JP2018172630A - Curable resin composition and cured film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition, where, even when containing a polar resin, the curable resin composition prevents infrared (preferably near infrared) radiation adsorption ability from being impaired due to repeated heat treatment at a high temperature.SOLUTION: A curable resin composition contains a phthalocyanine compound represented by a formula (I), and a resin. The resin has (i) an acid value of 30 mgKOH/g or more and 200 mgKOH/g or less and/or (ii) a base number of 30 mgKOH/g or more and 200 mgKOH/g or less.SELECTED DRAWING: None

Description

  The present invention relates to a curable resin composition containing a phthalocyanine compound and a resin, and a cured film obtained by curing the curable resin composition.

  Various display devices such as a liquid crystal display device, a solid-state imaging device, and a touch panel display device are provided with a color filter for realizing color display. The sensors of various display devices are sensitive not only to visible light but also to infrared rays. Therefore, an infrared cut filter (IRCF) is used to block infrared rays that pass through the color filter. Conventionally, the infrared cut filter and the color filter have been configured as separate members. However, the color filter layer absorbs light in the visible light wavelength band according to the recent needs for downsizing and thinning electronic devices. A solid-state imaging device or the like including a compound and a second compound having a maximum absorption wavelength in the infrared region has been proposed (Patent Document 1).

International Publication No. 2016/195031

  In the color filter manufacturing process, it is necessary to carry out a series of steps of resist coating, pre-baking, exposure, developing, and post-baking for RGB three colors. Therefore, when an infrared absorber is included in the color filter layer, the infrared absorber is included. Must be resistant to repeated heat treatments. On the other hand, in the applied resist, the resin used for the resist has polarity in order to remove an unnecessary portion of the resist with a developer after exposure. However, according to a study by the present inventors, it has been found that most of the infrared absorbers are easily decomposed when subjected to a plurality of heat treatments in a highly polar environment. Therefore, the present invention has been made to provide a curable resin composition that does not impair infrared (preferably near infrared) absorption ability by repeated heat treatment at a high temperature even when a resin having polarity is included.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by a curable resin composition containing a phthalocyanine compound having a specific structure, and completed the present invention. did.

［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。
Ｒ¹及びＲ²は、各々独立して、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアラルキル基、または置換基を有していてもよい複素環基である。
Ｘは、ハロゲン原子を表す。
ｍは、１以上１６以下の整数である。
ｙは、１以上１６以下の整数であり、且つ、ｙ≧ｍである。
ｍが２以上の場合、複数の−ＮＲ¹Ｒ²は同一でも異なっていてもよく、（ｙ−ｍ）が２以上の場合、複数のＸは同一でも異なっていてもよい。］
［２］ 前記式（Ｉ）で表されるフタロシアニン化合物が、式（ＩＩ）で表されるフタロシアニン化合物である［１］に記載の硬化性樹脂組成物。

［式（ＩＩ）中、Ｍ、Ｒ¹、Ｒ²、及びＸは前記に同じ。ａ〜ｄは、各々独立して、１以上４以下の整数である。］
［３］ Ｘがフッ素原子、塩素原子または臭素原子であり、Ｘとして少なくともフッ素原子または臭素原子を含む［１］または［２］に記載の硬化性樹脂組成物。
［４］ Ｒ¹及びＲ²の少なくとも一方は、置換基を有していてもよいアリール基または置換基を有していてもよいアラルキル基である［１］〜［３］のいずれかに記載の硬化性樹脂組成物。
［５］ −ＮＲ¹Ｒ²が式（Ｉｂ）で表される基である［１］〜［４］のいずれかに記載の硬化性樹脂組成物。

［式（Ｉｂ）中、Ｒ¹は前記に同じ。
Ａｒは、置換基を有していてもよいフェニル基または置換基を有していてもよいナフチル基である。］
［６］ −ＮＲ¹Ｒ²が式（Ａ）で表される基である［１］〜［４］のいずれかに記載の硬化性樹脂組成物。

［式（Ａ）中、Ｒ¹は前記に同じ。
Ｒ³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。
Ｒ⁴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。
ｋは、０以上５以下の整数を表す。
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ｋが２以上の場合、複数のＲ⁴は同一でも異なっていてもよい。］
［７］ Ｒ³がアリール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［６］に記載の硬化性樹脂組成物。
［８］ Ｒ¹が水素原子である［１］〜［７］のいずれかに記載の硬化性樹脂組成物。
［９］ 式（Ａ）が、式（Ａ−ａ）、式（Ａ−ｂ）、式（Ａ−ｃ）または式（Ａ−ｄ）である［６］〜［８］のいずれかに記載の硬化性樹脂組成物。

［式（Ａ−ａ）、式（Ａ−ｂ）、式（Ａ−ｃ）及び式（Ａ−ｄ）中、Ｒ⁴及びｋは前記に同じ。］
［１０］ ｋが０である［６］〜［７］、［９］のいずれかに記載の硬化性樹脂組成物。
［１１］ 前記Ｍが金属または金属酸化物である［１］〜［１０］のいずれかに記載の硬化性樹脂組成物。
［１２］ 前記Ｍが銅、亜鉛またはバナジルである［１］〜［１１］のいずれかに記載の硬化性樹脂組成物。
［１３］ 前記樹脂がアルカリ可溶性樹脂である［１］〜［１２］のいずれかに記載の硬化性樹脂組成物。
［１４］ さらに重合性化合物及び重合開始剤を含む［１］〜［１３］のいずれかに記載の硬化性樹脂組成物。
［１５］ さらに溶剤を含む［１］〜［１４］のいずれかに記載の硬化性樹脂組成物。
［１６］ 前記溶剤が、アルコール系溶剤、エーテル系溶剤、またはエステル系溶剤である［１５］に記載の硬化性樹脂組成物。
［１７］ ［１］〜［１６］のいずれかに記載の硬化性樹脂組成物から形成される硬化膜であって、７００〜１１００ｎｍの範囲での最大吸収波長において、０．１５０以上４．０００以下の吸光度を有することを特徴とする硬化膜。 That is, the curable resin composition according to the present invention has the gist in the following points.
[1] including a phthalocyanine compound represented by formula (I) and a resin,
Curing characterized in that the resin satisfies at least one condition of (i) an acid value of 30 mgKOH / g to 200 mgKOH / g, and (ii) a base value of 30 mgKOH / g to 200 mgKOH / g. Resin composition.

[In the formula (I),
M represents a nonmetal, a metal, a metal oxide, or a metal halide.
R ¹ and R ² are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. Or a heterocyclic group which may have a substituent.
X represents a halogen atom.
m is an integer of 1-16.
y is an integer from 1 to 16, and y ≧ m.
When m is 2 or more, the plurality of —NR ¹ R ² may be the same or different. When (ym) is 2 or more, the plurality of X may be the same or different. ]
[2] The curable resin composition according to [1], wherein the phthalocyanine compound represented by the formula (I) is a phthalocyanine compound represented by the formula (II).

[In the formula (II), M, R ¹ , R ² and X are the same as above. a to d are each independently an integer of 1 or more and 4 or less. ]
[3] The curable resin composition according to [1] or [2], wherein X is a fluorine atom, a chlorine atom, or a bromine atom, and X includes at least a fluorine atom or a bromine atom.
[4] At least one of R ¹ and R ² is any one of [1] to [3], which is an aryl group which may have a substituent or an aralkyl group which may have a substituent. Curable resin composition.
[5] The curable resin composition according to any one of [1] to [4], wherein —NR ¹ R ² is a group represented by the formula (Ib).

[In formula (Ib), R ¹ is the same as defined above.
Ar is a phenyl group which may have a substituent or a naphthyl group which may have a substituent. ]
[6] The curable resin composition according to any one of [1] to [4], wherein —NR ¹ R ² is a group represented by the formula (A).

[In formula (A), R ¹ is the same as defined above.
R ³ is an alkylene group having 1 to 20 carbon atoms which may have a substituent.
R ⁴ is an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 20 carbon atoms, and an optionally substituted carbon. It is a C2-C20 alkylamino group which may have a C2-C8 alkoxycarbonyl group, a halogen atom, a nitro group, a hydroxy group, a formyl group, an amino group, or a substituent.
k represents an integer of 0 or more and 5 or less.
When the group represented by the formula (A) is 2 or more, the groups represented by the plurality of formulas (A) may be the same or different. When k is 2 or more, the plurality of R ⁴ may be the same or different. ]
[7] The curable resin composition according to [6], wherein R ³ is an methylene group, an ethylene group or a propylene group which may have an aryl group.
[8] The curable resin composition according to any one of [1] to [7], wherein R ¹ is a hydrogen atom.
[9] The formula (A) is any one of [6] to [8], which is the formula (Aa), the formula (Ab), the formula (Ac), or the formula (Ad). Curable resin composition.

[In Formula (Aa), Formula (Ab), Formula (Ac), and Formula (Ad), R ⁴ and k are the same as above. ]
[10] The curable resin composition according to any one of [6] to [7], [9], wherein k is 0.
[11] The curable resin composition according to any one of [1] to [10], wherein M is a metal or a metal oxide.
[12] The curable resin composition according to any one of [1] to [11], wherein M is copper, zinc, or vanadyl.
[13] The curable resin composition according to any one of [1] to [12], wherein the resin is an alkali-soluble resin.
[14] The curable resin composition according to any one of [1] to [13], further including a polymerizable compound and a polymerization initiator.
[15] The curable resin composition according to any one of [1] to [14], further including a solvent.
[16] The curable resin composition according to [15], wherein the solvent is an alcohol solvent, an ether solvent, or an ester solvent.
[17] A cured film formed from the curable resin composition according to any one of [1] to [16], and having a maximum absorption wavelength in the range of 700 to 1100 nm, 0.150 to 4.000. A cured film having the following absorbance:

  According to the present disclosure, there is provided a curable resin composition in which infrared (preferably near infrared) absorption ability is not impaired by repeated heat treatment at high temperature even when a resin having polarity is included.

