JP7053285B2 - Phthalocyanine compound - Google Patents

Description

The present invention relates to a novel phthalocyanine compound.

Various display devices such as a liquid crystal display device, a solid-state image sensor, and a touch panel type display device are provided with a color filter for realizing color display. Further, the sensors of various display devices have sensitivity not only to visible light but also to infrared rays. Therefore, an infrared cut filter (IRCF) containing a near-infrared absorber is used to block infrared rays transmitted through the color filter. Patent Document 1 discloses a phthalocyanine pigment such as octachlorohepta (benzylamino) copper phthalocyanine as a near-infrared absorber. Further, as a phthalocyanine compound, a colorant disclosed in Patent Document 2 is also known. Further, Patent Document 3 discloses a composition for shielding heat rays, which comprises a phthalocyanine-based infrared absorber and an ultraviolet absorber.

Japanese Unexamined Patent Publication No. 9-52894 Japanese Unexamined Patent Publication No. 2004-83674 Japanese Unexamined Patent Publication No. 10-77360

However, as a result of studies by the present inventors, it was found that the phthalocyanine compound disclosed in Patent Document 1 is not sufficiently absorbed in the near infrared region. Further, the phthalocyanine compound disclosed in Patent Document 2 is assumed to be used as a "colorant", and like Patent Document 1, absorption in the near infrared region is not sufficient. Further, the phthalocyanine compound disclosed in Patent Document 3 is very expensive and is not practical for use in an inexpensive heat ray shielding film.

Therefore, the present invention has set the subject of providing a novel phthalocyanine compound showing good absorption in the near infrared region.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the phthalocyanine compound represented by the formula (I) can solve the above-mentioned problems, and completed the present invention.

［式（Ｉ）中、
Ｍは、非金属、金属、金属酸化物または金属ハロゲン化物を表す。
Ｒ¹¹～Ｒ²⁶は、それぞれ独立して、水素原子、塩素原子、臭素原子または式（Ａ）で表される置換基を表し、Ｒ¹¹～Ｒ²⁶の１つ以上は臭素原子であり、Ｒ¹¹～Ｒ²⁶の１つ以上は式（Ａ）で表される置換基である。］

［式（Ａ）中、
Ｒ¹は、水素原子、置換基を有していてもよい炭素数１～２０のアルキル基、置換基を有していてもよい炭素数６～２０のアリール基、置換基を有していてもよい炭素数７～２０のアラルキル基、または置換基を有していてもよい複素環基である。
Ｒ²は、置換基を有していてもよい炭素数１～２０のアルキレン基である。
Ｒ³は、置換基を有していてもよい炭素数１～２０のアルキル基、置換基を有していてもよい炭素数１～２０のアルコキシ基、置換基を有していてもよい炭素数２～８のアルコキシカルボニル基、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基、アミノ基、または置換基を有していてもよい炭素数１～２０のアルキルアミノ基である。
ｍは、０以上５以下の整数を表す。
＊は、結合手である。
式（Ａ）で表される基が２以上の場合、複数の式（Ａ）で表される基は同一でも異なっていてもよい。またｍが２以上の場合、複数の－Ｒ³は同一でも異なっていてもよい。］
［２］ Ｒ¹が水素原子である［１］に記載のフタロシアニン化合物。
［３］ Ｒ²が置換基を有していてもよいメチレン基、エチレン基またはプロピレン基である［１］または［２］に記載のフタロシアニン化合物。
［４］ 前記Ｍが金属である［１］～［３］のいずれか１項に記載のフタロシアニン化合物。
［５］ Ｒ¹¹～Ｒ²⁶における臭素原子の合計数が、Ｒ¹¹～Ｒ²⁶における塩素原子の合計数よりも多い［１］～［４］のいずれか１項に記載のフタロシアニン化合物。
［６］ 式（Ａ）が、式（Ａ－ａ）、式（Ａ－ｂ）、式（Ａ－ｃ）または式（Ａ－ｄ）である［１］～［５］のいずれか１項に記載のフタロシアニン化合物。

［式（Ａ－ａ）、式（Ａ－ｂ）、式（Ａ－ｃ）及び式（Ａ－ｄ）中、Ｒ³及びｍは前記に同じ。］ That is, the phthalocyanine compound according to the present invention has the following points.
[1] A phthalocyanine compound represented by the formula (I).

[In formula (I),
M represents a non-metal, metal, metal oxide or metal halide.
R ¹¹ to R ²⁶ each independently represent a hydrogen atom, a chlorine atom, a bromine atom or a substituent represented by the formula (A), and one or more of R ¹¹ to R ²⁶ are bromine atoms, and R One or more of ¹¹ to R ²⁶ is a substituent represented by the formula (A). ]

[In formula (A),
R ¹ has a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, and a substituent. It is also a good aralkyl group having 7 to 20 carbon atoms, or a heterocyclic group which may have a substituent.
R ² is an alkylene group having 1 to 20 carbon atoms which may have a substituent.
R ³ has an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, and carbon which may have a substituent. It is an alkylamino group having 1 to 20 carbon atoms which may have an alkoxycarbonyl group of 2 to 8, a halogen atom, a nitro group, a hydroxy group, a formyl group, an amino group, or a substituent.
m represents an integer of 0 or more and 5 or less.
* Is a bond.
When the number of groups represented by the formula (A) is two or more, the groups represented by the plurality of formulas (A) may be the same or different. Further, when m is 2 or more, a plurality of -R ³ may be the same or different. ]
[2] The phthalocyanine compound according to [1], wherein R ¹ is a hydrogen atom.
[3] The phthalocyanine compound according to [1] or [2], wherein R ² is a methylene group, an ethylene group or a propylene group which may have a substituent.
[4] The phthalocyanine compound according to any one of [1] to [3], wherein M is a metal.
[5] The phthalocyanine compound according to any one of [1] to [4], wherein the total number of bromine atoms in R ¹¹ to R ²⁶ is larger than the total number of chlorine atoms in R ¹¹ to R ²⁶ .
[6] Any one of [1] to [5], wherein the formula (A) is the formula (Aa), the formula (Ab), the formula (Ac) or the formula (Ad). The phthalocyanine compound described in.

[In the formula (Aa), the formula (Ab), the formula (Ac) and the formula (Ad), R ³ and m are the same as described above. ]

INDUSTRIAL APPLICABILITY According to the present invention, a novel phthalocyanine compound showing good absorption in the near infrared region is provided.

［式（Ｉ）中、
Ｍは、非金属、金属、金属酸化物または金属ハロゲン化物を表す。
Ｒ¹¹～Ｒ²⁶は、それぞれ独立して、水素原子、塩素原子、臭素原子または式（Ａ）で表される置換基を表し、Ｒ¹¹～Ｒ²⁶の１つ以上は臭素原子であり、Ｒ¹¹～Ｒ²⁶の１つ以上は式（Ａ）で表される置換基である。］

［式（Ａ）中、
Ｒ¹は、水素原子、置換基を有していてもよい炭素数１～２０のアルキル基、置換基を有していてもよい炭素数６～２０のアリール基、置換基を有していてもよい炭素数７～２０のアラルキル基、または置換基を有していてもよい複素環基である。
Ｒ²は、置換基を有していてもよい炭素数１～２０のアルキレン基である。
Ｒ³は、置換基を有していてもよい炭素数１～２０のアルキル基、置換基を有していてもよい炭素数１～２０のアルコキシ基、置換基を有していてもよい炭素数２～８のアルコキシカルボニル基、ハロゲン原子、ニトロ基、ヒドロキシ基、ホルミル基、アミノ基、または置換基を有していてもよい炭素数１～２０のアルキルアミノ基である。
ｍは、０以上５以下の整数を表す。
＊は、結合手である。
式（Ａ）で表される基が２以上の場合、複数の式（Ａ）で表される基は同一でも異なっていてもよい。またｍが２以上の場合、複数の－Ｒ³は同一でも異なっていてもよい。］ 1. 1. Phthalocyanine compound The present invention relates to a phthalocyanine compound represented by the formula (I) (hereinafter, may be referred to as a phthalocyanine compound (I)).

