JP6205193B2 - Colored curable composition and color filter using the same - Google Patents

Description

  The present invention relates to a colored curable composition, a cured film using the same, a color filter, a method for producing a color filter, a solid-state imaging device, a liquid crystal display device, and an organic EL display device.

The color filter is an indispensable component for a display of a solid-state image sensor or a liquid crystal display device. In order to form such a color filter, a colored curable composition is employed (Patent Documents 1 to 3).
Here, in recent years, it has been required to reduce the thickness of the color filter in order to reduce crosstalk (mixture of light).

JP 2011-032366 A JP 2008-070822 A JP 2010-008915 A

Here, even if the color filter is thinned, it is required that the spectral wavelength shape remains the same. If it does so, it will be necessary to raise the density | concentration of the coloring agent in solid content in a colored curable composition significantly. However, when the concentration of the colorant in the colored curable composition is increased, it becomes difficult to produce a colored layer pattern by a lithography technique.
The present invention is intended to solve such problems, and a colored curable composition that can form a colored layer pattern that is excellent in spectral characteristics and has high chemical resistance and high heat resistance even when it is thinned. The purpose is to provide.

Under such circumstances, the inventor of the present application studied forming a pattern colored layer by a dry etching process without employing a lithography technique. However, even when a colored layer is formed in a dry etching process, a high concentration of the colorant inevitably reduces the amount of the additive (curing agent), so that it has chemical resistance and heat resistance (diffusion due to heat). Is a problem. Therefore, as a result of further investigation by the inventors of the present application, by using a halogenated phthalocyanine dye as a colorant in a colored curable composition, even if the colorant concentration is kept high, the chemical resistance and heat resistance are high. It has been found that a colored layer pattern can be formed. Although this mechanism is not clear, it is thought to be due to an associative change due to halogenation or a dye-dye or dye-other molecule interaction.
Specifically, the above problem has been solved by the following means <1>, preferably <2> to <14>.
<1> A colorant including at least a halogenated phthalocyanine dye, a thermosetting compound, and a solvent that dissolves at least the halogenated phthalocyanine dye and the thermosetting compound, and the total content of the colorant is based on the total solid content The colored curable composition which is 60-90 mass%.
<2> The colored curable composition according to <1>, wherein the colorant further contains a yellow pigment.
<3> The colored curable composition according to <1> or <2>, wherein the content of the thermosetting compound in the colored curable composition is 5 to 40% by mass with respect to the total solid content.
<4> The colored curable composition according to any one of <1> to <3>, wherein the thermosetting compound is an epoxy compound.
<5> The colored curable composition according to any one of <1> to <4>, wherein the thermosetting compound has two or more epoxy groups in one molecule and has a molecular weight of 1000 or more.
<6> The colored curable composition according to any one of <1> to <5>, wherein the yellow dye is an azo dye and / or a methine dye.
<7> The colored curable composition according to any one of <1> to <6>, wherein the halogenated phthalocyanine dye is represented by the following general formula (1).
General formula (1)
(In General Formula (1), Z ^{1 to} Z ¹⁶ are each a hydrogen atom or a substituent, at least one of the substituents is a halogen atom, and at least one of the other substituents is aromatic. (M represents a hydrogen atom, a metal atom, a metal oxide or a metal halide.)
<8> In the general formula (1), 1 to 8 of Z ^{1 to} Z ¹⁶ are groups represented by the following general formula (1-2) or groups represented by the general formula (1-4). The colored curable composition according to <7>, wherein at least one is a group represented by the general formula (1-2).
General formula (1-2)
(In General Formula (1-2), X is an oxygen atom or a sulfur atom, and A ¹ is a phenyl group which may have a substituent, or a naphthyl group which may have a substituent. is there.)
General formula (1-4)
(In General Formula (1-4), R ′ represents an alkylene group having 1 to 3 carbon atoms, R ″ represents an alkyl group having 1 to 8 carbon atoms, and n1 represents an integer of 0 to 4).
<9> The colored curable composition according to any one of <1> to <6>, wherein the halogenated phthalocyanine dye is represented by the following general formula (1-1).
General formula (1-1)
(In the general formula (1-1), Z ^{1 to} Z ¹⁶ are a hydrogen atom, a halogen atom, a group represented by the following general formula (1-1-2), and the following general formula (1-3), respectively. Represents a group represented by the following general formula (1-4), and 1 to 8 of Z ^{1 to} Z ¹⁶ are represented by the general formula (1-1-2). Represents a group or a group represented by the general formula (1-4), at least one is a halogen atom, and at least one is a group represented by the general formula (1-1-2). Represents two hydrogen atoms, a metal atom, a metal oxide or a metal halide.)
General formula (1-1-2)
(In General Formula (1-1-2), X ¹ is an oxygen atom or a sulfur atom, and A ¹¹ is a phenyl group having 1 to 5 substituents R, or a naphthyl having 1 to 7 substituents R. The substituent R is a nitro group, COOR ¹ (R ¹ is a group represented by the general formula (1-3) or an alkyl group having 1 to 8 carbon atoms), OR ² (R ² is carbon. An alkyl group having 1 to 8 carbon atoms), a halogen atom, an aryl group, a cyano group, an alkyl group having 1 to 8 carbon atoms, a group represented by any one of the general formulas (4) to (6), or a general formula ( Represents a group selected from X).)
(In the general formula (4), R ⁴ is a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a dialkylamino group which may have a substituent, or a substituent. Represents a diarylamino group which may have a substituent or an alkylarylamino group which may have a substituent.
In General Formula (5), d represents an integer of 0 to 2, and when d is 0 or 1, R ⁵ is an alkyl group that may have a substituent or an aryl that may have a substituent. And when d is 2, R ⁵ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a dialkylamino group which may have a substituent, or a substituent. Represents a diarylamino group which may have a substituent, a substituent or an alkylarylamino group which may have a substituent.
In general formula (6), R ⁶ and R ⁷ are each an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkylcarbonyl group which may have a substituent, The arylcarbonyl group which may have a substituent, the alkylsulfonyl group which may have a substituent, and the arylsulfonyl group which may have a substituent are represented. )
(In general formula (X), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. N1 represents an integer of 1 to 3. When n1 is 2 or 3, a plurality of R ¹¹ are each Y ¹ is —O—, —S—, —NR ¹³ — (R ¹³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), —SO ₂ —, or , -C (= O)-, R ¹² represents a monovalent substituent.)
General formula (1-3)
(In General Formula (1-3), R ³ represents an alkylene group having 1 to ³ carbon atoms, R ⁴ represents an alkyl group having 1 to 8 carbon atoms, and n represents an integer of 1 to 4).
General formula (1-4)
(In General Formula (1-4), R ′ represents an alkylene group having 1 to 3 carbon atoms, R ″ represents an alkyl group having 1 to 8 carbon atoms, and n1 represents an integer of 0 to 4).
<10> A cured film obtained by curing the colored curable composition according to any one of <1> to <9>.
<11> A color filter having a colored layer using the colored curable composition according to any one of <1> to <9>.
<12> The color filter according to <11>, wherein the colored layer has a thickness of 0.1 to 1.0 μm.
<13> A step of forming a colored layer using the colored curable composition according to any one of <1> to <9>, a step of forming a photoresist layer on the colored layer, a photo by exposure and development. A method for producing a color filter, comprising: a step of patterning a resist layer to obtain a resist pattern; and a step of dry etching a colored layer using the resist pattern as an etching mask.
<14> A liquid crystal display device, an organic electroluminescence device, or a solid-state imaging device having the color filter according to <11> or <12> or the color filter produced by the method for producing a color filter according to <13>.