FIG. 1 is a graph showing the relationship between the wavelength and absorbance at 400 to 1100 nm for the coating film 1, the cured film 1-1, and the cured film 1-2. FIG. 2 is a graph showing the relationship between the wavelength and absorbance at 400 to 1100 nm for the coating film A, the cured film A-1, and the cured film A-2. FIG. 3 is a graph showing the relationship between the wavelength and absorbance at 400 to 1100 nm for the coating film B, the cured film B-1 and the cured film B-2.

[Curable resin composition]
<Phthalocyanine compound>
The curable resin composition according to the present invention includes a phthalocyanine compound represented by the formula (I).

[In the formula (I),
M represents a nonmetal, a metal, a metal oxide, or a metal halide.
R ¹ and R ² are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. Or a heterocyclic group which may have a substituent.
X represents a halogen atom.
m is an integer of 1-16.
y is an integer from 1 to 16, and y ≧ m.
When m is 2 or more, the plurality of —NR ¹ R ² may be the same or different. When (ym) is 2 or more, the plurality of X may be the same or different. ]

  M being nonmetallic means that M is an atom other than a metal, for example, two hydrogen atoms. Examples of the metal represented by M include iron, magnesium, nickel, cobalt, copper, palladium, and zinc. 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, and silicon chloride. As M, a metal or a metal oxide is more preferable, and copper or vanadyl is still more preferable.

The alkyl group in R ¹ , R ² and R ⁴ is linear, branched or cyclic, and the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms.
Carbon number of the said linear or branched alkyl group becomes like this. Preferably it is 1-20, More preferably, it is 1-8, More preferably, it is 1-4. Specific examples of the linear or branched alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n -Pentyl group, isopentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 2-methyl 1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1-isopropylbutyl group, 2-methyl- 1-isopropyl group, 1-tert-butyl-2-methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl Group, dodecyl group, undecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonidecyl group, eicosyl group, lauryl group, stearyl group, 3-methyl-2-butyl group, 2, 3 -Dimethyl-2-butyl group, 3,3-dimethyl-2-butyl group, 2-methyl-3-pentyl group, 3-methyl-2-pentyl group, 4-methyl-2-pentyl group, 2,2- Dimethyl-3-pentyl group, 2,3-dimethyl-3-pentyl group, 2,4-dimethyl-3-pentyl group, 4,4-dimethyl-2-pentyl group, 2-methyl-3-hexyl group, 5 -Methyl-2-hexyl group, 2,3,3-trimethyl-2-butyl group, 3,4-dimethyl-2-pentyl group, 2,3-dimethyl-2-pentyl group, 3,3-dimethyl 2-pentyl group, 3-ethyl-2-pentyl group, 4-methyl-3-hexyl group, 3-methyl-2-hexyl group, 2,2-dimethyl-3-hexyl group, 2,3-dimethyl- 2-hexyl group, 2,5-dimethyl-2-hexyl group, 2,5-dimethyl-3-hexyl group, 3,4-dimethyl-3-hexyl group, 3,5-dimethyl-3-hexyl group, 3 -Ethyl-2-methyl-3-pentyl group, 4-methyl-3-heptyl group, 5-methyl-2-heptyl group, 5-methyl-3-heptyl group, 6-methyl-2-heptyl group, 6- Methyl-3-heptyl group, 2,3,4-trimethyl-2-pentyl group, 2,3,4-trimethyl-3-pentyl group, 2-methyl-3-ethyl-2-pentyl group, 3-ethyl- 3-methyl-2-pentyl group, 3-ethyl-4-methyl Ru-2-pentyl group, 2-ethyl-3-methyl-2-pentyl group, 2,3-dimethyl-3-hexyl group, 2,4-dimethyl-3-hexyl group, 4,5-dimethyl-3- Hexyl group, 4-ethyl-3-hexyl group, 3-ethyl-2-hexyl group, 3,4-dimethyl-2-hexyl group, 3,5-dimethyl-2-hexyl group, 2-methyl-3-heptyl Group, 3-methyl-2-heptyl group, 3-methyl-4-heptyl group, 2,6-dimethyl-4-heptyl group, 3-ethyl-2,2-dimethyl-3-pentyl group, 2-methyl- 3-octyl group, 3,5-dimethyl-4-heptyl group, 2,4-dimethyl-3-ethyl-3-pentyl group, 2,3-dimethyl-4-heptyl group, 4-ethyl-2-methyl- 3-hexyl group, 2,4,5-trimethyl-3-hexyl Group, 3,4,5-trimethyl-2-hexyl group, 3-ethyl-4-methyl-2-hexyl group, 4-ethyl-3-methyl-2-hexyl group, 2,3-dimethyl-4-heptyl Group, 3,7-dimethyl-3-octyl group, 3,7-dimethyl-4-octyl group, 2,6-dimethyl-3-octyl group, 2-methyl-3-undecyl group, 7-ethyl-2- Examples thereof include a methyl-4-undecyl group, a 2-methyl-3-tridecyl group, and a 2-methyl-4-tridecyl group.
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, and a cyclooctyl group.

The number of carbon atoms of the aryl group in R ¹ and R ² are preferably 6-20, more preferably 6-12. 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, and a phenanthryl group.

Carbon number of the aralkyl group in R < ¹ > and R < ² > is preferably 7-20, more preferably 7-12. Examples of the aralkyl group include a benzyl group, a phenethyl group, and an α-methylbenzyl group.

The heterocyclic group in R ¹ and R ² is preferably a heterocyclic group having at least one selected from an oxygen atom, a sulfur atom, and a nitrogen atom as a ring-constituting atom. -Furyl group, 3-furyl group, furfuryl group, 2-thienyl group, 3-thienyl group, 2-thenyl group, 3-tenyl group, 2-thenoyl group, 3-thenoyl group, 2-pyridyl group, 3-pyridyl group Group, 4-pyridyl group, 2-quinolyl group, 4-quinolyl group, 8-quinolyl group, 1-isoquinoyl group, piperidino group, morpholino group, 2-piperidyl group, 3-piperidyl group, 4-piperidyl group, 2- Morpholinyl group, 3-morpholinyl group, indolyl group, isoindolyl group, 1H-indolyl group, indolinyl group, 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, 2H-pyrrolyl group Examples include 3-yl group, 3H-pyrrol-2-yl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, and oxazinyl group.

The alkyl group represented by R ¹ , R ² and R ⁴ may have a substituent. Examples of the substituent include an alkoxy group having 1 to 20 carbon atoms which may have a substituent, and a substituent. C2-C8 alkoxycarbonyl group which may have a group, halogen atom, nitro group, hydroxy group, amino group, C1-C20 alkylamino group which may have a substituent, formyl Group, a carbamoyl group, an optionally substituted alkylaminocarbonyl group having 2 to 21 carbon atoms, an optionally substituted alkoxysulfonyl group having 1 to 20 carbon atoms, and the like. Of these, an amino group is preferred as the substituent for the alkyl group represented by R ⁴ .
The aryl group, aralkyl group, and heterocyclic group represented by R ¹ and R ² may have a substituent, and the substituent may have 1 to 20 carbon atoms that may have a substituent. An alkyl group, an optionally substituted aryl group having 6 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 20 carbon atoms, and an optionally substituted carbon group. 2-8 alkoxycarbonyl group, optionally substituted aryloxycarbonyl group having 7 to 21 carbon atoms, optionally substituted alkylsulfonyloxycarbonyl group having 2 to 21 carbon atoms, 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 , May have a substituent An alkanoyl group having 2 to 21 carbon atoms, a carbamoyl group, an alkylaminocarbonyl group having 2 to 21 carbon atoms which may have a substituent, and an alkoxysulfonyl having 1 to 20 carbon atoms which may have a substituent Group, a C1-C20 alkylthio group which may have a substituent, an oxyalkyl ether group, etc. are mentioned.
The alkyl group represented by R ¹ , R ² and R ⁴ , and the aryl group, aralkyl group and heterocyclic group represented by R ¹ and R ² each have one or more substituents (more preferably 1 to 5, more preferably 1 to 2), and when having a plurality of the substituents, the substituents may be the same or different.

The alkyl group having 1 to 20 carbon atoms in the substituent is the same as the alkyl group represented by R ¹ , R ² and R ⁴ , and the alkyl group preferably has 1 to 8 carbon atoms, more preferably Is 1-4. The alkyl group may have a substituent, and examples of the substituent include the same substituents that the alkyl group represented by R ¹ , R ² and R ⁴ may have. The
Specific examples of the alkyl group having a substituent include a chloromethyl group, bromomethyl group, dichloromethyl group, dibromomethyl group, trichloromethyl group, tribromomethyl group, 1-chloroethyl group, 1-bromoethyl group, 2- Chloroethyl group, 2-bromoethyl group, 1,2-dichloroethyl group, 1,2-dibromoethyl group, 1,1-dichloroethyl group, 1,1-dibromoethyl group, 2,2-dichloroethyl group, 2, 2-dibromoethyl group, 1,1,2-trichloroethyl group, 1,1,2-tribromoethyl group, 1,2,2-trichloroethyl group, 1,2,2-tribromoethyl group, 1- Chloropropyl group, 1-bromopropyl group, 2-chloro-1-propyl group, 2-bromo-1-propyl group, 3-chloro-1-propyl group, 3-bromo-1-pro Group, 1-chloro-2-propyl group, 1-bromo-2-propyl group, 2,3-dichloro-1-propyl group, 2,3-dibromo-1-propyl group, 1,3-dichloro-2 -Propyl group, 1,3-dibromo-2-propyl group, 4-chloro-1-butyl group, 4-bromo-1-butyl group, 1-chloro-1-butyl group, 1-bromo-1-butyl group 1-chloro-2-butyl group, 1-bromo-2-butyl group, 2-chloro-1-butyl group, 2-bromo-1-butyl group, 1,3-dichloro-2-butyl group, 1, 3-dibromo-2-butyl group, 1,4-dichloro-2-butyl group, 1,4-dibromo-2-butyl group, 5-chloro-1-pentyl group, 5-bromo-1-pentyl group, 1 -Chloro-1-pentyl group, 1-bromo-1-pentyl group, 6-chloro-1-he Sil group, 6-bromo-1-hexyl group, 1-chloro-1-hexyl group, 1-bromo-1-hexyl group, 7-chloro-1-heptyl group, 7-bromo-1-heptyl group, 1- Chloro-1-heptyl group, 1-bromo-1-heptyl group, 8-chloro-1-octyl group, 8-bromo-1-octyl group, 1-chloro-1-octyl group, 1-bromo-1-octyl Group, 9-chloro-1-nonyl group, 9-bromo-1-nonyl group, 1-chloro-1-nonyl group, 1-bromo-1-nonyl group, 10-chloro-1-decyl group, 10-bromo -1-decyl group, 1-chloro-1-decyl group, 1-bromo-1-decyl group, 11-chloro-1-undecyl group, 11-bromo-1-undecyl group, 1-chloro-1-undecyl group 1-bromo-1-undecyl group, 12-chloro- And halogenated alkyl groups such as 1-dodecyl group, 12-bromo-1-dodecyl group, 1-chloro-1-dodecyl group, 1-bromo-1-dodecyl group, and the like.