[In formula (I),
M represents a non-metal, metal, metal oxide or metal halide.
R ¹¹ to R ²⁶ each independently represent a hydrogen atom, a chlorine atom, a bromine atom or a substituent represented by the formula (A), and one or more of R ¹¹ to R ²⁶ are bromine atoms, and R One or more of ¹¹ to R ²⁶ is a substituent represented by the formula (A). ]

[In formula (A),
R ¹ has a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, and a substituent. It is also a good aralkyl group having 7 to 20 carbon atoms, or a heterocyclic group which may have a substituent.
R ² is an alkylene group having 1 to 20 carbon atoms which may have a substituent.
R ³ has an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, and carbon which may have a substituent. It is an alkylamino group having 1 to 20 carbon atoms which may have an alkoxycarbonyl group of 2 to 8, a halogen atom, a nitro group, a hydroxy group, a formyl group, an amino group, or a substituent.
m represents an integer of 0 or more and 5 or less.
* Is a bond.
When the number of groups represented by the formula (A) is two or more, the groups represented by the plurality of formulas (A) may be the same or different. Further, when m is 2 or more, a plurality of -R ³ may be the same or different. ]

In formula (I), M is non-metal, which means that M is an atom other than metal, for example, two hydrogen atoms. Examples of the metal represented by M include iron, magnesium, nickel, cobalt, copper, palladium, zinc and the like. Examples of the metal oxide represented by M include titanyl and vanadyl. Examples of the metal halide represented by M include aluminum chloride, aluminum iodide, indium chloride, germanium chloride, tin chloride, silicon chloride and the like. As M, metal is more preferable, and copper is further preferable.

The number of bromine atoms in R ¹¹ to R ²⁶ is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, preferably 15 or less, more preferably 12 or less, still more preferably. 9 or less. As the number of bromine atoms increases, the wavelength of the phthalocyanine compound (I) becomes longer.

Further, it is desirable that the total number of bromine atoms in R ¹¹ to R ²⁶ is larger than the total number of chlorine atoms in R ¹¹ to R ²⁶ .

The number of substituents represented by the formula (A) in R ¹¹ to R ²⁶ is preferably 2 or more, more preferably 3 or more, preferably 10 or less, more preferably 8 or less, and further. The number is preferably 6 or less, and particularly preferably 5 or less.

The total number of chlorine atoms, bromine atoms, and substituents represented by the formula (A) in R ¹¹ to R ²⁶ is preferably 10 or more, more preferably 13 or more, still more preferably 15 or more. , Particularly preferably 16.

In formula (I), it is desirable that R ¹¹ , R ¹⁴ , R ¹⁵ , R ¹⁸ , R ¹⁹ , R ²² , R ²³ , and R ²⁶ are independently chlorine or bromine atoms, respectively.

Further, one or more selected from R ¹² , R ¹³ , R ¹⁶ , R ¹⁷ , R ²⁰ , R ²¹ , R ²⁴ , and R ²⁵ are preferably substituents represented by the formula (A). At least one of R ¹² to R ¹³ , at least one of R ¹⁶ to R ¹⁷ , at least one of R ²⁰ to R ²¹ , or at least one of R ²⁴ to R ²⁵ is a substituent represented by the formula (A). Is desirable.

The alkyl groups having 1 to 20 carbon atoms in R ¹ and R ³ are linear, branched or cyclic, and the alkyl groups preferably have 1 to 8 carbon atoms.
The linear or divided alkyl group has more preferably 1 to 8 carbon atoms, and further preferably 1 to 4 carbon atoms. Specific examples of the linear or split-chain alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and n. -Pentyl group, isopentyl group, neopentyl group, 1,2-dimethylpropyl group and the like can be mentioned.
The cyclic alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 8 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like.

The aryl group in R ¹ preferably has 6 to 12 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a naphthyl group, an anthryl group, a phenanthryl group and the like.

The carbon number of the aralkyl group in R ¹ is preferably 7 to 12. Examples of the aralkyl group include a benzyl group, a phenethyl group, an α-methylbenzyl group and the like.

The heterocyclic group in R ¹ is preferably a heterocyclic group having at least one selected from an oxygen atom, a sulfur atom, and a nitrogen atom as a constituent atom of the ring, and specifically, a frill group and a thienyl group. Examples thereof include a group, a pyridyl group, a quinolyl group, a piperidino group, a morpholino group, a piperidyl group and the like.

The alkyl group represented by R ¹ and R ³ may have a substituent, and the substituent has an alkoxy group having 1 to 20 carbon atoms and a substituent which may have a substituent. May have an alkoxycarbonyl group having 2 to 8 carbon atoms, a halogen atom, a nitro group, a hydroxy group, an amino group, an alkylamino group having 1 to 20 carbon atoms, a formyl group, and a carbamoyl. Examples thereof include an alkylaminocarbonyl group having 2 to 21 carbon atoms which may have a group and a substituent, an alkoxysulfonyl group having 1 to 20 carbon atoms which may have a substituent and the like. Of these, an amino group is preferable as the substituent of the alkyl group represented by R ³ .

The aryl group, aralkyl group, and heterocyclic group represented by R ¹ may have a substituent, and the substituent may be an alkyl group having 1 to 20 carbon atoms which may have a substituent. , An aryl group having 6 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent. An alkoxycarbonyl group of 8, an aryloxycarbonyl group having 7 to 21 carbon atoms which may have a substituent, an alkylsulfonyloxycarbonyl group having 2 to 21 carbon atoms which may have a substituent, a halogen atom, A nitro group, a hydroxy group, an amino group, an alkylamino group having 1 to 20 carbon atoms which may have a substituent, an arylamino group having 6 to 20 carbon atoms which may have a substituent, a formyl group, and the like. It may have an alkanoyl group having 2 to 21 carbon atoms which may have a substituent, a carbamoyl group, an alkylaminocarbonyl group having 2 to 21 carbon atoms which may have a substituent, and a substituent. Examples thereof include an alkoxysulfonyl group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms which may have a substituent, an oxyalkyl ether group and the like.

The alkyl group represented by R ¹ and R ³ , and the aryl group, aralkyl group, and heterocyclic group represented by R ¹ may have one or more of the substituents, and the substituents may be present. When there are a plurality of substituents, the substituents may be the same type or different types.

The alkyl group having 1 to 20 carbon atoms in the substituent is the same as the alkyl group represented by R ¹ and R ³ , and the alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 8 carbon atoms. 4. The alkyl group may have a substituent, and examples of the substituent include the same substituents that the alkyl groups represented by R ¹ and R ³ may have.

The aryl group in the substituent is the same as the aryl group in R ¹ . The aryl group may have a substituent, and examples of the substituent include the same substituents that the aryl group in R ¹ may have.

The alkoxy group having 1 to 20 carbon atoms in the substituent is a group in which a linear, branched or cyclic alkyl group is bonded to an oxygen atom. The alkoxy group has preferably 1 to 8 carbon atoms. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group and the like. The alkoxy group may have a substituent, and examples of the substituent include the same substituents that the alkyl groups represented by R ¹ and R ³ may have.

The alkoxycarbonyl group having 2 to 8 carbon atoms in the substituent is an alkoxycarbonyl group having a linear, branched or cyclic alkyl group moiety which may contain a hetero atom, and the alkoxycarbonyl group has the carbon number of carbon. It is preferably 2 to 5. Specific examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group and the like. The alkoxycarbonyl group may have a substituent, and examples of the substituent include the same substituents that the alkyl groups represented by R ¹ and R ³ may have.

Examples of the halogen atom in the substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the alkanoyl group having 2 to 21 carbon atoms in the substituent include an acetyl group, an ethylcarbonyl group, a propylcarbonyl group, a butylcarbonyl group, a pentylcarbonyl group, a hexylcarbonyl group, a benzoyl group, a p-tert-butylbenzoyl group and the like. Can be mentioned. The alkanoyl group may have a substituent, and examples of the substituent include the same substituents that the alkyl group represented by R ¹ may have.

The alkylamino group having 1 to 20 carbon atoms in the substituent is an alkylamino group having a linear, branched or cyclic alkyl group portion, and the alkylamino group preferably has 1 to 8 carbon atoms. Is. Specific examples of the alkylamino group include monoalkylamino groups such as methylamino group, ethylamino group and n-propylamino group; and dialkylamino groups such as 2-ethylhexylamino group, dimethylamino group and diethylamino group; And so on. The alkylamino group may have a substituent, and examples of the substituent include the same substituents that the alkyl groups represented by R ¹ and R ³ may have.

Further, the alkyl group of the alkylsulfonyloxycarbonyl group, the alkylaminocarbonyl group and the alkylthio group in the substituent is the same as the alkyl group having 1 to 20 carbon atoms represented by R ¹ and R ³ , and these groups are the same. It may have a substituent, and examples of the substituent include the same substituents that the alkyl groups represented by R ¹ and R ³ may have.
Further, the aryl group of the aryloxycarbonyl group and the arylamino group in the substituent is the same as the aryl group having 6 to 20 carbon atoms in ^R1 . These groups may have a substituent, and examples of the substituent include the same substituents that the aryl group in R ¹ may have.
Further, the alkoxy group of the alkoxysulfonyl group in the substituent is the same as the alkoxy group in the substituent, and the alkoxysulfonyl group may have a substituent, and the substituents are R ¹ and R ³ . Examples are similar to the substituents that the represented alkyl group may have.