The above problem has also been solved by the following means.
<15> A colored curable composition used for dry etching in any one of the above colored curable compositions.
<16> The colored curable composition according to any one of the above colored curable compositions, wherein the amount of the photopolymerizable compound is 5% by mass or less based on the total solid content.
<17> The colored curable composition according to any one of the above colored curable compositions, wherein the compounding amount of the halogenated phthalocyanine dye is 40 to 50% by mass or less based on the total solid content.
<18> The colored curable composition according to any one of the above colored curable compositions, wherein the blending amount of the halogenated phthalocyanine dye is 55 to 80% by mass of the colorant.
<19> The colored curable composition according to any one of the above colored curable compositions, wherein the compounding amount of the epoxy compound is 5 to 40% by mass of the total solid content.

  According to the present invention, it has become possible to provide a colored curable composition that can form a colored layer pattern that is excellent in spectral characteristics and has high chemical resistance and heat resistance even when it is thinned.

It is a schematic sectional drawing which shows the structural example of a color filter and a solid-state image sensor. It is a schematic sectional drawing of a 1st colored layer. It is a schematic sectional drawing which shows the state in which the photoresist layer was formed on the 1st colored layer. It is a schematic sectional drawing which shows the state in which the resist pattern was formed on the 1st colored layer. It is a schematic sectional drawing which shows the state in which the 1st colored pattern was formed by providing a through-hole group in the 1st colored layer by etching. It is a schematic sectional drawing which shows the state from which the resist pattern in FIG. 5 was removed. It is a schematic sectional drawing which shows the state in which the 2nd coloring pattern and the 2nd coloring radiation sensitive layer were formed. It is a schematic sectional drawing which shows the state from which the 2nd coloring radiation sensitive layer in FIG. 7 and a part of 2nd coloring pixel which comprises a 2nd coloring pattern were removed. It is a schematic sectional drawing which shows the state in which the 3rd coloring pattern and the 3rd coloring radiation sensitive layer were formed. It is a schematic sectional drawing which shows the state from which the 3rd coloring radiation sensitive layer in FIG. 9 was removed. It is a schematic sectional drawing of the transparent film in the heat resistance evaluation of an Example. It is a schematic surface figure of the transparent film in the heat resistance evaluation of an Example.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.

  The “colored layer” in the present invention means a pixel used for a color filter.

  The dye in the present invention means a coloring compound that is soluble in a specific organic solvent. Here, the specific organic solvent includes, for example, an organic solvent exemplified in the column of a solvent capable of dissolving at least a halogenated phthalocyanine dye and a thermosetting compound described later. Therefore, the coloring compound which dissolves in at least one organic solvent corresponds to the dye in the present invention.

  Hereinafter, the colored curable composition, the color filter and the manufacturing method thereof, the solid-state imaging device, the liquid crystal display device, and the organic EL display device of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

The colored curable composition of the present invention (hereinafter sometimes referred to as “the composition of the present invention”) includes a colorant containing at least a halogenated phthalocyanine dye, a thermosetting compound, and a halogenated phthalocyanine dye and a thermosetting compound. It contains a solvent that dissolves at least the compound, and the total content of the colorant is 60 to 90% by mass with respect to the total solid content.
As the colorant, a halogenated phthalocyanine dye is essential and may contain other colorants, and preferably contains other colorants. In this invention, it is preferable that it is 65-85 mass% with respect to the total solid, and, as for the total amount of a coloring agent, it is more preferable that it is 70-80 mass%.
Details of these will be described below.

<Halogenated phthalocyanine dye>
The composition of the present invention comprises a halogenated phthalocyanine dye. The halogenated phthalocyanine dye refers to a compound having a phthalocyanine skeleton and having one or more halogen atoms as a substituent. In this invention, it is preferable to have 5-15 halogen atoms in 1 molecule, and it is more preferable to have 6-14. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. A chlorine atom, a fluorine atom, or a bromine atom is preferable, a chlorine atom or a fluorine atom is more preferable, and a chlorine atom is further preferable.
The halogenated phthalocyanine dye used in the present invention is usually a compound having a maximum absorption wavelength in the region of 600 to 800 nm, and preferably having a maximum absorption wavelength in the region of 630 to 750 nm.

The phthalocyanine dye used in the present invention is preferably a compound represented by the following general formula (1).
(In General Formula (1), Z ^{1 to} Z ¹⁶ are each a hydrogen atom or a substituent, at least one of the substituents is a halogen atom, and at least one of the other substituents is aromatic. (M represents a hydrogen atom, a metal atom, a metal oxide or a metal halide.)

Here, in the general formula (1), Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ and Z ¹⁶ represent substituents substituted at eight α positions of the phthalocyanine nucleus. Therefore, these substituents are also referred to as α-position substituents. Similarly, Z ² , Z ³ , Z ⁶ , Z ⁷ , Z ¹⁰ , Z ¹¹ , Z ¹⁴ and Z ¹⁵ in the general formula (1) are substituents substituted at eight β-positions of the phthalocyanine nucleus. These substituents are also referred to as β-position substituents.
Z ^{1 to} Z ¹⁶ are each a hydrogen atom or a substituent, at least one of the substituents is a halogen atom, and at least one of the substituents is a group containing an aromatic group. It is preferable to have 5 to 15 halogen atoms in one molecule, and more preferable to have 6 to 14 halogen atoms. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. A chlorine atom, a fluorine atom, or a bromine atom is preferable, a chlorine atom or a fluorine atom is more preferable, and a chlorine atom is further preferable. The aromatic group in the group containing an aromatic group (preferably a group represented by the general formula (1-2) described later) is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group. The number of groups having an aromatic group is preferably 1 to 11 in one molecule, more preferably 1 to 10 and even more preferably 2 to 7. Further, Z ¹ to Z ¹⁶ are all substituents other than a halogen atom, preferably also a mode is a group having an aromatic group.
The substituent is not particularly defined as long as the phthalocyanine compound does not lose its function as a dye, and examples thereof include substituent T described later.

In General Formula (1), 1 to 8 of Z ^{1 to} Z ¹⁶ represent a group represented by the following General Formula (1-2) or a group represented by General Formula (1-4), and, it is preferable that at least one is a group represented by the general formula (1-2), more preferably, of Z ¹ to Z ^16, 2 to 6 one is represented by the general formula (1-2) Or a group represented by the general formula (1-4), and at least one is a group represented by the general formula (1-2).
General formula (1-2)
(In General Formula (1-2), X is an oxygen atom or a sulfur atom, and A ¹ is a phenyl group which may have a substituent, or a naphthyl group which may have a substituent. is there.)
General formula (1-4)
(In General Formula (1-4), R ′ represents an alkylene group having 1 to 3 carbon atoms, R ″ represents an alkyl group having 1 to 8 carbon atoms, and n1 represents an integer of 0 to 4).