The aryl group in the substituent is the same as the aryl group in R ¹ and R ² . The aryl group may have a substituent, and examples of the substituent include the same substituents that the aryl group in R ¹ and R ² may have.
As an aryl group having a substituent,
o-methylphenyl group, m-methylphenyl group, p-methylphenyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, o-propylphenyl group, m-propylphenyl group, p- Propylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl group, o-butylphenyl group, m-butylphenyl group, p-butylphenyl group, o-tert-butylphenyl group, m- tert-butylphenyl group, p-tert-butylphenyl group, 2,6-dimethylphenyl group, 2,6-diethylphenyl group, 2,6-dipropylphenyl group, 2,6-diisopropylphenyl group, 2,6 An alkyl-substituted aryl group such as a dibutylphenyl group or a 2,6-ditert-butylphenyl group;
o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, m-ethoxyphenyl group, p-ethoxyphenyl group, o-propoxyphenyl group, m-propoxyphenyl group, p- Propoxyphenyl group, o-isopropoxyphenyl group, m-isopropoxyphenyl group, p-isopropoxyphenyl group, o-butoxyphenyl group, m-butoxyphenyl group, p-butoxyphenyl group, 2,6-dimethoxyphenyl group Alkoxy-substituted aryl groups such as 2,6-diethoxyphenyl group, 2,6-dipropoxyphenyl group, 2,6-diisopropoxyphenyl group, 2,6-dibutoxyphenyl group;
2-fluorophenyl group, 2-chlorophenyl group, 2-bromophenyl group, 2-iodophenyl group, 3-fluorophenyl group, 3-chlorophenyl group, 3-bromophenyl group, 3-iodophenyl group, 4-fluorophenyl Group, 4-chlorophenyl group, 4-bromophenyl group, 4-iodophenyl group, 2,3-difluorophenyl group, 2,3-dichlorophenyl group, 2,4-difluorophenyl group, 2,4-dichlorophenyl group, 2 , 4-Dibromophenyl group, 2,5-difluorophenyl group, 2,5-dichlorophenyl group, 2,6-difluorophenyl group, 2,6-dichlorophenyl group, 2,6-dibromophenyl group, 3,4-difluoro Phenyl group, 3,4-dichlorophenyl group, 3,5-difluorophenyl group, 3,5-dichlorophene Group, 2,3,4-trifluorophenyl group, 2,3,4-trichlorophenyl group, 2,3,5-trifluorophenyl group, 2,3,5-trichlorophenyl group, 2,3,6 -Trifluorophenyl group, 2,3,6-trichlorophenyl group, 2,4,6-trifluorophenyl group, 2,4,6-trichlorophenyl group, 2,4,6-tribromophenyl group, 2, And halogenated aryl groups such as 4,6-triiodophenyl group, 2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group, pentachlorophenyl group; and the like.

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. Carbon number of the alkoxy group is preferably 1-8. Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, Isopentyloxy group, neopentyloxy group, 1,2-dimethyl-propoxy group, n-hexyloxy group, cyclohexyloxy group, 1,3-dimethylbutoxy group, 1-isopropylpropoxy group, 1,2-dimethylbutoxy group N-heptyloxy group, 1,4-dimethylpentyloxy group, 2-methyl-1-isopropylpropoxy group, 1-ethyl-3-methylbutoxy group, n-octyloxy group, 2-ethylhexyloxy group, 3- Methyl-1-isopropylbutoxy group, 2-methyl-1-isopropoxy group, 1-te t- butyl-2-methyl propoxy group, n- nonyloxy group, n- decyloxy group and the like. The alkoxy group may have a substituent, and examples of the substituent include the same substituents that the alkyl group represented by R ¹ , R ² and R ⁴ may have. The
As an alkoxy group having a substituent,
Methoxymethoxy group, methoxyethoxy group, ethoxyethoxy group, propoxyethoxy group, butoxyethoxy group, 3-methoxypropyloxy group, 3-ethoxypropyloxy group, dimethoxymethoxy group, diethoxymethoxy group, dimethoxyethoxy group, diethoxy Alkoxyalkoxy groups such as ethoxy groups;
Alkoxyalkoxyalkoxy groups such as methoxyethoxyethoxy group, ethoxyethoxyethoxy group, and butyloxyethoxyethoxy group;
Alkoxyalkoxyalkoxyalkoxy groups such as methoxymethoxymethoxymethoxy group and ethoxyethoxyethoxyethoxy group;
Chloromethoxy group, bromomethoxy group, dichloromethoxy group, dibromomethoxy group, trichloromethoxy group, tribromomethoxy group, 1-chloroethoxy group, 1-bromoethoxy group, 2-chloroethoxy group, 2-bromoethoxy group, 1 , 2-dichloroethoxy group, 1,2-dibromoethoxy group, 1,1-dichloroethoxy group, 1,1-dibromoethoxy group, 2,2-dichloroethoxy group, 2,2-dibromoethoxy group, 1,1 , 2-trichloroethoxy group, 1,1,2-tribromoethoxy group, 1,2,2-trichloroethoxy group, 1,2,2-tribromoethoxy group, 1-chloropropoxy group, 1-bromopropoxy group 2-chloro-1-propoxy group, 2-bromo-1-propoxy group, 3-chloro-1-propoxy group, 3-bromo-1- Roxy group, 1-chloro-2-propoxy group, 1-bromo-2-propoxy group, 2,3-dichloro-1-propoxy group, 2,3-dibromo-1-propoxy group, 1,3-dichloro-2 -Propoxy group, 1,3-dibromo-2-propoxy group, 4-chloro-1-butoxy group, 4-bromo-1-butoxy group, 1-chloro-1-butoxy group, 1-bromo-1-butoxy group 1-chloro-2-butoxy group, 1-bromo-2-butoxy group, 2-chloro-1-butoxy group, 2-bromo-1-butoxy group, 1,4-dichloro-2-butoxy group, 1, 4-dibromo-2-butoxy group, 5-chloro-1-pentyloxy group, 5-bromo-1-pentyloxy group, 1-chloro-1-pentyloxy group, 1-bromo-1-pentyloxy group, 6 -Chloro-1-hex Ruoxy group, 6-bromo-1-hexyloxy group, 1-chloro-1-hexyloxy group, 1-bromo-1-hexyloxy group, 7-chloro-1-heptyloxy group, 7-bromo-1-heptyl Oxy group, 1-chloro-1-heptyloxy group, 1-bromo-1-heptyloxy group, 8-chloro-1-octyloxy group, 8-bromo-1-octyloxy group, 1-chloro-1-octyl Oxy group, 1-bromo-1-octyloxy group, 9-chloro-1-nonyloxy group, 9-bromo-1-nonyloxy group, 1-chloro-1-nonyloxy group, 1-bromo-1-nonyloxy group, 10 -Chloro-1-decyloxy group, 10-bromo-1-decyloxy group, 1-chloro-1-decyloxy group, 1-bromo-1-decyloxy group, 11-chloro-1-u Ndecyloxy group, 11-bromo-1-undecyloxy group, 1-chloro-1-undecyloxy group, 1-bromo-1-undecyloxy group, 12-chloro-1-dodecyloxy group, 12-bromo- 1-dodecyloxy group, 1-chloro-1-dodecyloxy group, 1-bromo-1-dodecyloxy group, chloromethoxyethoxy group, bromomethoxyethoxy group, 1-chloroethoxyethoxy group, 1-bromoethoxyethoxy group, 1-chloro-3 ′, 6′-oxaheptyloxy group, 1-bromo-3 ′, 6′-oxaheptyloxy group, 1-chloro-3 ′, 6′-oxaoctyloxy group, 1-bromo-3 ', 6'-oxaoctyloxy group, 1-chloro-3', 6 ', 9'-oxadecyloxy group, 1-bromo-3', 6 ', 9'-oxadecyloxy group, 1-chloro -3 ′, 6 ′, 9 ′, 12′-oxatridecyloxy group, 1-bromo-3 ′, 6 ′, 9 ′, 12′-oxatridecyloxy group, chloromethoxypropoxy group, bromomethoxypropoxy group 1-chloroethoxypropoxy group, 1-bromoethoxypropoxy group, 1-chloro-4 ′, 8′-oxanonyloxy group, 1-bromo-4 ′, 8′-oxanonyloxy group, 1-chloro-4 Halogenated alkoxy groups such as ', 8'-oxadecyloxy group, 1-bromo-4', 8'-oxadecyloxy group;
And alkylaminoalkoxy groups such as dimethylaminoethoxy group and diethylaminoethoxy group.