In formula (A), R ¹ is preferably a hydrogen atom.

In the formula (A), the alkylene group having 1 to 20 carbon atoms represented by R ² may be linear, branched or cyclic. The carbon number of the alkylene group represented by R ² is preferably 10 or less, more preferably 5 or less, still more preferably 3 or less. In the formula (A), the alkylene group having 1 to 20 carbon atoms represented by R ² is preferably a methylene group (-CH _2- ), an ethylene group (-CH ₂ CH _2- ) or a propylene group (-CH (-CH ()). It is CH ₃ ) -CH _2- ), and is particularly preferably a methylene group.

Further, the alkylene group having 1 to 20 carbon atoms represented by R ² may have a substituent, and the substituent may be an aryl group having 6 to 20 carbon atoms which may have a substituent or the like. Can be mentioned. Examples of the aryl group and the substituent of the aryl group include the same substituents that the aryl group in R ¹ and the aryl group in R ¹ may have. The substituent of the alkylene group having 1 to 20 carbon atoms represented by R ² is preferably a phenyl group.

R ³ is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, a halogen atom, or an amino group. , More preferably a methyl group, an ethyl group, an aminomethyl group, an aminoethyl group, a methoxy group, an ethoxy group, a chlorine atom, a bromine atom, or an amino group.

In the formula (A), m is preferably 4 or less, more preferably 3 or less, still more preferably 2 or less, still more preferably 0 or 1 or more.

［式（Ａ－ａ）、式（Ａ－ｂ）、式（Ａ－ｃ）及び式（Ａ－ｄ）中、Ｒ³及びｍは前記に同じ。］ The formula (A) is preferably the formula (Aa), the formula (Ab), the formula (Ac) or the formula (Ad), and more preferably the formula (Aa), the formula (A). Ac) or formula (Ad).

[In the formula (Aa), the formula (Ab), the formula (Ac) and the formula (Ad), R ³ and m are the same as described above. ]

Preferred examples of the formula (A) include formulas (A-1) to (A-20), among which formulas (A-1) to (A-4) or formulas (A-17) to (A). -20) is more preferable. As the formula (A), (A-3), (A-4), (A-5), (A-9), (A-13), or (A-17) is more preferable, and the formula (A) is more preferable. -3) or the formula (A-17) is more preferable. In the formulas (A-1) to (A-20), * is a bond.

［式（Ａ－５）～（Ａ－８）中、ｎ１は１以上３以下の整数（好ましくは１または２、より好ましくは１）である。］

[In the formulas (A-5) to (A-8), n1 is an integer of 1 or more and 3 or less (preferably 1 or 2, more preferably 1). ]

［式（Ａ－９）～（Ａ－１２）中、ｎ２は１以上３以下の整数（好ましくは１または２、より好ましくは１）である。Ｒ³¹は、メチレン基またはエチレン基（好ましくはメチレン基）である。］

[In the formulas (A-9) to (A-12), n2 is an integer of 1 or more and 3 or less (preferably 1 or 2, more preferably 1). R ³¹ is a methylene group or an ethylene group (preferably a methylene group). ]

［式（Ａ－１３）～（Ａ－１６）中、ｎ３は１以上３以下の整数（好ましくは１または２、より好ましくは１）である。Ｒ³²は、炭素数１～３のアルキル基（好ましくはメチル基またはエチル基）である。］

[In the formulas (A-13) to (A-16), n3 is an integer of 1 or more and 3 or less (preferably 1 or 2, more preferably 1). R ³² is an alkyl group having 1 to 3 carbon atoms (preferably a methyl group or an ethyl group). ]

［式（Ａ－１７）～（Ａ－２０）中、ｎ４は１以上３以下の整数（好ましくは１または２、より好ましくは１）である。Ｒ³³は、ハロゲン原子（好ましくは塩素原子）である。］

[In the formulas (A-17) to (A-20), n4 is an integer of 1 or more and 3 or less (preferably 1 or 2, more preferably 1). R ³³ is a halogen atom (preferably a chlorine atom). ]

The following are exemplified as preferable phthalocyanine compound (I). In the following, "{number of substituents represented by the formula (A) in R ¹¹ to R ²⁶ (substituents represented by the formula (A))}-{number of chlorine atoms in R ¹¹ to R ²⁶ ( The phthalocyanine compound (I) is listed by the notation " ^Chloro )}-{Number of bromine atoms in R11 to ^R26 (bromo)}-Copper phthalocyanine", but the substituent represented by the formula (A), the chlorine atom, The total number of bromine atoms does not exceed 16.
・ {Tri-penta (2-chlorobenzylamino)}-{hexa-tetra (chloro)}-{hepta (bromo)}-copper phthalocyanine ・ {tri-penta (3-chlorobenzylamino)}-{hexa-tetra (Chloro)}-{Hepta (bromo)}-Copper phthalocyanine · {Tri-penta (4-chlorobenzylamino)}-{Hexa-tetra (chloro)}-{Hepta (bromo)}-Copper phthalocyanine · {Tri- Penta (2-methoxybenzylamino)}-{Hexa-tetra (chloro)}-{Hepta (bromo)}-Copper phthalocyanine · {Tri-penta (3-methoxybenzylamino)}-{Hexa-tetra (chloro)} -{Hepta (bromo)}-Copper phthalocyanine · {Tri-penta (4-methoxybenzylamino)}-{Hexa-tetra (chloro)}-{Hepta (bromo)}-Copper phthalocyanine · {Tri-penta (2-) Aminomethylbenzylamino)}-{Hexa-tetra (chloro)}-{Hepta (bromo)}-Copper phthalocyanine · {Tri-penta (3-aminomethylbenzylamino)}-{Hexa-tetra (chloro)}-{ Hepta (bromo)}-copper phthalocyanine {tri-penta (4-aminomethylbenzylamino)}-{hexa-tetra (chloro)}-{hepta (bromo)}-copper phthalocyanine-{tri-penta (2-amino) Benzylamino)}-{Hexa-tetra (chloro)}-{Hepta (bromo)}-Copper phthalocyanine · {Tri-penta (3-aminobenzylamino)}-{Hexa-tetra (chloro)}-{Hepta (bromo) )}-Copper phthalocyanine {tri-penta (4-aminobenzylamino)}-{hexa-tetra (chloro)}-{hepta (bromo)}-copper phthalocyanine {tri-penta (1-phenylethylamino)} -{Hexa-tetra (chloro)}-{Hepta (bromo)}-Copper phthalocyanine · {Tri-penta (1,1-diphenylmethylamino)}-{Hexa-tetra (chloro)}-{Hepta (bromo)} -Copper phthalocyanine {tri-penta (2-chlorobenzylamino)}-{Hepta-penta (chloro)}-{hexa (bromo)}-copper phthalocyanine-{tri-penta (3-chlorobenzylamino)}-{ Hepta-penta (chloro)}-{hexa (bromo)}-copper phthalocyanine · {tri-penta (4-chlorobenzylamino)}-{hepta-penta (chloro)}-{hexa (bromo)}-copper phthalocyanine {Tri-penta (2-methoxybenzylamino)}-{Hepta-penta (chloro)}-{hexa (bromo)}-copper phthalocyanine-{tri-penta (3-methoxybenzylamino)}-{Hepta- Penta (chloro)}-{hexa (bromo)}-copper phthalocyanine · {tri-penta (4-methoxybenzylamino)}-{hepta-penta (chloro)}-{hexa (bromo)}-copper phthalocyanine · {tri ~ Penta (2-aminomethylbenzylamino)}-{Hepta-penta (chloro)}-{Hexa (bromo)}-Copper phthalocyanine · {Tri-penta (3-aminomethylbenzylamino)}-{Hepta-penta ( Chloro)}-{Hexa (bromo)}-Copper phthalocyanine · {Tri-penta (4-aminomethylbenzylamino)}-{Hepta-penta (chloro)}-{Hexa (bromo)}-Copper phthalocyanine · {Tri- Penta (2-aminobenzylamino)}-{Hepta-penta (chloro)}-{Hexa (bromo)}-Copper phthalocyanine · {Tri-penta (3-aminobenzylamino)}-{Hepta-penta (chloro)} -{Hexa (bromo)}-Copper phthalocyanine · {Tri-penta (4-aminobenzylamino)}-{Hepta-penta (chloro)}-{Hexa (bromo)}-Copper phthalocyanine · {Tri-penta (1-) Phenylethylamino)}-{hepta-penta (chloro)}-{hexa (bromo)}-copper phthalocyanine {tri-penta (1,1-diphenylmethylamino)}-{hepta-penta (chloro)}-{ Hexa (bromo)} -copper phthalocyanine and the like are exemplified.