In general formula (1-2), X is an oxygen atom or a sulfur atom, and an oxygen atom is preferable. When X is an oxygen atom, the maximum absorption wavelength of the obtained phthalocyanine compound can be shifted to the short wavelength side.
A ¹ is a phenyl group which may have a substituent, or a naphthyl group which may have a substituent, and a phenyl group having 1 to 5 substituents or 1 to 7 substituents. The naphthyl group having is preferable, and the phenyl group having 1 to 5 substituents is more preferable.

The group represented by the general formula (1-2) is more preferably a group represented by the following general formula (1-1-2).
General formula (1-1-2)
(In General Formula (1-1-2), X ¹ is an oxygen atom or a sulfur atom, and A ¹¹ is a phenyl group having 1 to 5 substituents R, or a naphthyl having 1 to 7 substituents R. The substituent R is a nitro group, COOR ¹ (R ¹ is a group represented by the general formula (1-3) or an alkyl group having 1 to 8 carbon atoms), OR ² (R ² is carbon. An alkyl group having 1 to 8 carbon atoms), a halogen atom, an aryl group, a cyano group, an alkyl group having 1 to 8 carbon atoms, a group represented by any one of the general formulas (4) to (6), or a general formula ( Represents a group selected from X).)
(In the general formula (4), R ⁴ is a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a dialkylamino group which may have a substituent, or a substituent. Represents a diarylamino group which may have a substituent or an alkylarylamino group which may have a substituent.
In General Formula (5), d represents an integer of 0 to 2, and when d is 0 or 1, R ⁵ is an alkyl group that may have a substituent or an aryl that may have a substituent. And when d is 2, R ⁵ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a dialkylamino group which may have a substituent, or a substituent. Represents a diarylamino group which may have a substituent, a substituent or an alkylarylamino group which may have a substituent.
In general formula (6), R ⁶ and R ⁷ are each an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkylcarbonyl group which may have a substituent, The arylcarbonyl group which may have a substituent, the alkylsulfonyl group which may have a substituent, and the arylsulfonyl group which may have a substituent are represented. )
(In general formula (X), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. N1 represents an integer of 1 to 3. When n1 is 2 or 3, a plurality of R ¹¹ are Y ¹ is —O—, —S—, —NR ¹³ — (R ¹³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), —SO _2. -, or, -C (= O) - .R 12 representing a represents a monovalent substituent).

In general formula (1-1-2), X < ¹ > is an oxygen atom or a sulfur atom, and an oxygen atom is preferable. When X ¹ is an oxygen atom, the maximum absorption wavelength of the obtained phthalocyanine compound can be shifted to the short wavelength side.
A ¹¹ is a phenyl group having 1 to 5 substituents or a naphthyl group having 1 to 7 substituents, and a phenyl group having 1 to 5 substituents is more preferable.

  The number of substituents of the phenyl group is an integer of 1 to 5, but more preferably an integer of 1 to 3 from the viewpoint of the Gram extinction coefficient. When the substituent is a halogen atom, the number of substituents is 1 to 5 Any integer of is preferred. The number of substituents of the naphthyl group is an integer of 1 to 7, but from the viewpoint of the gram extinction coefficient (absorbance per gram), it is preferably an integer of 1 to 5, more preferably an integer of 1 to 3. 1 or 2 is more preferable.

The bonding position between the naphthyl group and X ¹ is not particularly limited, and may be either the following 1-position (1-naphthyl group) or 2-position (2-naphthyl group).
Similarly, the bonding position of the substituent to the naphthalene ring is not particularly limited.
For example, when the bonding position between the naphthyl group and X ¹ is the 1-position (1-naphthyl group), the bonding position of the substituent to the naphthalene ring is the 2-position, 3-position, 4-position, 5-position, 6 However, in view of heat resistance, solvent solubility, etc., the 2nd and 3rd positions are preferable, and the 2nd position is more preferable. Further, when the bonding position between the naphthyl group and X ¹ is the 2-position (2-naphthyl group), the bonding positions of the substituent to the naphthalene ring are the 1-position, 3-position, 4-position, 5-position, 6 However, the 3rd and 6th positions are preferable, and the 3rd position is more preferable in consideration of heat resistance and solvent solubility.

The substituent R of the phenyl group or naphthyl group is a nitro group, COOR ¹ (R ¹ is a group represented by the general formula (1-3) or an alkyl group having 1 to 8 carbon atoms), OR ² (R ² Is an alkyl group having 1 to 8 carbon atoms), a halogen atom, an aryl group, a cyano group, an alkyl group having 1 to 8 carbon atoms, a group represented by any one of the general formulas (4) to (6), or general It is a group selected from the formula (X).

  When a plurality of substituents R are present in the phenyl group or naphthyl group, the plurality of Rs may be the same or different.

When the substituent R of the phenyl or naphthyl group is COOR ^1, R ¹ in the COOR ¹ is represented by an optionally substituted alkyl group having 1 to 8 carbon atoms, or the following general formula, (1-3) Represents a group.
General formula (1-3)
(In General Formula (1-3), R ³ represents an alkylene group having 1 to ³ carbon atoms, R ⁴ represents an alkyl group having 1 to 8 carbon atoms, and n represents an integer of 1 to 4).

When R ¹ is an alkyl group having 1 to 8 carbon atoms, the alkyl group having 1 to 8 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms from the viewpoint of solvent solubility. Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, and n-pentyl. And linear, branched or cyclic alkyl groups such as a group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group. Examples of the substituent optionally present in the alkyl group having 1 to 8 carbon atoms include an alkyloxy group having 1 to 8 carbon atoms, a halogen atom or an aryl group.
As the alkyloxy group having 1 to 8 carbon atoms which is a substituent of the alkyl group which may be present in some cases, methoxy group, ethoxy group, n-propyloxy group, iso-propyloxy group, n-butyloxy group, iso- Linear chain such as butyloxy group, sec-butyloxy group, t-butyloxy group, n-pentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group And a branched or cyclic alkyloxy group. Among these, a C1-C4 alkyloxy group is preferable. Examples of the halogen atom that is a substituent of the alkyl group that may be present include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom or a chlorine atom is preferable. Examples of the aryl group that is a substituent of the alkyl group that may be present include a phenyl group, a p-methoxyphenyl group, a pt-butylphenyl group, and a p-chlorophenyl group. Among these, a phenyl group is preferable. A plurality of these substituents may be present. When a plurality of these substituents are present, they may be the same or different, and even in the same case, they may be the same or different. The number of substituents on the alkyl group is not particularly limited, but is preferably 1 to 3, and preferably 1 or 2.