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 that may contain a hetero atom, and the carbon number of the alkoxycarbonyl group is , Preferably 2-5. Specific examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert- Butoxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, neopentyloxycarbonyl group, 1,2-dimethyl-propyloxycarbonyl group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl group, 1,3- Dimethyl-butyloxycarbonyl group, 1-isopropylpropyloxycarbonyl group, 1,2-dimethylbutyloxycarbonyl group, n-heptyloxycarbonyl group, 1,4-dimethylpentyloxycal Nyl group, 2-methyl-1-isopropylpropyloxycarbonyl group, 1-ethyl-3-methylbutyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, 3-methyl-1-isopropylbutyloxy Carbonyl group, 2-methyl-1-isopropyloxycarbonyl group, 1-tert-butyl-2-methylpropyloxycarbonyl group, n-nonyloxycarbonyl group, methoxymethoxycarbonyl group, methoxyethoxycarbonyl group, ethoxyethoxycarbonyl group, Propoxyethoxycarbonyl group, butoxyethoxycarbonyl group, diethylaminoethoxycarbonyl group, methylthioethoxycarbonyl group, methoxypropyloxycarbonyl group, γ-methoxypropoxycarbonyl group, γ-ethoxypropoxycarbonyl group, methoxyethoxyethoxycarbonyl group, ethoxyethoxyethoxycarbonyl group, dimethoxymethoxycarbonyl group, diethoxymethoxycarbonyl group, dimethoxyethoxycarbonyl group, diethoxyethoxycarbonyl group, (3,6,9-oxa) Decyloxycarbonyl group, tetrahydrofurfuryloxycarbonyl group, pyranoxycarbonyl group, piperidinooxycarbonyl group, piperidinoethoxycarbonyl group, tetrahydropyrroleoxycarbonyl group, tetrahydropyranmethoxycarbonyl group, tetrahydrothiophenoxycarbonyl group, cyclohexyl An oxycarbonyl group etc. are mentioned. The alkoxycarbonyl group may have a substituent, and examples of the substituent include the same substituents that the alkyl group represented by R ¹ , R ² and R ⁴ may have. The
Examples of the alkoxycarbonyl group having a substituent include chloromethoxycarbonyl group, bromomethoxycarbonyl group, 2-chloroethoxycarbonyl group, 2-bromoethoxycarbonyl group, 3-chloro-1-propoxycarbonyl group, 3-bromo-1- Propoxycarbonyl group, 2-chloro-1-propoxycarbonyl group, 2-bromo-1-propoxycarbonyl group, 1-chloro-2-propoxycarbonyl group, 1-bromo-2-propoxycarbonyl group, 2,3-dichloro- 1-propoxycarbonyl group, 2,3-dibromo-1-propoxycarbonyl group, 1,3-dichloro-2-propoxycarbonyl group, 1,3-dibromo-2-propoxycarbonyl group, 1-chloro-2-butoxycarbonyl Group, 1-bromo-2-butoxycarbonyl group, -Chloro-1-butoxycarbonyl group, 2-bromo-1-butoxycarbonyl group, 4-chloro-1-butoxycarbonyl group, 4-bromo-1-butoxycarbonyl group, 1,4-dichloro-2-butoxycarbonyl group 1,4-dibromo-2-butoxycarbonyl group, 5-chloro-1-pentyloxycarbonyl group, 5-bromo-1-pentyloxycarbonyl group, 6-chloro-1-hexyloxycarbonyl group, 6-bromo- 1-hexyloxycarbonyl group, 7-chloro-1-heptyloxycarbonyl group, 7-bromo-1-heptyloxycarbonyl group, 8-chloro-1-octyloxycarbonyl group, 8-bromo-1-octyloxycarbonyl group 9-chloro-1-nonyloxycarbonyl group, 9-bromo-1-nonyloxycar Nyl group, 10-chloro-1-decyloxycarbonyl group, 10-bromo-1-decyloxycarbonyl group, 11-chloro-1-undecyloxycarbonyl group, 11-bromo-1-undecyloxycarbonyl group, 12 -Halogenated alkoxycarbonyl groups such as -chloro-1-dodecyloxycarbonyl group, 12-bromo-1-dodecyloxycarbonyl group, trichloroethoxycarbonyl group, trifluoromethoxycarbonyl group, hexafluoro-2-propoxycarbonyl group, etc. It is done.

  Examples of the halogen atom in the substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom, a bromine atom and an iodine atom, and more preferably a chlorine 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, and a p-tert-butylbenzoyl group. 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 , R ² and R ⁴ 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 moiety, and the alkylamino group preferably has 1 to 8 carbon atoms. It is. Specific examples of the alkylamino group include methylamino group, ethylamino group, n-propylamino group, n-butylamino group, sec-butylamino group, n-pentylamino group, n-hexylamino group, n -Monoalkylamino groups such as heptylamino group and n-octylamino group; 2-ethylhexylamino group, dimethylamino group, diethylamino group, di-n-propylamino group, di-n-butylamino group, di-sec- And dialkylamino groups such as butylamino group, di-n-pentylamino group, di-n-hexylamino group, di-n-heptylamino group, di-n-octylamino group and n-decylamino group; . The alkylamino group may have a substituent, and examples of the substituent include the same substituents that the alkyl group represented by R ¹ , R ² and R ⁴ may have. The

In addition, the alkylsulfonyl group, the alkylaminocarbonyl group, and the alkylthio group in the alkylthio group in the substituent are the same as the alkyl group having ¹ to 20 carbon atoms represented by R ¹ , R ^2, and R ^4. The group may have a substituent, and examples of the substituent include the same substituents that the alkyl group represented by R ¹ , R ² and R ⁴ may have. .
In addition, the aryloxycarbonyl group and the aryl group of the arylamino group in the substituent are the same as the aryl group in R ¹ and R ² . These groups may have a substituent, and examples of the substituent include the same substituents that the aryl group in R ¹ and R ² 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 examples of the substituent include R ¹ , R ² and Examples thereof are the same as the substituents that the alkyl group represented by R ⁴ may have.

R ¹ and R ² are preferably at least one of an aryl group which may have a substituent or an aralkyl group which may have a substituent.

  X is preferably a fluorine atom, a chlorine atom or a bromine atom, and X includes at least a fluorine atom or a bromine atom. X is more preferably a fluorine atom, or a bromine atom and / or a chlorine atom.

In the formula (I), since the total number of hydrogen atoms on the benzene nucleus of the phthalocyanine skeleton is 16, the maximum value of y is 16. Further, since X may be bonded to the benzene nucleus of the phthalocyanine skeleton, a relationship of y ≧ m is required.
m is preferably 4 or more, more preferably 6 or more, preferably 12 or less, more preferably 10 or less.
y is preferably 4 or more, more preferably 8 or more, and still more preferably 12 or more.
When m is 2 or more, the plurality of —NR ¹ R ² may be the same or different. When (ym) is 2 or more, the plurality of X may be the same or different.

  When X contains a bromine atom, the number of bromine atoms 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. More preferably, it is 9 or less. As the number of bromine atoms increases, the phthalocyanine compound represented by the formula (I) becomes longer in wavelength.

  Further, the total number of bromine atoms in X is preferably larger than the total number of chlorine atoms in X.

In addition, when X contains a bromine atom, the number of substituents in which —NR ¹ R ² is represented by the formula (A) is preferably 2 or more, more preferably 3 or more, and preferably 10 Below, more preferably 8 or less, still more preferably 6 or less, particularly preferably 5 or less.

When X contains a bromine atom, the total number of the bromine atom, chlorine atom, and —NR ¹ R ² in X represented by formula (A) in formula (I) is preferably Is 10 or more, more preferably 13 or more, still more preferably 15 or more, and particularly preferably 16.

  The phthalocyanine compound represented by the formula (I) is preferably a phthalocyanine compound represented by the formula (II).

[In the formula (II), M, R ¹ , R ² and X are the same as above. a to d are each independently an integer of 1 or more and 4 or less. ]
In the formula (II), a to d are each independently preferably 3 or less, more preferably 2 or less.

  The phthalocyanine compound represented by the formula (II) is preferably a phthalocyanine compound represented by the formula (III).

[In the formula (III), M, R ¹ , R ² and X are the same as defined above. e to h are each independently an integer of 1 or more and 2 or less. ]
In the formula (III), e to h are preferably each independently 2.

In formula (I) to formula (III), R ¹ is preferably a hydrogen atom.

In the formulas (I) to (III), —NR ¹ R ² is preferably a group represented by the formula (Ib).

[In formula (Ib), R ¹ is the same as defined above. Ar is a phenyl group which may have a substituent or a naphthyl group which may have a substituent. ]
The phenyl group or naphthyl group represented by Ar may have a substituent, and examples of the substituent include the same substituents that the aryl group in R ¹ and R ² may have. Is done.

In formulas (I) to (III), —NR ¹ R ² is more preferably a group represented by formula (Ic).

[In formula (Ic), R ¹ is the same as defined above.
Z has a halogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 20 carbon atoms, or a substituent. And represents an alkoxycarbonyl group having 1 to 8 carbon atoms.
j is an integer of 0 or more and 5 or less.
When j is 2 or more, the plurality of Z may be the same or different. ]

In the formula (Ic), examples of Z include the same substituents that the aryl group in R ¹ and R ² may have. j is preferably 3 or less, more preferably 0 or 1, and still more preferably 0.
In the formulas (Ib) and (Ic), R ¹ is preferably a hydrogen atom.

In formulas (I) to (III), —NR ¹ R ² is preferably a group represented by formula (A).

[In formula (A), R ¹ and R ⁴ are the same as above.
R ³ is an alkylene group having 1 to 20 carbon atoms which may have a substituent.
k represents an integer of 0 or more and 5 or less.
When the group represented by the formula (A) is 2 or more, the groups represented by the plurality of formulas (A) may be the same or different. When k is 2 or more, the plurality of R ⁴ may be the same or different. ]

The alkylene group having 1 to 20 carbon atoms represented by R ³ may be linear, branched or cyclic. The number of carbon atoms of the alkylene group represented by R ³ is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. In the formula (A), the alkylene group having 1 to 20 carbon atoms represented by R ³ is preferably a methylene group (—CH ₂ —), an ethylene group (—CH ₂ CH ₂ —) or a propylene group (—CH ( CH ₃ ) —CH ₂ —), particularly preferably a methylene group.
Moreover, the C1-C20 alkylene group represented by R < ³ > may have a substituent, and as said substituent, the C6-C20 aryl group which may have a substituent. Etc. Examples of the aryl group and the substituent of the aryl group are the same as the substituents that the aryl group in R ¹ and R ^{2 and} the aryl group in R ¹ and R ² may have. The substituent for the alkylene group having 1 to 20 carbon atoms represented by R ³ is preferably a phenyl group.