The phthalocyanine compound (I) is, for example, a compound represented by the formula (X) (hereinafter, may be referred to as a compound (X)) and an amine compound represented by the formula (Y) (hereinafter, an amine compound (Y). ) Can be produced by reacting).

［式（Ｘ）中、
Ｍは、非金属、金属、金属酸化物または金属ハロゲン化物を表す。
Ｒ¹¹¹～Ｒ¹²⁶は、それぞれ独立して、水素原子、塩素原子または臭素原子を表し、Ｒ¹¹¹～Ｒ¹²⁶の１つ以上は臭素原子であり、Ｒ¹¹¹～Ｒ¹²⁶の１つ以上は塩素原子である。］

[In formula (X),
M represents a non-metal, metal, metal oxide or metal halide.
R ¹¹¹ to R ¹²⁶ independently represent a hydrogen atom, a chlorine atom or a bromine atom, one or more of R ¹¹¹ to R ¹²⁶ is a bromine atom, and one or more of R ¹¹¹ to R ¹²⁶ is a chlorine atom. Is. ]

［式（Ｙ）中、Ｒ¹、Ｒ²、Ｒ³及びｍは前記に同じ。］

[In formula (Y), R ¹ , R ² , R ³ and m are the same as described above. ]

The amount of the amine compound (Y) used in reacting the compound (X) with the amine compound (Y) is preferably 1-fold mol or more, more preferably 5-fold mol or more, still more preferably 5 times mol or more with respect to the compound (X). It is 30 times mol or more, preferably 100 times mol or less, more preferably 90 times mol or less, and further preferably 80 times mol or less.

The reaction between the compound (X) and the amine compound (Y) can be carried out either in the presence of a solvent or in the absence of a solvent (that is, in the presence of the amine compound (Y)). Examples of the solvent that can be used include N-methyl-pyrrolidone (more specifically, 1-methyl-2-pyrrolidone, etc.), an amide-based solvent such as N, N-dimethylformamide, a nitro-based solvent such as pyridine, and benzo. Examples thereof include a nitrile solvent such as nitrile and dimethyl sulfoxide. Only one of these solvents may be used, or two or more of these solvents may be used in combination. The amount (total) of the solvent used is preferably 1 to 100 times by mass, more preferably 1 to 50 times by mass with respect to the compound (X) and the amine compound (Y).

In the reaction between the compound (X) and the amine compound (Y), the reaction temperature may be appropriately set, for example, 30 ° C. or higher is preferable, 60 ° C. or higher is more preferable, 80 ° C. or higher is further preferable, and 200 ° C. or lower is preferable. It is preferably 190 ° C. or lower, more preferably 190 ° C. or lower. The reaction time is not particularly limited and may be appropriately set according to the progress of the reaction. For example, 0.5 hours or more is preferable, 3 hours or more is more preferable, 12 hours or less is preferable, and 10 hours or less is preferable. More preferred.

The phthalocyanine compound (I) obtained by reacting the compound (X) with the amine compound (Y) can be filtered, silica gel column chromatography, alumina column chromatography, sublimation, recrystallization, crystallization and the like, if necessary. It can be appropriately purified by a known purification means. The chemical structure of the phthalocyanine compound (I) can be analyzed by known analytical methods such as mass spectrometry, single crystal X-ray structure analysis, Fourier transform infrared spectroscopy, and nuclear magnetic resonance spectroscopy.

The phthalocyanine compound (I) of the present invention shows good absorption in the near infrared region. Taking advantage of this property, for example, the phthalocyanine compound (I) of the present invention is translucent or transparent and has a heat ray shielding material for the purpose of shielding heat rays; a resist material; a heat ray absorbing laminated glass for automobiles; a heat ray shielding material. Film or heat ray shielding resin glass; Filter for plasma display; Near infrared ray absorber for non-contact fixing toner such as flash fixing; Near infrared ray absorber for heat retention heat storage fiber; Has camouflage performance (camouflage performance) against infrared reconnaissance Infrared absorber for fiber; Optical recording medium using semiconductor laser; Filter for liquid crystal display; Black matrix material; Near-infrared absorbing dye for writing or reading in optical character readers; Near-infrared light sensitizer; Photoheat exchangers such as heat-sensitive transfer and heat-sensitive slabs; Photoheat exchangers for laser fusion that heat-fuse resins using a laser beam; Thermal adhesive film (especially adhesive film for sealing metal terminals of power storage devices); Near infrared rays Absorption filter; Eye fatigue inhibitor or photoconductive material; Photosensitive dye for tumor treatment; Color brown tube selective absorption filter; Color toner; Infrared ink; Anti-tampering ink; Anti-tampering bar code ink; Near It is preferably used as an infrared absorbing ink; a marking agent for positioning a photograph or a film; a lens of goggles; a shielding plate; a dyeing agent for sorting in plastic recycling; a preheating auxiliary agent in the molding process of PET bottles; and the like. In the following, the heat ray-shielding material and the resist material, which are preferable uses of the phthalocyanine compound (I), will be described in detail.

2. 2. Heat-shielding material The heat-shielding material is made of a resin containing a phthalocyanine compound (I). That is, the present invention also includes a resin composition containing a phthalocyanine compound (I) and a resin. In particular, since the phthalocyanine compound (I) of the present invention is also excellent in heat resistance, a heat ray shielding material should be prepared by a highly productive molding method such as injection molding or extrusion molding using a general-purpose thermoplastic resin. Can be done.

The resin that can be preferably used as the heat ray-shielding material is preferably a resin that is practically transparent and does not absorb and scatter significantly. Specific examples of the transparent resin include polycarbonate resin; (meth) acrylic resin such as methyl methacrylate; polystyrene; polyvinyl chloride; polyvinyl chloride such as polyvinylidene chloride; polyolefin resin such as polyethylene and polypropylene; polybutyral resin; Vinyl acetate-based resins such as polyvinyl chloride; polyester resins, polyamide resins and the like can be mentioned. Further, as long as it is substantially transparent, not only the above-mentioned one type of resin but also a blend of two or more types of resin can be used, and the above-mentioned resin can be sandwiched between transparent glass and used. ..

The polycarbonate resin is produced by reacting a divalent phenol with a carbonate precursor by a solution method or a melting method. Typical examples of divalent phenols are 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], 1,1-bis (4-hydroxyphenyl) ethane, and 1,1-bis (4-hydroxy). Phenyl) cyclohexane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-) Hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone and the like.

Examples of the acrylic resin include methyl methacrylate alone, a polymerizable unsaturated monomer mixture containing methyl methacrylate, or a copolymer thereof. Examples of the polymerizable unsaturated monomer copolymerizable with methyl methacrylate include methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, and (meth) acrylic acid. 2-Ethylhexyl, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, ( Tribromophenyl (meth) acrylate, tetrahydroxyfurfuryl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethyl ethanedi (meth) ) Acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like.

As the vinyl chloride resin, not only a polymer containing only a vinyl chloride monomer but also a copolymer containing vinyl chloride as a main component can be used. Examples of the monomer that can be copolymerized with vinyl chloride include vinylidene chloride, ethylene, propylene, acrylonitrile, vinyl acetate, maleic acid, itaconic acid, acrylic acid, and methacrylic acid.

The heat ray-shielding material may contain various additives. Examples of the additive include a colorant, a heat ray absorber such as carbon black, a polymerization regulator, an antioxidant, an ultraviolet absorber, a flame retardant, a plasticizer, a rubber for improving impact resistance, a release agent and the like. Can be mentioned.

Extrusion molding, injection molding, casting polymerization, press molding, calendar molding, casting film forming method and the like can be appropriately adopted for forming the heat ray shielding material. Further, the heat ray shielding material can also be prepared, for example, by preparing a film containing a phthalocyanine compound (I) and hot-pressing or heat-laminating the obtained film on a transparent resin material. The phthalocyanine compound (I) It can also be produced by printing or coating an acrylic resin ink or a paint containing the above on a transparent resin material.

The heat ray shielding material is preferably used for building materials such as roofing materials and wall materials of tennis courts and pools, arcades, and ceiling dome; for offices / stores, agriculture, automobiles, window films, and the like. Further, the heat ray-shielding material is also preferably applied as a photothermal converter for laser fusion applications in which a resin is heat-sealed using a laser beam, and for heat-adhesive films (particularly adhesive films for sealing metal terminals of power storage devices). To.