When the substituent R of the phenyl group or naphthyl group is COOR ¹ and R ¹ is a group represented by the general formula (1-3), R ³ in the group represented by the general formula (1-3) is: It is an alkylene group of 1-3 from the point of the effect on ether solvent solubility.
Examples of the alkylene group having 1 to 3 carbon atoms include a methylene group, an ethylene group, an n-propylene group, and an iso-propylene group. Preferably, they are an ethylene group and a propylene group.
R ⁴ in the group represented by the general formula (1-3) is an alkyl group having 1 to 8 from the viewpoint of molecular weight, and more preferably an alkyl group having 1 to 4. Examples of the alkyl group having 1 to 8 carbon atoms include those described in the above R ¹ column. N in the group represented by the general formula (1-3) is an integer of 1 to 4 and preferably an integer of 1 to 3 from the viewpoint of molecular weight.

When the substituent R of the phenyl or naphthyl group is OR ^2, R ² in OR ² represents an alkyl group having 1 to 8 carbon atoms, preferably crystalline dye, from the viewpoint of handling of the good, 1 carbon atoms 3 alkyl groups are shown.
Examples of the alkyl group having 1 to 8 carbon atoms represented by R ² include the same substituents as those described in R ¹ of COOR ¹ , which is an example of the above-described substituent R, and a preferable range is also synonymous. is there.

  When the substituent R of the phenyl group or naphthyl group is a halogen atom, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom, a chlorine atom or an iodine atom is preferable. Among them, a chlorine atom and a fluorine atom are preferable because the molecular weight of the dye is reduced and the gram absorption coefficient is increased.

  When the substituent R of the phenyl group or naphthyl group is an aryl group, examples of the aryl group include aryl groups such as a phenyl group, a p-methoxyphenyl group, a pt-butylphenyl group, and a p-chlorophenyl group. Among them, a phenyl group is preferable because the molecular weight of the dye is reduced and the gram extinction coefficient is increased.

When the substituent R of the phenyl group or naphthyl group is an alkyl group, the alkyl group having 1 to 8 carbon atoms is the same as described above in R ¹ of COOR ¹ as an example of the substituent R. The preferable range is also synonymous.
Preferably, it is a C1-C3 alkyl group from the point of the crystallinity of a pigment | dye, and the good handleability.
As the substituent of the alkyl group which may be present in some cases, a halogen atom is exemplified, and a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are preferable, and a fluorine atom or a chlorine atom is more preferable. There may be a plurality of halogen atoms as substituents for the alkyl group, and when there are a plurality of halogen atoms, they may be the same or different. The number of substituents on the alkyl group is not particularly limited, but is preferably 1 to 3.

  The case where the substituent R of the phenyl group or naphthyl group is a group selected from the following general formulas (4) to (6) will be described.

R ⁴ in the general formula (4) represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a dialkylamino group which may have a substituent, a substituted group A diarylamino group which may have a group or an alkylarylamino group which may have a substituent, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, A dialkylamino group having 2 to 20 carbon atoms, a diarylamino group having 12 to 20 carbon atoms, or an alkylarylamino group having 7 to 20 carbon atoms is preferable, an alkyl group having 1 to 20 carbon atoms, and a total carbon number. A dialkylamino group having 2 to 20 carbon atoms, a diarylamino group having 12 to 20 carbon atoms in total, or an alkylarylamino group having 7 to 20 carbon atoms is more preferable, and a diarylamino group having 12 to 20 carbon atoms in total or Dialkylamino groups of primes from 2 to 20 are particularly preferred.
The alkyl moiety and the aryl moiety may further have a substituent, and the substituent is preferably an alkoxy group, an aryl group, an aryloxy group, an alkoxycarbonyl group, an alkylthio group, an arylthio group or a halogen atom, and an alkoxy group Are more preferable, and a methoxy group or an ethoxy group is more preferable. Moreover, the aspect which does not have a substituent is also preferable.

In General Formula (5), d represents an integer of 0 to 2, and when d is 0 or 1, R ⁵ is an alkyl group that may have a substituent or an aryl that may have a substituent. And when d is 2, the alkyl group which may have a substituent, the aryl group which may have a substituent, the dialkylamino group which may have a substituent, and the substituent Or a diarylamino group which may be substituted or an alkylarylamino group which may have a substituent. R ⁵ is preferably a dialkylamino group having 2 to 20 carbon atoms, a diarylamino group having 12 to 20 carbon atoms, or an alkylarylamino group having 7 to 20 carbon atoms when d is 2.
The alkyl moiety and the aryl moiety may further have a substituent, and examples of the substituent include a substituent T described later. An alkoxy group, an aryl group, an aryloxy group, an alkoxycarbonyl group, an alkylthio group, and an arylthio group. Or a halogen atom etc. are preferable, an alkoxy group is more preferable, and a methoxy group or an ethoxy group is further more preferable. Moreover, the aspect which does not have a substituent is also preferable.

In general formula (6), R ⁶ and R ⁷ are each an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkylcarbonyl group which may have a substituent, An arylcarbonyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, an alkyl group having 1 to 20 carbon atoms, and 6 carbon atoms An arylcarbonyl group having 2 to 20 carbon atoms, an alkylcarbonyl group having 2 to 20 carbon atoms, an arylcarbonyl group having 7 to 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms are preferable. More preferred are an alkylcarbonyl group having 2 to 20 carbon atoms, an arylcarbonyl group having 7 to 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms.
The alkyl moiety and the aryl moiety may further have a substituent, and examples of the substituent include a substituent T described later. An alkoxy group, an aryl group, an aryloxy group, an alkoxycarbonyl group, an alkylthio group, and an arylthio group. Or a halogen atom etc. are preferable, an alkoxy group is more preferable, and a methoxy group or an ethoxy group is further more preferable. Moreover, the aspect which does not have a substituent is also preferable. Examples of the alkyl group and the like which may have a substituent will be described later.

  The suitable example of the alkyl group which may have a substituent in the said general formula is shown. Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a dodecyl group, Hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group, phenoxyethyl group, benzyl group, phenylethyl group, N-butylaminosulfonylpropyl group, N-butylaminocarbonylmethyl group, N, N-dibutylaminosulfonylpropyl group, ethoxyethoxyethyl group, 2-chloroethyl group can be mentioned, more preferably methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, phenoxyethyl group, benzyl group, Phenylethyl group, N-butyl Examples thereof include aminosulfonylpropyl group, N-butylaminocarbonylmethyl group, N, N-dibutylaminosulfonylpropyl group, and ethoxyethoxyethyl group, particularly preferably methyl group, ethyl group, propyl group, tert-butyl group, phenoxyethyl. Group, benzyl group, phenylethyl group, N-butylaminosulfonylpropyl group, N-butylaminocarbonylmethyl group, N, N-dibutylaminosulfonylpropyl group and ethoxyethoxyethyl group.

  The suitable example of the aryl group which may have a substituent in the said General Formula (4)-(6) is shown. Such an aryl group includes a phenyl group, a 2-chlorophenyl group, a 2-methoxyphenyl group, a 4-butoxycarbonylphenyl group, a 4-N, N-dibutylaminocarbonylphenyl group, and a 4-N-butylaminosulfonylphenyl group. 4-N, N-dibutylaminosulfonylphenyl group, more preferably phenyl group, 4-butoxycarbonylphenyl group, 4-N, N-dibutylaminocarbonylphenyl group, 4-N-butylaminosulfonylphenyl group. 4-N, N-dibutylaminosulfonylphenyl group, particularly preferably phenyl group, 4-butoxycarbonylphenyl group, 4-N, N-dibutylaminocarbonylphenyl group, 4-N, N-dibutylaminosulfonyl group. A phenyl group is mentioned.