R ⁴ is preferably an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 20 carbon atoms, a halogen atom, or an amino group. And 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 formula (A), k is preferably 4 or less, more preferably 3 or less, still more preferably 2 or less, and still more preferably 0 or 1 or more.

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

  Formula (A) is preferably Formulas (Aa) to (Ad), and more preferably Formula (Aa), Formula (Ac), or Formula (Ad).

[In the formulas (Aa) to (Ad), R ⁴ and k are the same as above. ]

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

［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 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 phthalocyanine compound represented by the formula (I) is, for example, a method described in Japanese Patent No. 282624, Japanese Patent No. 3260317, or Japanese Patent No. 4266410, or a compound represented by the formula (X) (hereinafter referred to as the formula (X)). And may be referred to as compound (X)) and an amine compound represented by formula (Y) (hereinafter also referred to as amine compound (Y)).

［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、フッ素原子、塩素原子または臭素原子を表し、Ｒ¹¹¹〜Ｒ¹²⁶の１つ以上はフッ素原子または臭素原子である。
なお、Ｒ¹¹¹〜Ｒ¹²⁶の１つ以上が臭素原子の場合には、Ｒ¹¹¹〜Ｒ¹²⁶の１つ以上は塩素原子である。］

[In the formula (X),
M represents a nonmetal, a metal, a metal oxide, or a metal halide.
R ^{111 to} R ¹²⁶ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom, and one or more of R ^{111 to} R ¹²⁶ are a fluorine atom or a bromine atom.
When one or more of R ^{111 to} R ¹²⁶ is a bromine atom, one or more of R ^{111 to} R ¹²⁶ is a chlorine atom. ]

［式（Ｙ）中、Ｒ¹、Ｒ³、Ｒ⁴及びｋは前記に同じ。］

[In formula (Y), R ¹ , R ³ , R ⁴ and k are the same as above. ]

  The phthalocyanine compound represented by the formula (I) obtained by reacting the compound (X) with the amine compound (Y) may be filtered, silica gel column chromatography, alumina column chromatography, sublimation, It can refine | purify suitably by well-known purification means, such as a crystal | crystallization and a crystallization. The chemical structure of the phthalocyanine compound represented by formula (I) should be analyzed by a known analysis method such as mass spectrometry, single crystal X-ray structure analysis, Fourier transform infrared spectroscopy, or nuclear magnetic resonance spectroscopy. Can do.

In the phthalocyanine compounds represented by the formulas (I) to (III), as the phthalocyanine skeleton having one or more fluorines, specifically,
・ Dodecafluorotetrakis (anilino) phthalocyanine,
-Dodecafluorotetrakis (o-toluidino) phthalocyanine,
-Dodecafluorotetrakis (p-toluidino) phthalocyanine,
Dodecafluorotetrakis (2,4-xylidino) phthalocyanine,
Dodecafluorotetrakis (2,6-xylidino) phthalocyanine,
-Dodecafluorotetrakis (o-methoxyanilino) phthalocyanine,
-Dodecafluorotetrakis (p-methoxyanilino) phthalocyanine,
-Dodecafluorotetrakis (m-methoxyanilino) phthalocyanine,
-Dodecafluorotetrakis (o-fluoroanilino) phthalocyanine,
-Dodecafluorotetrakis (p-fluoroanilino) phthalocyanine,
-Dodecafluorotetrakis (tetrafluoroanilino) phthalocyanine,
Dodecafluorotetrakis (o-methoxycarbonylanilino) phthalocyanine,
-Dodecafluorotetrakis (p-methoxycarbonylanilino) phthalocyanine,
-Dodecafluorotetrakis (m-methoxycarbonylanilino) phthalocyanine,
Dodecafluorotetrakis (o-ethoxycarbonylanilino) phthalocyanine,
-Dodecafluorotetrakis (p-ethoxycarbonylanilino) phthalocyanine,
・ Dodecafluorotetrakis (methylamino) phthalocyanine,
・ Dodecafluorotetrakis (ethylamino) phthalocyanine,
・ Dodecafluorotetrakis (butylamino) phthalocyanine,
・ Dodecafluorotetrakis (octylamino) phthalocyanine,
-Octafluorooctakis (anilino) phthalocyanine,
-Octafluorooctakis (o-toluidino) phthalocyanine,
-Octafluorooctakis (p-toluidino) phthalocyanine,
-Octafluorooctakis (m-toluidino) phthalocyanine,
-Octafluorooctakis (2,4-xylidino) phthalocyanine,
-Octafluorooctakis (2,6-xylidino) phthalocyanine,
-Octafluorooctakis (o-methoxyanilino) phthalocyanine,
-Octafluorooctakis (p-methoxyanilino) phthalocyanine,
-Octafluorooctakis (m-methoxyanilino) phthalocyanine,
-Octafluorooctakis (o-fluoroanilino) phthalocyanine,
-Octafluorooctakis (p-fluoroanilino) phthalocyanine,
-Octafluorooctakis (tetrafluoroanilino) phthalocyanine,
-Octafluorooctakis (o-ethoxycarbonylanilino) phthalocyanine,
-Octafluorooctakis (p-ethoxycarbonylanilino) phthalocyanine,
-Octafluorooctakis (m-ethoxycarbonylanilino) phthalocyanine,
-Octafluorooctakis (methylamino) phthalocyanine,
-Octafluorooctakis (ethylamino) phthalocyanine,
・ Octafluorooctakis (butylamino) phthalocyanine,
-Octafluorooctakis (octylamino) phthalocyanine,
・ Pentadecafluoromonoanilinophthalocyanine,
・ Pentadecafluoromono (o-toluidino) phthalocyanine,
Pentadecafluoromono (p-toluidino) phthalocyanine,
・ Pentadecafluoromono (m-toluidino) phthalocyanine,
Pentadecafluoromono (2,4-xylidino) phthalocyanine,
Pentadecafluoromono (2,6-xylidino) phthalocyanine,
Pentadecafluoromono (o-methoxyanilino) phthalocyanine,
Pentadecafluoromono (p-methoxyanilino) phthalocyanine,
・ Pentadecafluoromono (m-methoxyanilino) phthalocyanine,
Pentadecafluoromono (o-fluoroanilino) phthalocyanine,
Pentadecafluoromono (p-fluoroanilino) phthalocyanine,
・ Pentadecafluoromono (tetrafluoroanilino) phthalocyanine,
Pentadecafluoromono (o-ethoxycarbonylanilino) phthalocyanine,
Pentadecafluoromono (p-ethoxycarbonylanilino) phthalocyanine,
Pentadecafluoromono (m-ethoxycarbonylanilino) phthalocyanine,
・ Pentadecafluoromono (methylamino) phthalocyanine,
・ Pentadecafluoromono (ethylamino) phthalocyanine,
・ Pentadecafluoromono (butylamino) phthalocyanine,
・ Pentadecafluoromono (octylamino) phthalocyanine,
Tetradecafluorobis (anilino) phthalocyanine,
Tetradecafluorobis (n-butylamino) phthalocyanine,
Tetradecafluorobis (cyclohexylamino) phthalocyanine,
Decafluorohexa (o-toluidino) phthalocyanine,
Nonafluorohepta (2,3,4,5,6-pentafluoroanilino) phthalocyanine,
Nonafluorohepta (2,4-xylidino) phthalocyanine,
・ Heptafluoronona (anilino) phthalocyanine,
-Octafluoroocta (benzylamino) phthalocyanine,
-Octafluoroocta (2-naphthylamino) phthalocyanine,
-Octafluoroocta (2-pyridino) phthalocyanine,
-Octafluoroocta (diethylamino) phthalocyanine,
-Octafluoroocta (diphenylamino) phthalocyanine,
Nonafluorohepta (di-n-butylamino) phthalocyanine,
Octafluorotetra (anilino) tetra (p-toluidino) phthalocyanine,
-Octafluorotetra (n-octylamino) tetra (m-chloroanilino) phthalocyanine,
-Octafluoropenta (anilino) tri (p-toluidino) phthalocyanine,
-Octafluorohexa (n-pentylamino) bis (p-cyanoanilino) phthalocyanine,
・ Tetra (anilino) phthalocyanine,
Tetra (m-nitroanilino) phthalocyanine,
Tetra (tert-butylamino) phthalocyanine,
-Hexa (p-N, N-dimethylaminoanilino) phthalocyanine,
-Octa (p-tert-butylanilino) phthalocyanine,
Hexafluorobis (anilino) phthalocyanine,
Hexafluorobis (1-naphthylamino) phthalocyanine,
-Hexafluorobis (m-bromoanilino) phthalocyanine,
Tetrafluorotetra (anilino) phthalocyanine,
Tetrafluorotetra (n-butylamino) phthalocyanine,
-Tetrafluorotetra (benzyl) phthalocyanine etc. are illustrated.
Among them, dodecafluorotetrakis (anilino) phthalocyanine, octafluorooctakis (anilino) phthalocyanine, pentadecafluoromonoanilinophthalocyanine, tetradecafluorobis (anilino) phthalocyanine, heptafluoronona (anilino) phthalocyanine, tetra (anilino) phthalocyanine, Hexafluorobis (anilino) phthalocyanine and tetrafluorotetra (anilino) phthalocyanine are preferred, and octafluorooctakis (anilino) phthalocyanine is more preferred.