3. 3. Resist material The resist material is, for example, a curable resin composition containing a phthalocyanine compound (I) and a resin. In particular, the phthalocyanine compound (I) varies in its ability to absorb infrared rays (preferably near infrared rays) even in a harsh environment (for example, containing a resin having polarity) because repeated heat treatment at a high temperature does not impair its ability to absorb infrared rays (preferably near infrared rays). It can be applied to various applications. The phthalocyanine compound (I) contained in the curable resin composition may be only one kind or two or more kinds.

The content of the phthalocyanine compound (I) is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, still more preferably 1 part by mass or more, and preferably 1 part by mass or more, based on 100 parts by mass of the solid content of the resin. Is 100 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 30 parts by mass or less.

The content of the phthalocyanine compound (I) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, based on 100% by mass of the total solid matter of the curable resin composition. It is preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less.

Further, in the curable resin composition, in addition to the phthalocyanine compound (I), known infrared absorbers typified by carbon black, titanium black, composite oxide black pigment and the like are contained within a range that does not impair the effects of the present invention. However, the content of the phthalocyanine compound (I) in 100% by mass of the infrared absorber contained in the curable resin composition is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably. It is 90% by mass or more, and more preferably 95% by mass or more.

In the present specification, the "total solid content" means the total amount of the components forming the cured product (components excluding the solvent and the like that volatilize during the formation of the cured product). Specifically, it means the total mass of the solid content of the curable resin composition excluding the solvent.

<Resin>
The acid value of the resin is preferably 30 mgKOH / g or more, more preferably 40 mgKOH / g or more, preferably 200 mgKOH / g or less, and more preferably 180 mgKOH / g or less.
The acid value of the resin is determined from the acid value of the solution and the solid content of the solution to 1 g of the solid content after measuring the acid value of the resin solution using an automatic titrator using a 0.1-specified KOH aqueous solution as the titrator. It can be calculated as an acid value.

The base value of the resin is preferably 30 mgKOH / g or more, more preferably 40 mgKOH / g or more, preferably 200 mgKOH / g or less, and more preferably 180 mgKOH / g or less.
The base value of the resin is determined from the base value of the solution and the solid content of the solution to 1 g of the solid content after measuring the base value of the resin solution with an automatic titrator using an HCl aqueous solution of 0.1 definition as the titration solution. It can be obtained by converting it into a base value and converting it into an equivalent amount of potassium hydroxide.

It is desirable that the resin satisfies at least one condition of (i) an acid value of 30 mgKOH / g or more and 200 mgKOH / g or less, and (ii) a base value of 30 mgKOH / g or more and 200 mgKOH / g or less.

The polymerization average molecular weight (Mw) of the resin is preferably 5,000 or more, more preferably 8,000 or more, still more preferably 10,000 or more, preferably 100,000 or less, and more preferably 50,000 or less. More preferably, it is 20,000 or less.

The solid content of the resin is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and preferably 90% by mass, based on 100% by mass of the total solid content of the curable resin composition. % Or less, more preferably 85% by mass or less, still more preferably 80% by mass or less.

As the resin, an alkali-soluble resin is preferable, and an alkali-soluble resin having an acid group is more preferable. As the resin, a polymer (also referred to as a base polymer) obtained by polymerizing a monomer component containing a monomer having an acid group and a polymerizable double bond, or the base polymer may be bonded to an acid group. Examples thereof include a polymer obtained by reacting a compound having a functional group and a polymerizable double bond (also referred to as a polymer having a double bond in a side chain or a polymer containing a side chain double bond). The monomers (compounds) preferably used in the present invention are exemplified below, and one or more of these can be used.

(I) Monomer having an acid group and a polymerizable double bond Examples of the monomer having an acid group and a polymerizable double bond include (meth) acrylic acid, crotonic acid, silicic acid, vinyl benzoic acid and the like. Unsaturated monocarboxylic acids; unsaturated polyvalent carboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid; monosuccinate (2-acryloyloxyethyl), monosuccinate (2-methacryloyloxyethyl) Unsaturated monocarboxylic acids in which the chain is extended between the unsaturated group and the carboxyl group; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; light ester P-1M (manufactured by Kyoeisha Chemical Co., Ltd.), etc. Phosphoric acid group-containing unsaturated compounds; and the like. Among these, carboxylic acid-based monomers (unsaturated monocarboxylic acids, unsaturated polyvalent carboxylic acids, unsaturated acid anhydrides) are preferable, and more preferably (unsaturated monocarboxylic acids, unsaturated polyvalent carboxylic acids, unsaturated acid anhydrides), from the viewpoint of versatility, availability, and the like. Meta) Acrylic acid.

(Ii) Monomer having an amino group and a polymerizable double bond Even if the monomer component contains a monomer having an amino group and a polymerizable double bond as a monomer component constituting the resin. good. As the monomer having an amino group and a polymerizable double bond, a monomer represented by the formula (IV) is preferable.

[In formula (IV), R ⁵³ has a hydrogen atom or a methyl group, and R ⁵⁴ to R ⁵⁵ each independently represent a hydrocarbon atom or a hydrocarbon group which may have a substituent. R ⁵⁴ and R ⁵⁵ may be combined with each other to form an annular structure. Y represents a single bond or a divalent linking group. ]

Each of R ⁵⁴ and R ⁵⁵ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 12) and an alicyclic hydrocarbon group having 3 to 20 carbon atoms (preferably 3 to 12), respectively. , Or an aromatic hydrocarbon group having 6 to 20 (preferably 6 to 10) carbon atoms, and the aliphatic hydrocarbon group and the alicyclic hydrocarbon group are either saturated or unsaturated. May be good.
Examples of the substituent of the hydrocarbon group represented by R ⁵⁴ to R ⁵⁵ include a halogen atom, a hydroxyl group, and an alkoxy group having 1 to 6 carbon atoms.

The divalent linking group represented by Y includes an alkanediyl group having 1 to 10 carbon atoms (preferably 1 to 6), an arylene group having 6 to 20 carbon atoms (preferably 6 to 14), and -CONH-R. ^56- (* 1) group, -COO-R ^57- (* 1) group and the like can be mentioned. Here, R ⁵⁶ and R ⁵⁷ each independently represent a single bond, an alkanediyl group having 1 to 10 carbon atoms (preferably 1 to 6), or an alkyleneoxyalkylene group having 2 to 10 carbon atoms. * 1) indicates that it is a bond that binds to N.

Preferred examples of the monomer having an amino group and a polymerizable double bond include dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate.

(Iii) Monomer component In addition to the above-mentioned monomers (i) to (ii), as a monomer component constituting the resin,
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, -sec-butyl (meth) acrylate. , (Meta) acrylic acid-tert-butyl, (meth) acrylic acid n-amyl, (meth) acrylic acid-sec-amyl, (meth) acrylic acid-tert-amyl, (meth) acrylic acid n-hexyl, ( 2-Ethylhexyl acrylate, (meth) isodecyl acrylate, tridecyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate , (Meta) lauryl acrylate, (meth) stearyl acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclo (meth) acrylate Decanyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate Hydroxybutyl, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (Meta) glycidyl acrylate, (meth) β-methyl glycidyl acrylate, (meth) β-ethyl glycidyl acrylate, (meth) acrylate (3,4-epoxycyclohexyl) methyl, α-hydroxymethyl (meth) acrylic Methyl acid, ethyl α-hydroxymethyl (meth) acrylate, 1,4-dioxaspiro [4.5] deca-2-yl (meth) acrylic acid, (meth) acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, 4 -(Meta) Acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolan, 4- (meth) Acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolan, 4- (meth) Acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2,2-dimethyl-1,3-dioxolan, alkoxylated phenylphenol (meth) acrylate, etc. (Meta) acrylic acid ester-based monomer;
Aromatic vinyl-based monomers such as styrene, vinyltoluene, α-methylstyrene, and methoxystyrene;
N substitutions such as N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-tert-butylmaleimide, N-dodecylmaleimide, N-benzylmaleimide, N-naphthylmaleimide, etc. Maleimide-based monomer;
Dimethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'-[oxybis (methylene) ] Bis-2-propenoate, dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate and other acrylic ether dimers;
Α- (Unsaturated alkoxyalkyl) acrylate-based monomers such as alkyl- (α-metharyloxymethyl) acrylate and α- (allyloxymethyl) acrylate;
(Meta) acrylamides;
Macromonomers having a (meth) acryloyl group at one end of the polymer molecular chain;
Conjugated diene;
Vinyl esters;
Vinyl ethers;
N-vinyl compounds;
Unsaturated isocyanates; etc. are exemplified.