  The suitable example of the dialkylamino group which may have a substituent in the said General Formula (4)-(6) is shown. Examples of such a dialkylamino group include N, N-dimethylamino group, N, N-dibutylamino group, N, N-di (2-ethylhexyl) amino group, N-methyl-N-benzylamino group, N, N-di (2-ethoxyethyl) amino group, N.I. N-di (2-hydroxyethyl) amino group may be mentioned.

  The suitable example of the diarylamino group which may have a substituent in the said General Formula (4)-(6) is shown. Examples of such a diarylamino group include an N, N-diphenylamino group, an N, N-di (4-methoxyphenyl) amino group, and an N, N-di (4-acylphenyl) amino group.

  The suitable example of the alkylarylamino group which may have a substituent in the said General Formula (4)-(6) is shown. Examples of such an alkylarylamino group include an N-methyl-N-phenylamino group, an N-benzyl-N-phenylamino group, and an N-methyl-N- (4-methoxyphenyl) amino group.

  The suitable example of the alkylcarbonyl group which may have a substituent in the said General Formula (4)-(6) is shown. Examples of such an alkylcarbonyl group include an acetyl group, a propylcarbonyl group, a heptyl-3-carbonyl group, a 2-ethylhexyloxymethylcarbonyl group, a phenoxymethylcarbonyl group, and a 2-ethylhexyloxycarbonylmethylcarbonyl group.

  The suitable example of the arylcarbonyl group which may have a substituent in the said General Formula (4)-(6) is shown. Examples of such an arylcarbonyl group include a benzoyl group, a 4-methoxybenzoyl group, and a 4-ethoxycarbonylbenzoyl group.

  The suitable example of the alkylsulfonyl group which may have a substituent in the said General Formula (4)-(6) is shown. Examples of such an alkylsulfonyl group include a methanesulfonyl group, an octanesulfonyl group, a dodecylsulfonyl group, a benzylsulfonyl group, and a phenoxypropylsulfonyl group.

  The suitable example of the arylsulfonyl group which may have a substituent in the said General Formula (4)-(6) is shown. Examples of such an arylsulfonyl group include a phenylsulfonyl group, a 2-methoxyphenylsulfonyl group, and a 4-ethoxycarbonylphenylsulfonyl group.

  The suitable example of the alkylsulfonylamino group which may have a substituent in the said General Formula (4)-(6) is shown. As such alkylsulfonylamino group, methylsulfonylamino group, butylsulfonylamino group, hydroxypropylsulfonylamino group, 2-ethylhexylsulfonylamino group, n-octylsulfonylamino group, phenoxyethylsulfonylamino group, allylsulfonylamino group Is mentioned.

  Examples of the vinylsulfonylamino group which may have a substituent in the general formulas (4) to (6) include a vinylsulfonylamino group and a 1-methylvinylsulfonylamino group.

  Examples of the arylsulfonylamino group which may have a substituent in the general formulas (4) to (6) include a phenylsulfonylamino group, a p-methoxyphenylsulfonylamino group, a p-ethoxycarbonylsulfonylamino group, and the like. Is mentioned.

  Examples of the alkylcarbonylamino group which may have a substituent in the general formulas (4) to (6) include a methylcarbonylamino group, a 2-ethylhexanoylamino group, an n-heptylcarbonylamino group, and ethoxyethoxy. Examples include a methylcarbonylamino group.

  Examples of the arylcarbonylamino group that may have a substituent in the general formulas (4) to (6) include a benzoylamino group, a 2-methoxybenzoylamino group, and a 4-vinylbenzoylamino group.