Specific examples of the phthalocyanine skeleton having one or more bromines in the phthalocyanine compounds represented by the formulas (I) to (III) are as follows. In the following, “{number of substituents represented by formula (A) (substituent represented by formula (A))}-{number of chlorine atoms (chloro)}-{number of bromine atoms (bromo )}-Copper phthalocyanine ", the phthalocyanine compounds represented by the formula (I) are listed, but the total number of substituents, chlorine atoms and bromine atoms represented by the formula (A) 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)}-{ Puta (bromo)}-copper phthalocyanine / {tri-penta (2-aminomethylbenzylamino)}-{hexa-tetra (chloro)}-{hepta (bromo)}-copper phthalocyanine / {tri-penta (3-amino) Methylbenzylamino)}-{hexa-tetra (chloro)}-{hepta (bromo)}-copper phthalocyanine / {tri-penta (4-aminomethylbenzylamino)}-{hexa-tetra (chloro)}-{hepta (Bromo)}-copper phthalocyanine · {tri-penta (2-aminobenzylamino)}-{hexa-tetra (chloro)}-{hepta (bromo)}-copper phthalocyanine · {tri-penta (3-aminobenzylamino) )}-{Hexa-tetra (chloro)}-{hepta (bromo)}-copper phthalocyanine / {tri-penta (4-aminoben) Ruamino)}-{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-pe Ta (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, etc.

  The amount of the amine compound (Y) used when the compound (X) is reacted with the amine compound (Y) is preferably 1 time mol or more, more preferably 5 times mol or more, still more preferably relative to the compound (X). 30 times mol or more, Preferably it is 100 times mol or less, More preferably, it is 90 times mol or less, More preferably, it is 80 times mol or less.

  The reaction of compound (X) and 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 amine compound (Y)). Examples of the solvent that can be used include N-methyl-pyrrolidone (more specifically, 1-methyl-2-pyrrolidone, etc.), amide solvents such as N, N-dimethylformamide, nitro solvents such as pyridine, benzoate, and the like. Examples thereof include nitrile solvents such as nitrile, dimethyl sulfoxide and the like. These solvents may use only 1 type and may use 2 or more types together. 1-100 mass times is preferable with respect to compound (X) and an amine compound (Y), and, as for the usage-amount (total) of the said solvent, 1-50 mass times is more preferable.

  In the reaction between the compound (X) and the amine compound (Y), the reaction temperature may be appropriately set. For example, it is preferably 30 ° C. or higher, more preferably 60 ° C. or higher, further preferably 80 ° C. or higher, and 200 ° C. or lower. Preferably, 190 degrees C or less is more preferable. The reaction time is not particularly limited and may be appropriately set according to the progress of the reaction. For example, 0.5 hour 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 content of the phthalocyanine compound represented by the formula (I) is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 1 part by mass with respect to 100 parts by mass of the solid content of the resin. It is above, Preferably it is 100 mass parts or less, More preferably, it is 50 mass parts or less, More preferably, it is 30 mass parts or less.
The content of the phthalocyanine compound represented by the formula (I) is preferably 100% by mass or more, more preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably, in the total solid amount of the curable resin composition. Is 1% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less.
Further, in the curable resin composition, in addition to the phthalocyanine compound represented by the formula (I), known infrared absorbers represented by carbon black, titanium black, composite oxide black pigment, and the like impair the effects of the present invention. The content of the phthalocyanine compound represented by the formula (I) is preferably 50% by mass or more in 100% by mass of the infrared absorber contained in the curable resin composition. Preferably it is 70 mass% or more, More preferably, it is 90 mass% or more, More preferably, it is 95 mass% or more.
In the present specification, the “total amount of solids” means the total amount of components that form a cured product (components other than the solvent that volatilizes when the cured product is formed). Specifically, it means the total mass of the solid content of the curable resin composition excluding the solvent.

<Resin>
The curable resin composition of the present invention contains a resin, and the resin has at least (i) an acid value of 30 mgKOH / g or more and 200 mgKOH / g or less, and (ii) a base number of 30 mgKOH / g or more and 200 mgKOH / g or less. Satisfy one or more conditions.

The acid value of the resin is 30 mgKOH / g or more, more preferably 40 mgKOH / g or more, 200 mgKOH / g or less, more preferably 180 mgKOH / g or less.
The acid value of the resin was determined by measuring the acid value of the resin solution with an automatic titration apparatus using a 0.1 N aqueous KOH solution as the titrant, and then determining the acid value per 1 g of solid content from the acid value of the solution and the solid content of the solution. The acid value can be obtained.

The base number of the resin is 30 mgKOH / g or more, more preferably 40 mgKOH / g or more, 200 mgKOH / g or less, more preferably 180 mgKOH / g or less.
The base number of the resin was determined by measuring the base number of the resin solution with an automatic titration apparatus using a 0.1N aqueous HCl solution as the titrant, and then calculating the base number per 1 g of solid content from the base number of the solution and the solid content of the solution. It can be determined by converting the base value to the equivalent of potassium hydroxide.

  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, 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, in a total solid content of 100% by mass of the curable resin composition. % Or less, More preferably, it is 85 mass% or less, More preferably, it is 80 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 an acid group can be bonded to the base polymer. 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). Although the monomer (compound) preferably used for the following by this invention is illustrated below, these can use 1 type (s) or 2 or more types.

(I) Monomer having acid group and polymerizable double bond As the monomer having acid group and polymerizable double bond, (meth) acrylic acid, crotonic acid, cinnamic acid, vinylbenzoic acid, etc. Unsaturated monocarboxylic acids; unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid; succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl) Unsaturated monocarboxylic acids in which the chain between the unsaturated group and the carboxyl group is extended; Unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; Light ester P-1M (manufactured by Kyoeisha Chemical) Of phosphoric acid group-containing unsaturated compounds. Among these, from the viewpoint of versatility and availability, carboxylic acid monomers (unsaturated monocarboxylic acids, unsaturated polyvalent carboxylic acids, unsaturated acid anhydrides) are preferred, and more preferably ( (Meth) acrylic acid.

(Ii) A monomer having an amino group and a polymerizable double bond As a monomer component constituting the resin, a monomer having an amino group and a polymerizable double bond may be included in the monomer component. Good. As the monomer having an amino group and a polymerizable double bond, a monomer represented by the formula (IV) is preferable.

[In the formula (IV), R ⁵³ has a hydrogen atom or a methyl group, R ^{54 to} R ⁵⁵ each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent, R ⁵⁴ and R ⁵⁵ may be bonded to each other to form a cyclic structure. Y represents a single bond or a divalent linking group. ]

R ⁵⁴ and R ⁵⁵ are each independently an aliphatic hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 12) or an alicyclic hydrocarbon group having 3 to 20 carbon atoms (preferably 3 to 12 carbon atoms). Or an aromatic hydrocarbon group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms), and the aliphatic hydrocarbon group and the alicyclic hydrocarbon group are either saturated or unsaturated. Also 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.

Examples of the divalent linking group represented by Y include 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. 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 a bond that bonds with 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 monomers (i) to (ii) described above, as a monomer component constituting the resin,
(Meth) methyl acrylate, (meth) ethyl acrylate, (meth) acrylate n-propyl, (meth) acrylate i-propyl, (meth) acrylate n-butyl, (meth) acrylate-sec-butyl , (Meth) 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 (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate , (Meth) acrylic acid lauryl, (meth) acrylic acid stearyl, (meth) acrylic acid base Zyl, phenyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (meth) acrylic acid 2- Hydroxypropyl, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methacrylic acid 2- Methoxyethyl, 2-ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, (meth) Β-ethylglycidyl acrylate, (meth) acrylic acid (3 4-epoxycyclohexyl) methyl, methyl α-hydroxymethyl (meth) acrylate, ethyl α-hydroxymethyl (meth) acrylate, 1,4-dioxaspiro [4.5] dec-2-yl (meth) acrylic acid, (Meth) acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl- 2-isobutyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2,2-dimethyl-1, Such as 3-dioxolane and alkoxylated phenylphenol (meth) acrylate Meth) acrylic acid ester monomer;
Aromatic vinyl monomers such as styrene, vinyltoluene, α-methylstyrene, methoxystyrene;
N-substituted such as N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-tert-butylmaleimide, N-dodecylmaleimide, N-benzylmaleimide, N-naphthylmaleimide Maleimide monomers;
Dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2 ′-[oxybis (methylene) Acrylic ether dimers such as bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate;
Α- (unsaturated alkoxyalkyl) acrylate monomers such as alkyl- (α-methallyloxymethyl) acrylate and α- (allyloxymethyl) acrylate;
(Meth) acrylamides;
Macromonomers having a (meth) acryloyl group at one end of the polymer molecular chain;
Conjugated dienes;
Vinyl esters;
Vinyl ethers;
N-vinyl compounds;
Examples thereof include unsaturated isocyanates.

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

  As a method for polymerizing the monomer component, commonly used techniques such as bulk polymerization, solution polymerization, emulsion polymerization and the like can be used, and the method may be appropriately selected according to the purpose and application. Among these, solution polymerization is preferred because it is industrially advantageous and structural adjustments such as molecular weight are easy. The polymerization mechanism of the monomer component can be a polymerization method based on a mechanism such as radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization, 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 is a free radical, electromagnetic wave (for example, infrared ray, ultraviolet ray, X-ray, etc.), It is a group that can be polymerized by irradiation with an active energy ray such as an electron beam.

The content of the polymerizable compound (solid content) 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, preferably 100 parts by mass of the solid content of the resin. 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, and further preferably 10% by mass or more, in the total solid content of 100% by mass of the curable resin composition. Yes, preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less.

  As the polymerizable compound, a (meth) acrylate compound (preferably a polyfunctional (meth) acrylate compound having two or more functions); a polyfunctional vinyl ether compound; a vinyl ether group-containing (meth) acrylate compound; a polyfunctional allyl ether compound; (Meth) acrylic acid esters; polyfunctional (meth) acryloyl group-containing isocyanurates; polyfunctional allyl group-containing isocyanurates; polyfunctional urethane (meth) acrylates; polyfunctional aromatic vinyls; Examples thereof include acids and unsaturated acid anhydrides.