(Iv) A compound having a functional group capable of binding to an acid group and a polymerizable double bond Examples of the compound having a functional group capable of binding to an acid group and a polymerizable double bond include glycidyl (meth) acrylate and (meth). Examples thereof include β-methylglycidyl acrylate, β-ethylglycidyl (meth) acrylate, vinylbenzyl glycidyl ether, allylglycidyl ether, methyl (meth) acrylate (3,4-epoxycyclohexyl), vinylcyclohexene oxide and the like.

As a method for polymerizing the monomer component, commonly used methods such as bulk polymerization, solution polymerization, and emulsion polymerization can be used, and may be appropriately selected depending on the purpose and application. Above all, solution polymerization is industrially advantageous and is suitable because it is easy to adjust the structure such as molecular weight. Further, as the polymerization mechanism of the monomer component, a polymerization method based on a mechanism such as radical polymerization, anion polymerization, cationic polymerization, or coordination polymerization can be used, but the polymerization method based on the radical polymerization mechanism is industrially used. Is also preferable because it is advantageous.

<Polymerizable compound>
The curable resin composition may contain a polymerizable compound. The polymerizable compound is a compound having a polymerizable unsaturated bond (also referred to as a functional group) in the molecule, and the polymerizable unsaturated group includes free radicals, electromagnetic waves (for example, infrared rays, ultraviolet rays, X-rays, etc.), and the like. It is a group that can be polymerized by irradiation with active energy rays such as electron beams.

The content (solid content) of the polymerizable compound is preferably 1 part by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, and preferably 10 parts by mass or more, based on 100 parts by mass of the solid content of the resin. It is 100 parts by mass or less, more preferably 90 parts by mass or less, still more preferably 80 parts by mass or less.
The content (solid content) of the polymerizable compound is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, based on 100% by mass of the total solid content of the curable resin composition. Yes, preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less.

The polymerizable compound includes a (meth) acrylate compound (preferably a bifunctional or higher functional (meth) acrylate compound); a polyfunctional vinyl ether compound; a vinyl ether group-containing (meth) acrylate compound; a polyfunctional allyl ether compound; an allyl group-containing compound. (Meta) acrylic acid esters; polyfunctional (meth) acryloyl group-containing isocyanurates; polyfunctional allyl group-containing isocyanurates; polyfunctional urethane (meth) acrylates; polyfunctional aromatic vinyls; unsaturated polyvalent carboxylics Acids and unsaturated acid anhydrides; etc. may also be mentioned.

As a (meth) acrylate compound,
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, cyclohexanedimethanol Bifunctional (meth) acrylate compounds such as di (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate, and bisphenol Falkylene oxide di (meth) acrylate;
Trimethylolpropane Tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerintri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tetra (meth) acrylate, ethylene oxide Additional pentaerythritol tetra (meth) acrylate, ethylene oxide-added dipentaerythritol hexa (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tetra (meth) acrylate, propylene oxide-added pentaerythritol tetra. (Meta) acrylate, propylene oxide-added dipentaerythritol hexa (meth) acrylate, ε-caprolactone-added trimethylolpropanetri (meth) acrylate, ε-caprolactone-added dimethylolpropanetetra (meth) acrylate, ε-caprolactone-added pentaerythritol tetra Examples thereof include trifunctional or higher functional (meth) acrylate compounds such as (meth) acrylate and ε-caprolactone-added dipentaerythritol hexa (meth) acrylate; and the like.

The functional number of the polymerizable compound is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, still more preferably 5 because the curability can be further enhanced and the hardness of the cured product can be further improved. That is all. Further, from the viewpoint of further suppressing curing shrinkage, the functional number is preferably 10 or less, more preferably 8 or less. Generally, as the number of functional groups of the polymerizable compound increases, many infrared absorbers are decomposed by repeated heat treatment, and the infrared absorbing ability of the cured product tends to decrease, but the curable resin containing the phthalocyanine compound (I) tends to decrease. If it is a composition, even if the number of functional groups of the polymerizable compound is increased, it is possible to suppress a decrease in the infrared absorption ability of the cured product. When having two or more functional groups, the same functional group may be used, but different functional groups may be used.

The polymerizable compound is more preferably a polyfunctional (meth) acrylate compound, and further preferably a trifunctional or higher functional (meth) acrylate compound, from the viewpoints of reactivity, economy, availability and the like.

<Polymer initiator>
The curable resin composition of the present invention may contain a polymerization initiator.
The content (solid content) of the polymerization initiator is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and further preferably 1 part by mass or more with respect to 100 parts by mass of the solid content of the resin. It is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 10 parts by mass or less.
The content (solid content) of the polymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1 in the total solid content of 100% by mass of the curable resin composition. It is by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less.

The polymerization initiator is preferably a radically polymerizable polymerization initiator. The radically polymerizable polymerization initiator is one that generates a polymerization initiation radical by irradiation with an active energy ray such as an electromagnetic wave or an electron beam. Further, if necessary, one kind or two or more kinds of a photosensitizer, a photoradical polymerization accelerator and the like may be used in combination. Sensitivity and curability are further improved by using a photosensitizer and / or a photoradical polymerization accelerator in combination with the polymerization initiator.

Specifically, as the polymerization initiator, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one (“IRGACURE907”, manufactured by BASF), 2-benzyl-2-dimethyl. Amino-1- (4-morpholinophenyl) -butanone-1 ("IRGACURE369E", manufactured by BASF), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-) Aminoketone compounds such as yl-phenyl) -butane-1-one ("IRGACURE379", manufactured by BASF); 2,2-dimethoxy-1,2-diphenylethane-1-one ("IRGACURE651", manufactured by BASF). , Phenylglyceric acid methyl ester ("DAROCUR MBF", manufactured by BASF) and other benzyl ketal compounds; 1-hydroxy-cyclohexyl-phenyl-ketone ("IRGACURE184", manufactured by BASF), 2-hydroxy-2- Methyl-1-phenyl-Propane-1-one ("DAROCUR1173", manufactured by BASF), 1- [4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1- On ("IRGACURE2959", manufactured by BASF), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propane-1-one Hydroketone compounds such as ("IRGACURE127", manufactured by BASF), [1-hydroxy-cyclohexyl-phenyl-ketone + benzophenone] ("IRGACURE500", manufactured by BASF); alkylphenone-based compounds; benzophenone-based compounds; benzoin-based Compounds; thioxanthone compounds; halomethylated triazine compounds; halomethylated oxadiazole compounds; biimidazole compounds; oxime ester compounds; titanosen compounds; benzoic acid ester compounds; alkidine compounds, etc .; phosphin oxide compounds; Oxym ester-based compounds; and the like.
The polymerization initiator is preferably an aminoketone compound because it has a higher hardness.

<Solvent>
The curable resin composition may contain a solvent. The solvent is preferably used as a diluent or the like. As the solvent, one type or two or more types that are normally used can be used, and may be appropriately selected depending on the purpose and application, and methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, etc. Alcohol-based solvents such as sec-butyl alcohol, tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, n-hexanol, propylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol; butyl cellosolve, propylene Ether solvents such as glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol, dimethyl ether; ester solvents such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; acetone, methyl ethyl ketone, methyl butyl ketone, methyl Ketone solvents such as isobutyl ketone, diisobutyl ketone, cyclohexanone, diacetone alcohol; aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane; amide solvents such as N, N-dimethylformamide The solvent is preferably an alcohol solvent, an ether solvent, or an ester solvent.

The amount of the solvent used may be appropriately set according to the purpose and application, and is not particularly limited, but is preferably 5% by mass or more, more preferably 10% in the total amount of 100% by mass of the curable resin composition of the present invention. It is by mass or more, more preferably 30% by mass or more, preferably 90% by mass or less, more preferably 88% by mass or less, still more preferably 85% by mass or less.

<Other ingredients>
The curable resin composition of the present invention may also contain one or more other components (also referred to as other components), if necessary (for example, depending on the required characteristics of each applied application). good.
Other components include a coupling agent; a polymerization inhibitor; a fluorine additive; a polymerizable compound other than the above-mentioned polymerizable compound; a filler; a photosensitizer; a photoradical polymerization accelerator; a coloring material (also referred to as a coloring agent). Dispersant; Heat resistance improver; Leveling agent; Development aid; Filler; Thermosetting resin such as epoxy resin, phenol resin, polyvinylphenol; Curing aid such as polyfunctional thiol compound; Plastic agent; Ultraviolet absorber; Oxidation Inhibitors; matting agents; antifoaming agents; antistatic agents; slip agents; surface modifiers; rocking agents; rocking aids; quinonediazide compounds; polyhydric phenol compounds; cationically polymerizable compounds; acid generators; leveling Agents; etc.