Examples of the substituent T are shown below.
An alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, Hexyl group, heptyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group), alkenyl group (preferably having 2 to 2 carbon atoms) 18 alkenyl groups such as vinyl group, allyl group and 3-buten-1-yl group), aryl groups (preferably aryl groups having 6 to 24 carbon atoms such as phenyl group and naphthyl group), heterocyclic ring Group (preferably a heterocyclic group having 1 to 18 carbon atoms such as 2-thienyl group, 4-pyridyl group, 2-furyl group, 2- Limidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group), silyl group (preferably a silyl group having 3 to 18 carbon atoms, for example, trimethylsilyl Group, triethylsilyl group, tributylsilyl group, tert-butyldimethylsilyl group, tert-hexyldimethylsilyl group), hydroxyl group, cyano group, nitro group, alkoxy group (preferably an alkoxy group having 1 to 24 carbon atoms, Methoxy group, ethoxy group, 1-butoxy group, 2-butoxy group, isopropoxy group, tert-butoxy group, dodecyloxy group, and cycloalkyloxy group, for example, cyclopentyloxy group, cyclohexyloxy group) An aryloxy group (preferably having 6 to 2 carbon atoms) An aryloxy group of, for example, phenoxy group, 1-naphthoxy group), a heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 18 carbon atoms, such as 1-phenyltetrazole-5-oxy group, 2- Tetrahydropyranyloxy group), silyloxy group (preferably a silyloxy group having 1 to 18 carbon atoms, for example, trimethylsilyloxy group, tert-butyldimethylsilyloxy group, diphenylmethylsilyloxy group), acyloxy group (preferably carbon number) An acyloxy group having 2 to 24, for example, an acetoxy group, a pivaloyloxy group, a benzoyloxy group, a dodecanoyloxy group, an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 24 carbon atoms, for example, ethoxycarbonyloxy Group, tert-butoki In the case of a sicarbonyloxy group or a cycloalkyloxycarbonyloxy group, for example, a cyclohexyloxycarbonyloxy group, an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 24 carbon atoms, for example, phenoxy Carbonyloxy group), carbamoyloxy group (preferably a carbamoyloxy group having 1 to 24 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group, N-phenylcarbamoyloxy group, N- Ethyl-N-phenylcarbamoyloxy group), sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 24 carbon atoms, for example, N, N-diethylsulfamoyloxy group, N-propylsulfamoyl group) Oxy group), alkyl A sulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 24 carbon atoms, for example, a methylsulfonyloxy group, a hexadecylsulfonyloxy group, a cyclohexylsulfonyloxy group), an arylsulfonyloxy group (preferably having 6 to 24 carbon atoms) An arylsulfonyloxy group such as a phenylsulfonyloxy group, an acyl group (preferably an acyl group having 1 to 24 carbon atoms, such as a formyl group, acetyl group, pivaloyl group, benzoyl group, tetradecanoyl group, cyclohexa Noyl group), alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 24 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, octadecyloxycarbonyl group, cyclohexyloxycarbonyl group, 2,6-di-ter -Butyl-4-methylcyclohexyloxycarbonyl group), aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 24 carbon atoms, such as phenoxycarbonyl group), carbamoyl group (preferably carbamoyl having 1 to 24 carbon atoms) Groups such as carbamoyl, N, N-diethylcarbamoyl, N-ethyl-N-octylcarbamoyl, N, N-dibutylcarbamoyl, N-propylcarbamoyl, N-phenylcarbamoyl, N-methylN -Phenylcarbamoyl group, N, N-dicyclohexylcarbamoyl group), amino group (preferably an amino group having 24 or less carbon atoms, for example, amino group, methylamino group, N, N-dibutylamino group, tetradecylamino group) Group, 2-ethylhexylamino group, cyclohexyl Silamino group), anilino group (preferably 6 to 24 anilino group, for example, anilino group, N-methylanilino group), heterocyclic amino group (preferably 1 to 18 heterocyclic amino group, for example, 4-pyridylamino Group), a carbonamide group (preferably a carbonamide group having 2 to 24 carbon atoms, for example, an acetamido group, a benzamide group, a tetradecanamide group, a pivaloylamide group, a cyclohexaneamide group), a ureido group (preferably a ureido having 1 to 24 carbon atoms). Group, for example, ureido group, N, N-dimethylureido group, N-phenylureido group), imide group (preferably an imide group having 24 or less carbon atoms, for example, N-succinimide group, N-phthalimide group), An alkoxycarbonylamino group (preferably an alkoxycarbonyl group having 2 to 24 carbon atoms) Group, for example, methoxycarbonylamino group, ethoxycarbonylamino group, tert-butoxycarbonylamino group, octadecyloxycarbonylamino group, cyclohexyloxycarbonylamino group), aryloxycarbonylamino group (preferably having 7 to 24 carbon atoms). An aryloxycarbonylamino group such as a phenoxycarbonylamino group, a sulfonamide group (preferably a sulfonamide group having 1 to 24 carbon atoms, such as a methanesulfonamide group, a butanesulfonamide group, a benzenesulfonamide group, hexadecane A sulfonamido group, a cyclohexanesulfonamido group), a sulfamoylamino group (preferably a sulfamoylamino group having 1 to 24 carbon atoms, such as N, N-dipropylsulfamoylamino group, N Ethyl-N-dodecylsulfamoylamino group), azo group (preferably an azo group having 1 to 24 carbon atoms, for example, phenylazo group, 3-pyrazolylazo group), alkylthio group (preferably having 1 to 24 carbon atoms). An alkylthio group, for example, a methylthio group, an ethylthio group, an octylthio group, a cyclohexylthio group, an arylthio group (preferably an arylthio group having 6 to 24 carbon atoms, for example, a phenylthio group), a heterocyclic thio group (preferably a carbon number) 1 to 18 heterocyclic thio groups, for example, 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group), alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 24 carbon atoms) , For example, dodecanesulfinyl group), arylsulfinyl group (preferably having 6 to 2 carbon atoms) 4 arylsulfinyl group, for example, phenylsulfinyl group), alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 24 carbon atoms, for example, methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, isopropyl Sulfonyl group, 2-ethylhexylsulfonyl group, hexadecylsulfonyl group, octylsulfonyl group, cyclohexylsulfonyl group), arylsulfonyl group (preferably arylsulfonyl group having 6 to 24 carbon atoms, such as phenylsulfonyl group, 1-naphthylsulfonyl group) Group), a sulfamoyl group (preferably a sulfamoyl group having 24 or less carbon atoms, such as a sulfamoyl group, an N, N-dipropylsulfamoyl group, an N-ethyl-N-dodecylsulfamoyl group, an N-ethyl group). Ru-N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group), sulfo group, phosphonyl group (preferably phosphonyl group having 1 to 24 carbon atoms, such as phenoxyphosphonyl group, octyloxyphosphonyl group, Phenylphosphonyl group) and a phosphinoylamino group (preferably a phosphinoylamino group having 1 to 24 carbon atoms such as a diethoxyphosphinoylamino group and a dioctyloxyphosphinoylamino group).

  When the above-described substituent is a substitutable group, it may be further substituted with any of the above-described groups. In addition, when it has two or more substituents, those substituents may be the same or different.

  The case where the substituent R of the phenyl group or naphthyl group is a group represented by the general formula (X) will be described.

R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
n1 represents an integer of 1 to 3, and 1 or 2 is more preferable. When n1 is 2 or 3, the plurality of R ¹¹ may be the same or different.
Y ¹ represents —O—, —S—, —NR ¹³ —, —SO ₂ —, or —C (═O) —, and represents —O—, —SO ₂ —, or —C (═O). -Is preferable, and -O- or -C (= O)-is more preferable.
R ¹² represents a monovalent substituent, and examples of the substituent include the above-described substituent T. The substituent T may be further substituted with the substituent T. R ¹² is preferably an alkyl group which may have a substituent, an acyl group which may have a substituent, a sulfonyl group which may have a substituent, an alkoxy group which may have a substituent, Or an alkylamino group which may have a substituent, more preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and 1 to 12 carbon atoms which may have a substituent. Or an alkylamino group having 1 to 12 carbon atoms which may have a substituent.
The mass of the R ¹² portion per molecule is preferably 200-2500, and more preferably 250-1500.
R ¹³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

  When the above-described monovalent group is a group that can be further substituted, it may be further substituted with any of the above-described groups. In addition, when it has two or more substituents, those substituents may be the same or different.

Next, general formula (1-4) is demonstrated.
In General Formula (1-4), R ′ is an alkylene group having 1 to 3 carbon atoms from the viewpoint of ether solubility and molecular weight. Examples of the alkylene group having 1 to 3 carbon atoms include a methylene group, an ethylene group, an n-propylene group, and an iso-propylene group. Preferably, they are an ethylene group and a propylene group.
R ″ is an alkyl group having 1 to 8 carbon atoms, and preferably an alkyl group having 1 to 2 carbon atoms, from the viewpoint of ether solubility and molecular weight. -3) has the same meaning as R ³ , and the preferred range is also the same.
n1 is an integer of 0 to 4 and more preferably an integer of 1 to 2 from the viewpoint of ether solubility and molecular weight.

  Next, M which is the central part of the general formula (1) will be described. In the general formula (1), M represents two hydrogen atoms, a metal atom, a metal oxide, or a metal halide. Examples of the metal atom include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin. Examples of the metal oxide include titanyl and vanadyl. Examples of the metal halide include aluminum chloride, indium chloride, germanium chloride, tin (II) chloride, tin (IV) chloride, and silicon chloride. Preferably, it is a metal atom, a metal oxide or a metal halide, specifically, copper, zinc, cobalt, nickel, iron, vanadyl, titanyl, indium chloride, tin (II) chloride, more preferably copper. Vanadyl and zinc, more preferably zinc and copper, and most preferably zinc. It is preferable that the central metal is zinc or copper because of high heat resistance. Further, it is particularly preferable that the central metal is zinc because the transmittance in the vicinity of 520 nm to 545 nm, which is a green wavelength, is higher than that of copper, and the luminance can be improved when the color filter is formed. Further, it is particularly preferable because it has high solvent solubility in general-purpose solvents such as acetone, methanol, and methyl cellosolve, and has high solubility in resins and high contrast.