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, bisphenol F alkylene oxide di (meth) acrylate;
Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol tri (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 ditrimethylolpropane tetra (meth) acrylate, ethylene oxide Addition pentaerythritol tetra (meth) acrylate, ethylene oxide addition dipe Taerythritol hexa (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added ditrimethylolpropane tetra (meth) acrylate, propylene oxide-added pentaerythritol tetra (meth) acrylate, propylene oxide-added dipentaerythritol hexa (Meth) acrylate, ε-caprolactone-added trimethylolpropane tri (meth) acrylate, ε-caprolactone-added ditrimethylolpropane tetra (meth) acrylate, ε-caprolactone-added pentaerythritol tetra (meth) acrylate, ε-caprolactone-added dipentaerythritol Trifunctional or more polyfunctional (meth) acrylate compounds such as hexa (meth) acrylate; Can be mentioned.

  Since the curability is further improved and the hardness of the cured product can be further improved, the functional number of the polymerizable compound is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and still more preferably 5 That's it. Further, from the viewpoint of further suppressing curing shrinkage, the functional number is preferably 10 or less, more preferably 8 or less. In general, as the number of functional groups of a polymerizable compound increases, many infrared absorbers are decomposed by repeated heat treatment, and the infrared absorption ability in a cured product tends to decrease, but the phthalocyanine compound represented by the formula (I) If the number of functional groups of the polymerizable compound is increased, it is possible to suppress a decrease in infrared absorbing ability in the cured product. In addition, when it has two or more functional groups, the same functional group may be sufficient, but a different functional group may be sufficient.

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

<Polymerization 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 parts by mass or more, more preferably 0.5 parts by mass or more, and still more preferably 1 part by mass or more with respect to 100 parts by mass of the solid content of the resin. Yes, preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more 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 100% by mass of the total solid content of the curable resin composition. It is at least mass%, preferably at most 20 mass%, more preferably at most 15 mass%, still more preferably at most 10 mass%.

  The polymerization initiator is preferably a radically polymerizable polymerization initiator. The radical polymerizable polymerization initiator is one that generates a polymerization initiating radical by irradiation with an active energy ray such as an electromagnetic wave or an electron beam. Moreover, you may use together 1 type (s) or 2 or more types of photosensitizers, radical photopolymerization promoters, etc. as needed. By using a photosensitizer and / or a radical photopolymerization accelerator in combination with the polymerization initiator, sensitivity and curability are further improved.

Specific examples of the polymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-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-morpholine-4- Aminoketone compounds such as yl-phenyl) -butan-1-one (“IRGACURE379”, manufactured by BASF); 2,2-dimethoxy-1,2-diphenylethane-1-one (“IRGACURE651”, manufactured by BASF) , Such as phenyl glyoxylic acid methyl ester ("DAROCUR MBF", manufactured by BASF) Ketal compounds: 1-hydroxy-cyclohexyl-phenyl-ketone (“IRGACURE184”, manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (“DAROCUR1173”, manufactured by BASF), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (“IRGACURE2959”, manufactured by BASF), 2-hydroxy-1- {4- [ 4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one (“IRGACURE127”, manufactured by BASF), [1-hydroxy-cyclohexyl-phenyl-ketone + Hyde such as benzophenone] ("IRGACURE500", manufactured by BASF) Ketone compounds; alkylphenone compounds; benzophenone compounds; benzoin compounds; thioxanthone compounds; halomethylated triazine compounds; halomethylated oxadiazole compounds; biimidazole compounds; oxime ester compounds; titanocene compounds; Acid ester compounds; acridine compounds and the like; phosphine oxide compounds; oxime ester compounds;
Since the polymerization initiator is more excellent in hardness, an aminoketone-based compound is preferable.

<Solvent>
The curable resin composition may contain a solvent. A solvent is preferably used as a diluent or the like. As the solvent, one or more commonly used solvents can be used, and may be appropriately selected according to the purpose and application. Methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, alcohol 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; ethyl acetate, butyl acetate, propylene glycol Ester solvents such as rumonomethyl ether acetate and propylene glycol monoethyl ether acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone and diacetone alcohol; aromatics such as toluene and xylene Hydrocarbon solvents; aliphatic hydrocarbon solvents such as hexane; amide solvents such as N, N-dimethylformamide; and the like. As the solvent, alcohol solvents, ether solvents, or ester solvents are preferable. .

  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 at least mass%, more preferably at least 30 mass%, preferably at most 90 mass%, more preferably at most 88 mass%, still more preferably at most 85 mass%.

<Other ingredients>
The curable resin composition of the present invention may also contain one or more other components (also referred to as other components) as necessary (for example, depending on the required characteristics of each application to be applied). Good.
Other components include a coupling agent; a polymerization inhibitor; a fluorine additive; a polymerizable compound other than the polymerizable compound described above; a filler; a photosensitizer; a photoradical polymerization accelerator; a colorant (also referred to as a colorant). 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; Plasticizer; Ultraviolet absorber; Antibacterial agent; matting agent; antifoaming agent; antistatic agent; slip agent; surface modifier; thixotropic agent; thixotropic agent; quinonediazide compound; polyhydric phenol compound; cationic polymerizable compound; Is mentioned.

<Method for producing curable resin composition>
It does not specifically limit as a manufacturing method of the curable resin composition of this invention, It can prepare by mixing and dispersing the component mentioned above using various mixers and dispersers. A dispersion process and a mixing process are not specifically limited, What is necessary is just to perform by a normal method. Further, it may further include other steps that are normally performed. In the case where the curable resin composition contains a color material, it is preferable to produce it through a color material dispersion treatment step.

[Curing film]
The curable resin composition of the present invention can form a cured film, for example, by irradiation (exposure) with an active energy ray. Specifically, it is preferable to form a cured film by applying a curable resin composition on a substrate (also referred to as a base material), drying it, and irradiating (exposing) an active energy beam to the coated surface. .

  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, Sheet or film made of thermoplastic resin such as ring-opening polymer of polyolefin, polysulfone, cyclic olefin or hydrogenated product thereof; Sheet or film made of thermosetting resin such as epoxy resin or unsaturated polyester resin; aluminum plate, copper plate Metal substrates such as nickel plates and stainless steel plates; ceramic substrates; semiconductor substrates having photoelectric conversion elements; members composed of various materials such as glass substrates (color filters for LCD) having a color material layer on the surface; It is done.

  If necessary, the substrate may be subjected to corona discharge treatment, ozone treatment, chemical treatment with a silane coupling agent, etc., and inorganic or organic components such as a gas barrier layer or a protective film on both sides or one side of the substrate. A component coating film may be formed. Moreover, when using a cured film for the member for display apparatuses, it is suitable to form electrodes, such as ITO, on a board | 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, and cast coating, and any method can be preferably used. The coating film after being applied to the substrate can be dried using a hot plate, IR oven, 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., and are usually performed at a temperature of 50 to 150 ° C. for 10 seconds to 300 seconds. Is preferred.

  As the light source of the active energy ray and the method of the exposure device, the light source and the method of the exposure device exemplified in JP 2013-227485 A [0161] can be used. In the irradiation process of the active energy beam, the active energy beam 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 insolubilized or hardly soluble in the developer.

Further, if necessary, after the step of irradiating the active energy beam, a step of developing with a developer to remove an unexposed portion and forming a pattern (also referred to as a developing step) may be performed. Thereby, a patterned cured film can be obtained. The development treatment in the development step can be usually performed at a development temperature of 10 to 50 ° C. by a method such as immersion development, spray development, brush development, or ultrasonic development. In addition, when using alkaline aqueous solution as a developing solution, it is preferable to wash | clean with water after image development.
The developer 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 developer include ether solvents and alcohol solvents. In addition to the alkaline agent, the alkaline aqueous solution may contain a surfactant, an organic solvent, a buffering agent, a dye, a pigment, and the like as necessary.

Further, if necessary, a post-curing step (also referred to as a post-bake or post-treatment step) may be performed. Examples of the post-curing step include a step of performing post-heating (also referred to as a heat treatment step) in addition to 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. By performing such 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, further 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 effects of the present invention can be more fully 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 of the present invention 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, and still more preferably 0.400 or more. The absorbance is preferably 4.000 or less, more preferably 3.000 or less, still more preferably 2.000 or less, and still more preferably 1.000 or less.

[Uses of curable resin composition]
The cured product (cured film) formed from the curable resin composition of the present invention is a component of various display devices such as a liquid crystal display device, a solid-state imaging device, and a touch panel display device, as well as ink, printing plate, and printed wiring. It is preferably used for various applications such as various optical members such as plates, semiconductor elements, and photoresists, and electrical and electronic equipment. Especially, it is suitable to use for the color filter used for a liquid crystal display device, a solid-state image sensor, etc., and a touchscreen type display apparatus.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.

(Synthesis Example 1)
According to the method described in Example 2 of Japanese Patent No. 3260317, phthalocyanine compound 1 represented by the following formula was synthesized.

(Synthesis Example 2)
In a 300 ml three-necked flask, 7.3 g of brominated chlorinated copper phthalocyanine (containing CI Pigment Green 36, 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 poured 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 crystals were collected by suction filtration. Then, it vacuum-drys at 80 degreeC, The target phthalocyanine compound 2 (Hereafter, it may be called tetra or penta (2-chlorobenzyl amino) -penta or tetra (chloro) -hepta (bromo)-copper phthalocyanine). Obtained (5.6 g, yield 77 wt% based on starting material).

(Synthesis Example 3)
Phthalocyanine compound 3 (tetra-or penta (4-methoxybenzylamino)- Penta or tetra (chloro) -hepta (bromo) -copper phthalocyanine) was obtained (6.2 g, yield 85 wt% based on starting material).

(Synthesis Example 4)
Phthalocyanine compound 4 (tetra-or penta (3-aminomethylbenzylamino) was synthesized in the same manner as in Synthesis Example 2 except that 2-chlorobenzylamine in Synthesis Example 2 was changed to m-xylylenediamine while maintaining the molar ratio. -Pentaor tetra (chloro) -hepta (bromo) -copper phthalocyanine) was obtained (5.3 g, yield 73 wt% based on starting material).