<Manufacturing method of curable resin composition>
The method for producing the curable resin composition of the present invention is not particularly limited, and the above-mentioned contained components can be prepared by mixing and dispersing using various mixers and dispersers. The dispersion step and the mixing step are not particularly limited and may be carried out by a usual method. Moreover, it may further include other steps which are usually performed. When the curable resin composition contains a coloring material, it is preferable to produce the curable resin composition through a process of dispersing the coloring material.

(Hardened film)
The curable resin composition of the present invention can form a cured film by, for example, irradiating (exposing) an active energy ray. Specifically, it is preferable to apply a curable resin composition on a substrate (also referred to as a substrate), dry it, and irradiate (expose) the coated surface with active energy rays to form a cured film. ..

The substrate (also referred to as a base material) to which the curable resin composition is applied is not particularly limited, and is a transparent glass substrate such as white plate glass, blue plate glass, silica-coated blue plate glass; polyethylene terephthalate (PET), polyester, polycarbonate, etc. Sheets or films made of thermoplastic resins such as ring-opening polymers of polyolefins, polysulfones and cyclic olefins and their hydrogenated additives; sheets or films made of thermosetting resins such as epoxy resins and unsaturated polyester resins; aluminum plates, copper plates , Metal substrates such as nickel plates and stainless plates; Ceramic substrates; Semiconductor substrates with photoelectric conversion elements; Members composed of various materials such as glass substrates (color filters for LCDs) having a color material layer on the surface; etc. Be done.

The substrate may be subjected to corona discharge treatment, ozone treatment, chemical treatment with a silane coupling agent, etc., if necessary, or inorganic components such as a gas barrier layer or a protective film or organic components on both sides or one side of the substrate. A coating film of the component may be formed. When the cured film is used as a member for a display device, it is preferable to form an electrode such as ITO on the substrate.

The method for applying the curable resin composition to the substrate is not particularly limited, and examples thereof include spin coating, slit coating, roll coating, cast coating, and the like, and any method can be preferably used. The coating film after being applied to the substrate can be dried using a hot plate, an IR oven, a convection oven or the like. The drying conditions are appropriately selected according to the boiling point of the solvent component contained, the type of the curing component, the film thickness, the performance of the dryer, etc., but usually, the drying is performed at a temperature of 50 to 150 ° C. for 10 seconds to 300 seconds. Is preferable.

As the method of the light source and the exposure machine of the active energy ray, the method of the light source and the exposure machine exemplified in JP-A-2013-227485 [0161] can be used. In the process of irradiating the active energy ray, the active energy ray may be irradiated through a predetermined mask pattern depending on the application. In this case, the exposed portion is cured, and the cured portion is insoluble or sparingly soluble in the developing solution.

Further, if necessary, after the step of irradiating the active energy light beam, a step of developing with a developing solution to remove an unexposed portion to form a pattern (also referred to as a developing step) may be performed. This makes it possible to obtain a patterned cured film. The developing process in the developing step can usually be performed at a developing temperature of 10 to 50 ° C. by a method such as immersion development, spray development, brush development, and ultrasonic development. When an alkaline aqueous solution is used as the developing solution, it is preferable to wash it with water after developing.
The developing solution is not particularly limited as long as it dissolves the curable resin composition of the present invention, but an organic solvent or an alkaline aqueous solution is usually used, and a mixture thereof may be used. Examples of the organic solvent suitable as the developing solution include ether-based solvents and alcohol-based solvents. In addition to the alkaline agent, the alkaline aqueous solution may contain a surfactant, an organic solvent, a buffer, a dye, a pigment and the like, if necessary.

Further, if necessary, a post-curing step (also referred to as a post-baking or post-treatment step) may be performed. Examples of the post-curing step include a step of exposing with a light amount of 0.5 to 5 J / cm ² using a light source such as a high-pressure mercury lamp, and a step of post-heating (also referred to as a heat treatment step). By performing such a post-treatment, it becomes possible to further strengthen the hardness and adhesion of the patterned cured film. The temperature in the heat treatment step is preferably 60 ° C. or higher (more preferably 100 ° C. or higher, still more preferably 200 ° C. or higher, preferably 300 ° C. or lower). By performing the heat treatment step in this temperature range, the reactive compound is decomposed, and the action and effect of the present invention can be more sufficiently exhibited. The heat treatment time is not particularly limited, but is preferably 10 seconds to 300 minutes.

The cured film formed from the curable resin composition preferably has a maximum absorption wavelength in the range of 700 to 1100 nm, preferably 0.150 or more, more preferably 0.300 or more, still more preferably 0.400 or more, preferably 0.400 or more. It has an absorbance of 4.000 or less, more preferably 3.000 or less, still more preferably 2.000 or less, still more preferably 1.000 or less.

(Use of curable resin composition, etc.)
The cured product (cured film) formed from the curable resin composition of the present invention includes components of various display devices such as a liquid crystal display device, a solid-state image pickup element, and a touch panel display device, as well as ink, a printing plate, and printed wiring. It is preferably used in various applications such as various optical members such as plates, semiconductor elements, photoresists, and electric / electronic devices. Above all, it is preferable to use it for a color filter used for a liquid crystal display device, a solid-state image sensor, or the like, or a touch panel type display device.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples as well as the present invention, and appropriate modifications are made to the extent that it can meet the purposes of the preceding and the following. Of course, it is possible to carry out, and all of them are included in the technical scope of the present invention.

(Example 1)
In a 300 ml three-necked flask, 7.3 g of brominated chlorinated copper phthalocyanine (CI Pigment Green 36, containing an average of 7 bromine groups and an average of 9 chlorine groups per molecule), 2- 56.6 g of chlorobenzylamine and 83.4 g of 1-methyl-2-pyrrolidone were added and reacted at 180 ° C. for about 5 hours with stirring. The obtained reaction solution was put into about 400 ml of methanol for crystallization, and the precipitate was collected by suction filtration. The obtained precipitate was purified by stirring and washing in 300 ml of methanol, and then the crystals were collected by suction filtration. Then, vacuum drying is performed at 80 ° C. to obtain the desired phthalocyanine compound 1 (hereinafter, referred to as tetra or penta (2-chlorobenzylamino) -penta or tetra (chloro) -hepta (bromo) -copper phthalocyanine). Obtained (5.6 g, yield 77 wt% with respect to starting material).

(Example 2)
Phthalocyanine compound 2 (tetra or penta (4-methoxybenzylamino)-in the same manner as in Example 1 except that 2-chlorobenzylamine in Example 1 was changed to 4-methoxybenzylamine while maintaining the molar ratio. Penta or tetra (chloro) -hepta (bromo) -copper phthalocyanine) was obtained (6.2 g, yield 85 wt% with respect to starting material).

(Example 3)
Phthalocyanine compound 3 (tetra or penta (3-aminomethylbenzylamino)) was the same as in Example 1 except that 2-chlorobenzylamine in Example 1 was changed to m-xylylenediamine while maintaining the molar ratio. -Penta or tetra (chloro) -hepta (bromo) -copper phthalocyanine) was obtained (5.3 g, yield 73 wt% with respect to starting material).

(Example 4)
Phthalocyanine compound 4 (tri or tetra (4-aminobenzylamino)-in the same manner as in Example 1 except that 2-chlorobenzylamine in Example 1 was changed to 4-aminobenzylamine while maintaining the molar ratio. Hexa or penta (chloro) -hepta (bromo) -copper phthalocyanine) was obtained (4.9 g, yield 67 wt% with respect to starting material).

(Example 5)
Phthalocyanine compound 5 (tetra or penta (1-phenylethylamino)) was the same as in Example 1 except that 2-chlorobenzylamine in Example 1 was changed to DL-1-phenylethylamine while maintaining the molar ratio. -Penta or tetra (chloro) -hepta (bromo) -copper phthalocyanine) was obtained (6.3 g, yield 86 wt% with respect to starting material).

(Example 6)
Phthalocyanine compound 6 (tri or tetra (1,1-diphenylmethylamino)-in the same manner as in Example 1 except that 2-chlorobenzylamine in Example 1 was changed to benzhydrylamine while maintaining the molar ratio. Hexa or penta (chloro) -hepta (bromo) -copper phthalocyanine) was obtained (5.8 g, yield 79 wt% with respect to starting material).

(Comparative Example 1)
Octachlorohepta (benzylamino) copper phthalocyanine (hereinafter referred to as comparative phthalocyanine compound A) was synthesized according to the method described in Example 1 of JP-A-9-52894.