The compound represented by the general formula (1) is more preferably represented by the following general formula (1-1).
General formula (1-1)
(In General Formula (1-1), Z ^{1 to} Z ¹⁶ are each represented by a hydrogen atom, a halogen atom, a group represented by General Formula (1-1-2), or General Formula (1-3). Or a group represented by the general formula (1-4), and 1 to 8 of Z ^{1 to} Z ¹⁶ are groups represented by the general formula (1-1-2) or general Represents a group represented by the formula (1-4), at least one is a halogen atom, and at least one is a group represented by the general formula (1-1-2). Represents hydrogen atom, metal atom, metal oxide or metal halide.)

In the general formula (1-1), the general formula (1-1-2), the general formula (1-3), and the general formula (1-4) are represented by the general formula (1-1) described in the general formula (1). -2), general formula (1-3), and general formula (1-4), and the preferred range is also synonymous. Therefore, Z ^{1 to} Z ¹⁶ in the general formula (1-1) are more preferably in the same range as Z ^{1 to} Z ^{16 in} the general formula (1).
M in the general formula (1-1) has the same meaning as M in the general formula (1), and the preferred range is also the same.
Z ^{1 to} Z ¹⁶ in the general formula (1-1) preferably have a group represented by the general formula (1-1-2) or the general formula (1-4). A ¹¹ in the general formula (1-1-2) is a phenyl group having 1 to 5 substituents R, and the substituent R is represented by COOR ¹ (R ¹ is represented by the general formula (1-3). A group selected from the group represented by formula (4), general formula (5), general formula (6) or general formula (X), and -COOH.

The compound represented by the general formula (1) is also preferably represented by the following general formula (1-5). By including the compound represented by the following general formula (1-5), chemical resistance can be further improved.
(In General Formula (1-5), Z ^{1 to} Z ¹⁶ each represent a hydrogen atom, a halogen atom, or a group represented by General Formula (1-5-1), and among Z ^{1 to} Z ¹⁶ , (At least one represents a group represented by (1-5-1) and at least one is a halogen atom. M represents two hydrogen atoms, a metal atom, a metal oxide, or a metal halide.)
Formula (1-5-1)
(In General Formula (1-5-1), L ¹ represents a divalent linking group, Ar represents an arylene group, and A represents a group represented by the following General Formula (1-5-2). (* Represents the site of binding to the phthalocyanine ring.)
Formula (1-5-2)
(In the general formula (1-5-2), L ² represents a single bond or a divalent linking group. R ^{5 to} R ⁷ each represents a hydrogen atom or a monovalent substituent. * Represents a general formula. (Represents the site of binding to Ar in (1-5-1).)

In General Formula (1-5-1), L ¹ represents a divalent linking group. L ¹ is ^one of —O—, —S—, —C (═O) —, —CH ₂ —, —C (═S) —, —NR ^A —, —SO—, —SO ₂ —, or divalent linking group is preferably composed of two or more thereof, -O -, - S -, - C (= O) -, - CH 2 -, - SO 2 - from one or combinations of two or more Are more preferable, -O- or -S- is more preferable, and -O- is particularly preferable.
R ^A represents a hydrogen atom, an alkyl group or an aryl group, and the alkyl group is an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, hexyl group, cyclohexyl group, etc.), and the aryl group is a carbon atom. It is an aryl group of several 6 to 10 (phenyl group, naphthyl group, etc.). R ^A is preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

  In general formula (1-5-1), Ar represents an arylene group. The arylene group here refers to a so-called aromatic ring group and does not include a heterocyclic group. Ar is preferably a phenylene group or a naphthylene group, more preferably a phenylene group or a naphthylene group, and even more preferably a phenylene group.

In general formula (1-5-2), L ² is preferably a divalent linking group. Examples of the divalent linking group include —O—, —S—, —C (═O) —, —CH ₂ —, —CH (OH) —, —C (═S) —, —NR ^B —, —. SO -, - SO ₂ - is preferably one or a divalent linking group composed of a combination of two or more, -O -, - C (= O) -, - CH 2 -, - CH (OH More preferably, it is a divalent linking group consisting of one or a combination of-)-, -NR ^B- .
The general formula (1-5-2) preferably has an acrylate structure or a methacrylate structure. For example, in general formula (1-5-2), L ² preferably has a C (═O) O— structure on the double bond side.
R ^B has the same meaning as R ^A described above, and the preferred range is also the same.

In general formula (1-5-2), R ^{5 to} R ⁷ each represent a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include the above-described substituent T, and an alkyl group is preferable, and an alkyl group having 1 to 10 carbon atoms (a methyl group, an ethyl group, a hexyl group, a cyclohexyl group) and the like are more preferable. R ^{5 to} R ⁷ are more preferably a hydrogen atom or a methyl group, R ⁶ and R ⁷ are particularly preferably a hydrogen atom, and R ⁵ is particularly preferably a hydrogen atom or a methyl group.
In particular, the general formula (1-5-2) is preferably represented by a * -L ^2A- (meth) acryloyloxy group. L ^2A has the same meaning as the above divalent linking group, and is one or more of —O—, —C (═O) —, —CH ₂ —, —CH (OH) —, —NR ^B —. It is more preferable that the group is a combination of the above.

Examples of Z ^{1 to} Z ¹⁶ in general formula (1) and general formula (1-1) used in the present invention will be given below, but the present invention is not limited to these.

Although the example of the phthalocyanine compound used by this invention is given to the following, it cannot be overemphasized that this invention is not limited to these.
The following table shows the substituents represented by the following general formula and their numbers.
Ar in the following table represents the following structure.
In the above formula, Ph is a phenyl group.

In the above, Pc represents a phthalocyanine nucleus, Zn represents a central metal, a substituent substituted at the α-position immediately after Pc, and a substituent substituted at the β-position after the substituent substituted at the α-position. Represents a substituent independent of the substitution position. x and y are positive numbers whose number of substituents is 0 or more.

  Since the phthalocyanine compound is a mixture having different substitution positions and substitution numbers, it is difficult to uniquely describe it as a structural formula. Further, the number of substitutions shown in the following table is a value obtained by approximating the average value of the number of substituents in the mixture, and may be a small number.

Method for Producing Halogenated Phthalocyanine Compound The method for producing the phthalocyanine compound used in the present invention is not particularly limited, and a conventionally known method can be used. A method of cyclizing a phthalonitrile compound and a metal salt, preferably in a molten state or in an organic solvent, can be used particularly preferably. Hereinafter, preferred embodiments of the method for producing a phthalocyanine compound will be described. However, the present invention is not limited to the following preferred embodiments.
That is, the following formula (I):
A phthalonitrile compound (1) represented by the following formula (II):
A phthalonitrile compound (2) represented by the following formula (III):
And a phthalonitrile compound (3) represented by the following formula (IV):
And a phthalonitrile compound (4) represented by the formula: A phthalocyanine compound can be produced by cyclization reaction with one selected.
In the above formulas (I) to (IV), Z ^{1 to} Z ¹⁶ are defined by the structure of the desired phthalocyanine compound (1). Specifically, in the above formulas (I) to (IV), Z ^{1 to} Z ¹⁶ are the same as the definitions of Z ^{1 to} Z ^{16 in} the above formula (1), respectively, and thus the description thereof is omitted here. To do.

