visible ultraviolet absorption spectrum.
That is, the pressure dependence is recognized in the absorption maximum value, and the absorption maximum value also fluctuates due to pressure fluctuation. By using this property, the substituted metal phthalocyanine, the substituted metal subphthalocyanine or an analog thereof can be used as an indicator for measuring the solvent polarity.
The use as such an indicator will be described below.
Supercritical carbon dioxide and subcritical carbon dioxide are widely used in various technical fields such as the semiconductor field, the image forming field, and the electrophotographic field. For example, in production processes used for solvents, etc. Since contamination with foreign substances (for example, quasi-solvents) is likely to cause unexpected troubles, there is a strong demand for checking such contamination.
Therefore, focusing on the fact that solvent polarity fluctuates due to such contamination, a method for measuring the fluctuation can be considered, but instead of directly measuring the measurement, the indicator linked to the fluctuation is indirectly measured. Some indicator is envisaged.
The above substituted metal phthalocyanine, substituted metal subphthalocyanine or analogs thereof are stable even at high temperature, and can be used as an indicator in the low temperature region as well as the high temperature region, and supercritical dioxide under a wide range of temperature conditions. By adding this to carbon or a subcritical carbon dioxide solvent and measuring the absorption maximum value of the visible ultraviolet absorption spectrum with a photometer, it is possible to indirectly measure the fluctuation of the solvent polarity.

  According to the method of the present invention, a predetermined substituted metal phthalocyanine compound, subphthalocyanine compound, or a specific analog thereof can be easily and easily used without using an acid solvent, or a specific organic solvent or water. Can be dissolved.

  Next, the best mode for carrying out the present invention will be described by way of examples. However, the present invention is not limited to these examples.

で表わされ、式中の各符号が表１に示されるとおりの各種フタロシアニン系対象化合物を５ｍｇ封入するか、或いは該対象化合物及び準溶媒をそれぞれ５ｍｇ封入し、油浴又は水浴による３５℃の恒温槽に入れ、オートクレーブを一定温度に達せしめたのち、オートクレーブに二酸化炭素を高圧ポンプで内圧２０ＭＰａになるように圧入した。その後１時間攪拌したのち、内容液の紫外可視吸収スペクトルを測定し、対象化合物の溶解性について下記の評価基準により判定した。その結果も表１に示す。
◎：完全に溶解した。
○：溶解した。
△：目視で呈色を確認した。
×：溶解しなかった。 Contents A general formula is added to a 50 ml stainless steel autoclave with an observation window.

In the formula, 5 mg of various phthalocyanine target compounds as shown in Table 1 are encapsulated, or 5 mg of each of the target compound and quasi-solvent is encapsulated, and 35 ° C. in an oil bath or a water bath. After putting it in a thermostat and allowing the autoclave to reach a constant temperature, carbon dioxide was press-fitted into the autoclave with a high-pressure pump to an internal pressure of 20 MPa. Then, after stirring for 1 hour, the ultraviolet-visible absorption spectrum of the content liquid was measured, and the solubility of the target compound was determined according to the following evaluation criteria. The results are also shown in Table 1.
(Double-circle): It melt | dissolved completely.
○: Dissolved.
(Triangle | delta): The coloration was confirmed visually.
X: Not dissolved.

で表わされ、式中の各符号が表２に示されるとおりの、フルオロ基又はフルオロアルキル基を有する各種フタロシアニン系対象化合物に代えた以外は実施例１と同様にして溶解性について判定した。その結果も表２に示す。 The phthalocyanine-based compound of Example 1 has the general formula

The solubility was determined in the same manner as in Example 1 except that the various phthalocyanine-based compounds having a fluoro group or a fluoroalkyl group as shown in Table 2 were used. The results are also shown in Table 2.

で表わされ、式中の各符号が表３に示されるとおりの各種サブフタロシアニン系対象化合物に代えた以外は実施例１と同様にして溶解性について判定した。その結果も表３に示す。 The phthalocyanine-based compound of Example 1 has the general formula

The solubility was determined in the same manner as in Example 1 except that each symbol in the formula was replaced with various subphthalocyanine-based compounds as shown in Table 3. The results are also shown in Table 3.

で表わされ、式中の各符号が表４に示されるとおりの、α‐ピリジノポルフィラジン、β‐ピリジノポルフィラジン又はピラジノポルフィラジンに代えた以外は実施例１と同様にして溶解性について判定した。その結果も表４に示す。 The phthalocyanine-based compound of Example 1 is an analog of the general formula

And dissolved in the same manner as in Example 1 except that α-pyridinoporphyrazine, β-pyridinoporphyrazine or pyrazinoporphyrazine was used as indicated in Table 4 The sex was determined. The results are also shown in Table 4.