(Comparative Example 2)
A comparative phthalocyanine compound B represented by the following formula was synthesized according to the method described in Example 7 of Japanese Patent No. 3721298.

(Comparative Example 3)
A comparative phthalocyanine compound C represented by the following formula was synthesized according to the method described in Example 16 of Japanese Patent No. 4278923.

(Measurement of absorbance at 780 nm in solution)
A solution prepared by diluting phthalocyanine compounds 1 to 6 and comparative phthalocyanine compound A to 0.001 wt% with a THF solvent was prepared, and the spectral spectrum was measured using a spectrophotometer UV-1800 manufactured by Shimadzu Corporation and a 1 cm quartz cell. The absorbance at 780 nm, which is the near-infrared emission wavelength of a typical semiconductor laser, was determined. The obtained absorbance is shown in Table 1. From Table 1, when the absorbances at 780 nm are compared, it can be seen that the phthalocyanine compounds 1 to 6 have much higher absorption efficiency than the conventionally known comparative phthalocyanine compounds A.

(Preparation of Curable Resin Composition 1)
As a near-infrared absorbing dye, 0.044 g of a phthalocyanine compound, 0.483 g of an acrylic binder resin (acid value: 100 mgKOH / g) in which benzyl methacrylate (BzMA) and methacrylic acid (MAA) are copolymerized, and dipenta as a polymerizable compound. Curing by mixing 0.324 g of erythritol hexaacrylate (light acrylate (registered trademark) DPE-6A manufactured by Kyoeisha Chemical Co., Ltd.), 0.03 g of IRGACURE (registered trademark) manufactured by BASF, and 3.90 g of PGMEA as a polymerization initiator. A sex resin composition 1 (negative type photosensitive resin composition 1) was obtained. The solid content concentration in the curable resin composition 1 is 18.4% by mass, the content of the polymerizable compound with respect to 100 parts by mass of the acrylic binder resin is 67 parts by mass, and the concentration of the phthalocyanine compound 1 in the solid content. Was 5.0% by mass.
For the acid value of the resin, 1.5 g of the resin solution is precisely weighed and dissolved in a mixed solvent of 90 g of acetone / 10 g of water, and an automatic titration device (manufactured by Hiranuma Sangyo Co., Ltd.) is used as a titration solution using a 0.1-specified KOH aqueous solution. , The acid value of the resin solution was measured according to the trade name "COM-555"), and then the acid value per 1 g of the solid content was determined from the acid value of the solution and the solid content of the solution.

(Creation of cured film)
Next, the curable resin composition 1 was applied onto a glass substrate by a spin coating method, and then prebaked at 100 ° C. for 3 minutes to form a coating film 1 having a film thickness of 2.0 μm. Then, the obtained substrate was cooled to room temperature, and an exposure machine (NSR-2205i12D manufactured by Nikon Corporation, numerical aperture of 0.50) was used on the coating film on the substrate via a photomask to 300 mJ / at a wavelength of 365 nm. It was exposed with an exposure amount of cm ² . Subsequently, paddle development for 30 seconds was performed twice in total using a 0.3 wt% tetramethylammonium hydroxide aqueous solution in an automatic coating and developing apparatus. After drying, post-baking was performed at 230 ° C. for 30 minutes in an oven to form a cured film 1-1. Then, the obtained cured film 1-1 was further baked in an oven at 230 ° C. for 30 minutes to obtain a cured film 1-2.

(Measurement of absorbance)
The spectral spectra of the coating film 1, the cured film 1-1, and the cured film 1-2 were measured using a spectrophotometer UV-1800 manufactured by Shimadzu Corporation, and the absorbance at 400 to 1100 nm was determined.
Table 2 shows the absorbances of the coating film 1, the cured film 1-1 and the cured film 1-2 at the maximum absorption wavelength λmax (A) when the maximum absorption wavelength of the coating film is λmax (A).
Table 2 shows the maximum absorption wavelength λmax (E) of each film and the absorbance at the maximum absorption wavelength λmax (E) of each film for the coating film 1, the cured film 1-1 and the cured film 1-2.

(Evaluation of dye heat resistance)
When the maximum absorption wavelength of the coating film is λmax (A), the absorbance at λmax (A) of the cured film 1-1 and the cured film 1-2 is calculated, and the residual rate of the dye due to heating is calculated as an index of heat resistance. Was calculated from the following formula and summarized in Table 3.
-Dye residual rate (first time) = (absorbance at λmax (A) of cured film 1-1) / (absorbance at λmax (A) of coating film 1) x 100 (%)
-Dye residual rate (second time) = (absorbance at λmax (A) of cured film 1-2) / (absorbance at λmax (A) of coating film 1) x 100 (%)

In Example 1, the absorbance was measured in the same manner as in Example 1 except that the phthalocyanine compound 1 was changed to the phthalocyanine compounds 2 to 6 and the comparative phthalocyanine compounds B to C, and the heat resistance was evaluated. The results are shown in Tables 2 and 3.

From Table 2, it can be seen that the curable resin composition containing the phthalocyanine compounds 1 to 6 can absorb infrared light (preferably near infrared light). Further, in the case of the curable resin composition containing the phthalocyanine compounds 1 to 6, the maximum absorption wavelength λmax (maximum absorption wavelength λmax) of each film is used in both the cured film after post-baking and the cured film after further baking at 230 ° C. for 30 minutes. In E), the absorbance of 0.150 or more is satisfied. That is, it can be seen that the curable resin composition containing the phthalocyanine compound (I) can maintain its infrared (preferably near-infrared) absorption capacity in a high state even when exposed to repeated heat treatment at a high temperature.

Further, the phthalocyanine compound of the present invention can be applied to a coating film after being applied on a glass substrate by a spin coating method, a cured film after post-baking, or a cured film after being further baked at 230 ° C. for 30 minutes. However, the peak top of each film is within the range of -25 ≦ Δλmax (E) ≦ 25, and the deviation is small.

From Table 3, it can be seen that the curable resin composition containing the phthalocyanine compounds 1 to 6 can maintain the dye residual ratio in the cured film in a high state. That is, it can be seen that, in the case of a curable resin composition containing the phthalocyanine compound (I), a curable resin composition in which the infrared ray (preferably near infrared ray) absorption ability is not impaired by repeated heat treatment at a high temperature is provided. Further, in Comparative Examples 2 to 3, the dye residual rate (first time) was 9.2 to 10.0%, and the dye residual rate (second time) was 1.7 to 3.5%, whereas Examples 1 to 6 were used. The dye residual rate (first time) was significantly improved to 88.7 to 91.9%, and the dye residual rate (second time) was significantly improved to 79.7 to 82.5%. From these experimental examples, it is clear how excellent the effect of the present invention is.

Claims (5)

A phthalocyanine compound represented by the formula (I).

[In formula (I),
M represents copper .
R ¹¹ to R ²⁶ each independently represent a chlorine atom, a bromine atom or a substituent represented by the formula (A), and one or more of R ¹¹ to R ²⁶ are bromine atoms, and R ¹¹ to R 26 are represented. Of R ²⁶ , 3 or more and 5 or less are substituents represented by the formula (A). ]

[In formula (A),
R ¹ has a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, and a substituent. It is also a good aralkyl group having 7 to 20 carbon atoms, or a heterocyclic group which may have a substituent.
R ² is an alkylene group having 1 to 20 carbon atoms which may have a substituent.
R ³ has an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, and carbon which may have a substituent. It is an alkylamino group having 1 to 20 carbon atoms which may have an alkoxycarbonyl group of 2 to 8, a halogen atom, a nitro group, a hydroxy group, a formyl group, an amino group, or a substituent.
m represents an integer of 0 or more and 5 or less.
* Is a bond.
When the number of groups represented by the formula (A) is two or more, the groups represented by the plurality of formulas (A) may be the same or different. Further, when m is 2 or more, a plurality of -R ³ may be the same or different. ] The phthalocyanine compound according to claim 1, wherein R ¹ is a hydrogen atom. The phthalocyanine compound according to claim 1 or 2, wherein R ² is a methylene group, an ethylene group or a propylene group which may have a substituent. The phthalocyanine compound according to any one of claims 1 to 3 , wherein the total number of bromine atoms in R ¹¹ to R ²⁶ is larger than the total number of chlorine atoms in R ¹¹ to R ²⁶ . The phthalocyanine compound according to any one of claims 1 to 4 , wherein the formula (A) is the formula (Aa), the formula (Ab), the formula (Ac) or the formula (Ad). ..

[In the formula (Aa), the formula (Ab), the formula (Ac) and the formula (Ad), R ³ and m are the same as described above. ]