(Synthesis Example 5)
Phthalocyanine compound 5 (triortetra (4-aminobenzylamino)-) was synthesized in the same manner as in Synthesis Example 2 except that 2-chlorobenzylamine in Synthesis Example 2 was changed to 4-aminobenzylamine while maintaining the molar ratio. Hexa or penta (chloro) -hepta (bromo) -copper phthalocyanine may be referred to) (4.9 g, 67 wt% yield based on starting material).

(Synthesis Example 6)
The phthalocyanine compound 6 (tetra-or penta (1-phenylethylamino) was synthesized in the same manner as in Synthesis Example 2 except that 2-chlorobenzylamine in Synthesis Example 2 was changed to DL-1-phenylethylamine while maintaining the molar ratio. -Pentaor tetra (chloro) -hepta (bromo) -copper phthalocyanine) was obtained (6.3 g, yield 86 wt% based on starting material).

(Synthesis Example 7)
Phthalocyanine compound 7 (triortetra (1,1-diphenylmethylamino)-is synthesized in the same manner as in Synthesis Example 2 except that 2-chlorobenzylamine in Synthesis Example 2 is changed to benzhydrylamine while maintaining the molar ratio. Hexa or penta (chloro) -hepta (bromo) -copper phthalocyanine) was obtained (5.8 g, yield 79 wt% based on starting material).

(Synthesis Example 8)
A comparative phthalocyanine compound A represented by the following formula was synthesized according to the method described in Example 7 of Japanese Patent No. 3712298.

(Synthesis Example 9)
According to the method described in Example 16 of Japanese Patent No. 4278923, a comparative phthalocyanine compound B represented by the following formula was synthesized.

Example 1
(Preparation of curable resin composition 1)
As a near-infrared absorbing dye, 0.044 g of phthalocyanine compound 1, 0.483 g of an acrylic binder resin (acid value: 100 mgKOH / g) copolymerized with benzyl methacrylate (BzMA) and methacrylic acid (MAA), and dipenta as a polymerizable compound Erythritol hexaacrylate (Kyoeisha Chemical Co., Ltd. Light Acrylate (registered trademark) DPE-6A) 0.324 g, BASF IRGACURE (registered trademark) 369E 0.03 g and PGMEA 3.90 g as a polymerization initiator were cured. Resin composition 1 (negative 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.
The acid value of the resin was determined by accurately weighing 1.5 g of the resin solution and dissolving it in a mixed solvent of 90 g of acetone / 10 g of water, and using a 0.1 N KOH aqueous solution as a titrant, After measuring the acid value of the resin solution according to the trade name “COM-555”), 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 thickness of 2.0 μm. Thereafter, the obtained substrate was cooled to room temperature, and the coating film on the substrate was exposed to 300 mJ / mm at a wavelength of 365 nm using an exposure machine (NSR-2205i12D manufactured by Nikon Corporation, lens numerical aperture 0.50) through a photomask. It exposed with the exposure amount of cm < ² >. Subsequently, paddle development for 30 seconds was performed twice in total using an aqueous 0.3 wt% tetramethylammonium hydroxide solution in an automatic coating and developing apparatus. After drying, post-baking was performed in an oven at 230 ° C. for 30 minutes to form a cured film 1-1. Next, 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)
About the coating film 1, the cured film 1-1, and the cured film 1-2, the spectrum was measured using Shimadzu Corporation spectrophotometer UV-1800, respectively, and the light absorbency in 400-1100 nm was calculated | required.
Table 1 shows the absorbance at the maximum absorption wavelength λmax (A) for the coating film 1, the cured film 1-1, and the cured film 1-2, where λmax (A) is the maximum absorption wavelength of the coating film.
Table 1 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.
Furthermore, the relationship between the wavelength in 400-1100nm and a light absorbency is shown in FIG.

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

Examples 2-7, Comparative Examples 1-2
In Example 1, except that the phthalocyanine compound 1 was changed to phthalocyanine compounds 2 to 7 and comparative phthalocyanine compounds A to B, the absorbance was measured in the same manner as in Example 1 to evaluate the heat resistance. The results are summarized in Tables 1 and 2, and the relationship between the wavelength and the absorbance at 400 to 1100 nm of Comparative Examples 1 and 2 in which the comparative phthalocyanine compounds A and B are changed are shown in FIGS.

Table 1 shows that the curable resin composition containing the phthalocyanine compounds 1 to 7 can absorb infrared (preferably near infrared) light. Furthermore, in the case of a curable resin composition containing phthalocyanine compounds 1 to 7, the maximum absorption wavelength λmax of each film, both in the cured film after post-baking and in the cured film after further baking at 230 ° C. for 30 minutes, In E), an absorbance of 0.150 or more is satisfied. That is, in the case of a curable resin composition containing a phthalocyanine compound represented by the formula (I), infrared rays (preferably, even if it contains a polar resin or is subjected to repeated heat treatment at high temperature, It can be seen that the near-infrared absorption ability can be maintained in a high state.
In addition, the phthalocyanine compounds 2 to 7 in which —NR ¹ R ² in the formula (I) is a group represented by the formula (A) are also applied to the coating film after being applied on a glass substrate by a spin coating method. Also in the cured film after post-baking and in the cured film after further baking at 230 ° C. for 30 minutes, the peak top in each film is in the range of −25 ≦ Δλmax (E) ≦ 25, and the deviation is There are small features.

  From Table 2, it can be seen that if the curable resin composition contains phthalocyanine compounds 1 to 7, the residual ratio of the dye in the cured film can be maintained in a high state. That is, if it is a curable resin composition containing a phthalocyanine compound represented by the formula (I), it can absorb infrared rays (preferably near infrared rays) by repeated heat treatment at a high temperature even when it contains a polar resin. It can be seen that a curable resin composition is provided in which no damage is caused. Moreover, in Comparative Examples 1-2, the pigment residual ratio (first time) is 9.2 to 10.0%, and the pigment residual ratio (second time) is 1.7 to 3.5%. Then, the dye residual ratio (first time) is 88.7 to 93.2% (about 9 to 10 times that of Comparative Examples 1 and 2), and the dye residual ratio (second time) is 79.7 to 88.0% (comparative). Therefore, it is clear from these experimental examples how the effect of the present invention is excellent.

Claims (17)

Including a phthalocyanine compound represented by formula (I) and a resin;
Curing characterized in that the resin satisfies at least one condition of (i) an acid value of 30 mgKOH / g to 200 mgKOH / g, and (ii) a base value of 30 mgKOH / g to 200 mgKOH / g. Resin composition.

[In the formula (I),
M represents a nonmetal, a metal, a metal oxide, or a metal halide.
R ¹ and R ² are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. Or a heterocyclic group which may have a substituent.
X represents a halogen atom.
m is an integer of 1-16.
y is an integer from 1 to 16, and y ≧ m.
When m is 2 or more, the plurality of —NR ¹ R ² may be the same or different. When (ym) is 2 or more, the plurality of X may be the same or different. ] The curable resin composition according to claim 1, wherein the phthalocyanine compound represented by the formula (I) is a phthalocyanine compound represented by the formula (II).

[In the formula (II), M, R ¹ , R ² and X are the same as above. a to d are each independently an integer of 1 or more and 4 or less. ]   The curable resin composition according to claim 1 or 2, wherein X is a fluorine atom, a chlorine atom or a bromine atom, and X contains at least a fluorine atom or a bromine atom. The curable property according to any one of claims 1 to 3, wherein at least one of R ¹ and R ² is an aryl group which may have a substituent or an aralkyl group which may have a substituent. Resin composition. -NR < ¹ > R < ² > is group represented by a formula (Ib), The curable resin composition of any one of Claims 1-4.

[In formula (Ib), R ¹ is the same as defined above.
Ar is a phenyl group which may have a substituent or a naphthyl group which may have a substituent. ] -NR < ¹ > R < ² > is group represented by Formula (A), The curable resin composition of any one of Claims 1-4.

[In formula (A), R ¹ is the same as defined above.
R ³ is an alkylene group having 1 to 20 carbon atoms which may have a substituent.
R ⁴ is an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 20 carbon atoms, and an optionally substituted carbon. It is a C2-C20 alkylamino group which may have a C2-C8 alkoxycarbonyl group, a halogen atom, a nitro group, a hydroxy group, a formyl group, an amino group, or a substituent.
k represents an integer of 0 or more and 5 or less.
When the group represented by the formula (A) is 2 or more, the groups represented by the plurality of formulas (A) may be the same or different. When k is 2 or more, the plurality of R ⁴ may be the same or different. ] The curable resin composition according to claim 6, wherein R ³ is a methylene group, an ethylene group or a propylene group which may have an aryl group. The curable resin composition according to any one of claims 1 to 7 R ¹ is a hydrogen atom. The formula (A) is the formula (A-a), the formula (A-b), the formula (A-c), or the formula (A-d), and the curability according to claim 6. Resin composition.

[In Formula (Aa), Formula (Ab), Formula (Ac), and Formula (Ad), R ⁴ and k are the same as above. ]   The curable resin composition according to any one of claims 6 to 7, wherein k is 0.   Said M is a metal or a metal oxide, The curable resin composition of any one of Claims 1-10.   The curable resin composition according to claim 1, wherein M is copper, zinc, or vanadyl.   The said resin is alkali-soluble resin, The curable resin composition of any one of Claims 1-12.   Furthermore, the curable resin composition of any one of Claims 1-13 containing a polymeric compound and a polymerization initiator.   Furthermore, the curable resin composition of any one of Claims 1-14 containing a solvent.   The curable resin composition according to claim 15, wherein the solvent is an alcohol solvent, an ether solvent, or an ester solvent.   It is a cured film formed from the curable resin composition of any one of Claims 1-16, Comprising: Absorption of 0.150 or more and 4.000 or less in the maximum absorption wavelength in the range of 700-1100 nm. A cured film comprising:

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