で表わされ、式中の各符号が表５に示されるとおりの各種対象化合物に代えた以外は実施例１と同様にして溶解性について判定した。その結果も表５に示す。 The phthalocyanine-based compound of Example 1 has the general formula

The solubility was determined in the same manner as in Example 1 except that each symbol in the formula was replaced with various target compounds as shown in Table 5. The results are also shown in Table 5.

で表わされ、式中の各符号が表６に示されるとおりの各種対象化合物に代えた以外は実施例１と同様にして溶解性について判定した。その結果も表６に示す。 The phthalocyanine-based compound of Example 1 has the general formula

The solubility was determined in the same manner as in Example 1 except that each symbol in the formula was replaced with various target compounds as shown in Table 6. The results are also shown in Table 6.

で表わされ、式中の各符号が表７に示されるとおりの各種対象化合物に代えた以外は実施例１と同様にして溶解性について判定した。その結果も表７に示す。 The phthalocyanine-based compound of Example 1 has the general formula

The solubility was determined in the same manner as in Example 1 except that each symbol in the formula was replaced with various target compounds as shown in Table 7. The results are also shown in Table 7.

で表わされ、式中の各符号が表８に示されるとおりの各種対象化合物に代えた以外は実施例１と同様にして溶解性について判定した。その結果も表８に示す。 The phthalocyanine-based compound of Example 1 has the general formula

The solubility was determined in the same manner as in Example 1 except that each symbol in the formula was replaced with various target compounds as shown in Table 8. The results are also shown in Table 8.

で示されるニッケル（ＩＩ）−２，３，９，１０，１６，１７，２３，２４−オクタキス（ブトキシ）フタロシアニンを入れ、３５℃にて各種有機溶媒を加え、１時間攪拌した後、測定を行なった。５００ｎｍ〜９００ｎｍに存在するフタロシアニンのＱ帯に相当する吸収極大の波長を記録した。これから、各有機溶媒ごとにそれを加えたフタロシアニンのそれぞれの溶媒極性（Ｅ_T（３０）値）に対するＱ帯の値の関係を求めたところ、吸収極大をλｎｍで表すと、図１に示すような該波長と該溶媒極性との相関が得られ、これより、次の数式
Ｅ_T（３０）ｋｃａｌ／ｍｏｌ＝０．６４１９×λ−４３４．７７９
で示される関係式の成り立つことが分かった。
一方、種々の圧力下の超臨界二酸化炭素に溶解させたニッケル（ＩＩ）−２，３，９，１０，１６，１７，２３，２４−オクタキス（ブトキシ）フタロシアニンの吸収スペクトルを測定した。そのスペクトルを図２に示す。その結果、７ＭＰａ以降、吸光度は減少し、吸収極大値も短波長シフトする。そのときのＥＴ（３０）値を上記数式の関係から求め、まとめた。まとめた図を図３に示す。これより、超臨界二酸化炭素は、圧力１０ＭＰａの時は、シスデカリンと同等の極性を有し、２５ＭＰａのときは、テトラメチルシランと同等の極性を有していることが分かった。このように、高圧下での超臨界二酸化炭素の溶媒極性を見積もる上で、フタロシアニンが良好なインジケーターとして利用することができる。 3ml stainless steel cell with window for visible ultraviolet absorption spectrum measurement

The nickel (II) -2,3,9,10,16,17,23,24-octakis (butoxy) phthalocyanine represented by is added, various organic solvents are added at 35 ° C., and the mixture is stirred for 1 hour. I did it. The wavelength of the absorption maximum corresponding to the Q band of phthalocyanine existing at 500 nm to 900 nm was recorded. From this, when the relationship of the Q band value to the respective solvent polarity (E _T (30) value) of phthalocyanine added with each organic solvent was determined, the absorption maximum is expressed as λ nm as shown in FIG. Thus, the correlation between the wavelength and the solvent polarity is obtained, and from this, the following formula E _T (30) kcal / mol = 0.419 × λ−434.779
It was found that the relation shown by
On the other hand, the absorption spectra of nickel (II) -2,3,9,10,16,17,23,24-octakis (butoxy) phthalocyanine dissolved in supercritical carbon dioxide under various pressures were measured. The spectrum is shown in FIG. As a result, after 7 MPa, the absorbance decreases and the absorption maximum value also shifts by a short wavelength. The ET (30) values at that time were determined from the relationship of the above mathematical formulas and summarized. The summary figure is shown in FIG. From this, it was found that supercritical carbon dioxide has the same polarity as cisdecalin when the pressure is 10 MPa, and has the same polarity as tetramethylsilane when the pressure is 25 MPa. Thus, phthalocyanine can be used as a good indicator in estimating the solvent polarity of supercritical carbon dioxide under high pressure.

The graph which shows the relationship between each solvent polarity (E _T (30) value) of phthalocyanine which added it for every organic solvent, and Q band absorption maximum wavelength. Absorption spectrum of nickel (II) -2,3,9,10,16,17,23,24-octakis (butoxy) phthalocyanine dissolved in supercritical carbon dioxide. The graph which shows the relationship between the absorption maximum value of the absorption spectrum of FIG. 2, and ET (30) value, and a pressure.

Claims (4)

General formula

[Wherein M is a metal, X is N or CR ⁵ , Y is N or CR ⁶ , Z is N or CR ⁷ , and when X and Y are not N, Z is not N, and X is Y is CR ⁶ when N, Z is CR ⁷ when Y is N, and R ¹ to R ⁷ are the same or different from each other, and H, alkyl group, alkenyl group, alkynyl group, haloalkyl group, alkoxyalkyl group, Optionally substituted alkoxyl group, alkylthio group, alkylsulfinyl group, alkylsulfonyl group, halogen, hydroxyl group, thio group, cyano group, amino group, acylamino group, nitro group, CO ₂ D, SO ₃ D (above D Represents H, NH ₄ or an alkyl group), CONR ⁸ R ⁹ (wherein R ⁸ and R ⁹ are the same or different from each other and represent H or an alkyl group), an aryl group, an aralkyl group Group, aryloxy group, arylthio group, arylsulfinyl group, arylsulfonyl group, or adjacent groups together, an alkylenedioxy group, a crown ether residue or —CO—NR ¹⁰ —CO— (where R ¹⁰ is H, an alkyl group, a formula

Or expression

An acid imide group represented by (1) is formed. However, the case where R ¹ to R ⁷ are all H is excluded. ]
And general formula

[Wherein B is a metal, Q is N or CR ¹⁴ , T is N or CR ¹⁵ , W is N or CR ¹⁶ , and when Q and T are not N, W is not N, and Q is When N is N, T is CR ¹⁵ , and when T is N, W is CR ¹⁶ and R ¹¹ to R ¹⁶ are the same as or different from each other, and H, an alkyl group, an alkenyl group, an alkynyl group, a haloalkyl group, an alkoxyalkyl group, Optionally substituted alkoxyl group, alkylthio group, alkylsulfinyl group, alkylsulfonyl group, halogen, hydroxyl group, thio group, cyano group, amino group, acylamino group, nitro group, CO ₂ G, SO ₃ G (above G Represents H, NH ₄ or an alkyl group), CONR ¹⁷ R ¹⁸ (wherein R ¹⁷ and R ¹⁸ are the same as or different from each other, and represent H or an alkyl group), An aryl group, an aralkyl group, an aryloxy group, an arylthio group, an arylsulfinyl group, an arylsulfonyl group, or adjacent groups together, an alkylenedioxy group, a crown ether residue, or —CO—NR ¹⁹ —CO -Where R ¹⁹ is H, an alkyl group, a formula

Or expression

An acid imide group represented by (1) is formed. However, when all of Q, T, and W are not N, the case where R ¹¹ to R ¹⁶ are all H is excluded. ]
Wherein at least one selected from a substituted metal phthalocyanine, a substituted metal subphthalocyanine and an analog thereof represented by the formula (1) is mixed under pressure with supercritical carbon dioxide or subcritical carbon dioxide and dissolved. A method for dissolving substituted metal phthalocyanines, substituted metal subphthalocyanines and analogs thereof.   The substituted metal phthalocyanine or subphthalocyanine has, as its central metal, one selected from the group consisting of Cu, Fe, Al, Ni, Co, Zn, Ti, Cr, V, Rh, Ru, Si and Mo. Method. From being dissolved, and supercritical carbon dioxide under temperature 31.1 ° C. critical temperature above 500 ° C. or less, according to claim 1 or 2, wherein the pressure is carried out under the following operating conditions critical pressure on 50MPa of 7.38MPa the method of. A solution of a substituted metal phthalocyanine, a substituted metal subphthalocyanine or an analog thereof obtained by the method according to any one of claims 1 to 3 .

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