The cyclization reaction can be synthesized by a conventionally known method such as the method described in JP-A No. 64-45474.
In the above embodiment, the cyclization reaction is carried out by melting one kind selected from the group consisting of the phthalonitrile compounds of formulas (I) to (IV) and a metal, a metal oxide, a metal carbonyl, a metal halide, and an organic acid metal in a molten state or organic. It is preferable to react in a solvent. Metals, metal oxides, metal carbonyls, metal halides and organic acid metals that can be used at this time are those obtained from the middle newspaper (M in the general formula (1)) of the phthalocyanine compound obtained after the reaction. If there is, there is no particular limitation. Accordingly, metals such as iron, copper, zinc, vanadium, titanium, indium, and tin listed in the item M in the general formula (1), metal halide compounds such as chloride, bromide, and iodide of the metal, Examples thereof include metal oxides such as vanadium oxide, titanyl oxide and copper oxide, organic acid metals such as acetate, complex compounds such as acetylacetonate, and metal carbonyls such as carbonyl iron. Specifically, metals such as iron, copper, zinc, vanadium, titanium, indium, magnesium, and tin; metal halides such as chloride, bromide, and iodide of the metal, such as vanadium chloride, titanium chloride, and chloride Copper, zinc chloride, cobalt chloride, nickel chloride, iron chloride, indium chloride, aluminum chloride, tin chloride, gallium chloride, germanium chloride, magnesium chloride, copper iodide, zinc iodide, cobalt iodide, indium iodide, iodide Aluminum, gallium iodide, copper bromide, zinc bromide, cobalt bromide, aluminum bromide, gallium bromide; vanadium monoxide, vanadium trioxide, vanadium tetroxide, vanadium pentoxide, titanium dioxide, iron monoxide, three Iron dioxide, iron trioxide, manganese oxide, nickel monoxide, cobalt monoxide, cobalt dioxide , Cobalt dioxide, cuprous oxide, cupric oxide, copper trioxide, barium oxide, zinc oxide, germanium monoxide, germanium dioxide and other metal oxides; copper acetate, zinc acetate, cobalt acetate, copper benzoate, And organic acid metals such as zinc benzoate; and complex compounds such as acetylacetonate; and metal carbonyls such as cobalt carbonyl, iron carbonyl and nickel carbonyl. Of these, preferred are metals, metal oxides and metal halides, more preferred are metal halides, still more preferred are vanadium iodide, copper iodide and zinc iodide, and particularly preferred is iodine. Copper iodide and zinc iodide, most preferably zinc iodide. When zinc iodide is used, the central metal is zinc. Among metal halides, it is preferable to use iodide because it is excellent in solubility in solvents and resins, and the spectrum of the obtained phthalocyanine compound is sharp and easily falls within the desired wavelength of 640 to 750 nm. is there. The detailed mechanism of sharpening the spectrum when using iodide during the cyclization reaction is unknown, but when iodide is used, the iodine remaining in the phthalocyanine compound after the reaction may not interact with the phthalocyanine compound. It is presumed that iodine is present between the layers of the phthalocyanine compound due to the action. However, the mechanism is not limited to the above mechanism. In order to obtain the same effect as when metal iodide is used for the cyclization reaction, the obtained phthalocyanine compound may be treated with iodine.

In the above embodiment, the cyclization reaction can be carried out in the absence of a solvent, but it is preferably carried out using an organic solvent. The organic solvent may be any inert solvent that has a low reactivity with the phthalonitrile compound as a starting material, and preferably exhibits no reactivity. For example, benzene, toluene, xylene, nitrobenzene, monochlorobenzene, o -Inert solvents such as chlorotoluene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, ethylene glycol, and benzonitrile; methanol, ethanol, 1-propanol, 2-propanol, 1- Alcohols such as butanol, 1-hexanol, 1-pentanol, 1-octanol; and pyridine, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidinone, N, N-dimethylacetophenone, Triethylamine, tri n- butylamine, dimethyl sulfoxide, aprotic polar solvents such as sulfolane.
Of these, 1-chloronaphthalene, 1-methylnaphthalene, 1-octanol, dichlorobenzene and benzonitrile are preferably used, and more preferably 1-octanol, dichlorobenzene and benzonitrile are used. These solvents may be used alone or in combination of two or more.

  The reaction conditions of the phthalonitrile compound of formulas (I) to (IV) and the metal compound in the above embodiment are not particularly limited as long as the reaction proceeds. For example, the reaction condition is 100 parts by mass of an organic solvent. On the other hand, the total amount of the phthalonitrile compounds of the above formulas (I) to (IV) is 1 to 500 parts by weight, preferably 10 to 350 parts by weight, and the metal compound is based on 4 moles of the phthalonitrile compound. , Preferably 0.8 to 2.0 mol, more preferably 0.8 to 1.5 mol. The cyclization is not particularly limited, but the reaction is preferably performed at a reaction temperature of 30 to 250 ° C, more preferably 80 to 200 ° C. Although reaction time is not specifically limited, Preferably it is 3 to 20 hours. After the reaction, a phthalocyanine compound that can be used in the next step can be efficiently and highly purified by filtration, washing, and drying according to a conventionally known method for synthesizing phthalocyanine compounds.

  In the said aspect, the phthalonitrile compound of the formula (I)-(IV) which is a starting material can be synthesize | combined by a conventionally well-known method, and a commercial item can also be used for it.

<Halogenated phthalocyanine multimer>
The halogenated phthalocyanine dye used in the present invention may be a multimer (halogenated phthalocyanine multimer). In the present specification, a multimer is a compound containing two or more halogenated phthalocyanine structures, and includes a structure such as a dimer, trimer or polymer.

  The halogenated phthalocyanine multimer is a halogenated phthalocyanine multimer comprising at least one of structural units represented by the following general formula (A), general formula (B), and general formula (C), or general A halogenated phthalocyanine multimer represented by the formula (D) is preferred.

Structural unit represented by general formula (A)

In general formula (A), X ¹ represents a linking group formed by polymerization, and L ¹ represents a single bond or a divalent linking group. DyeI represents a structure containing a halogenated phthalocyanine skeleton.

In the above general formula (A), X ¹ represents a linking group formed by polymerization. That is, it refers to a portion that forms a repeating unit corresponding to the main chain formed by the polymerization reaction. Two sites represented by * are repeating units. X ¹ is not particularly limited as long as it is a linking group formed from a known polymerizable monomer, but linking groups represented by the following (XX-1) to (X-24) are particularly preferred, (XX -1) and (XX-2) (meth) acrylic linking chains, (XX-10) to (XX-17) styrenic linking chains, and (XX-24). Most preferred is a vinyl-based connecting chain. In (XX-1) to (X-24), it represents that L ₁ is linked at the site indicated by *. Me represents a methyl group. R in (XX-18) and (XX-19) represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

In general formula (A), L ¹ represents a single bond or a divalent linking group. When L ₁ represents a divalent linking group, the divalent linking group may be a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (eg, methylene group, ethylene group, trimethylene group, propylene group, butylene). Group), a substituted or unsubstituted arylene group having 6 to 30 carbon atoms (for example, phenylene group, naphthalene group, etc.), substituted or unsubstituted heterocyclic linking group, -CH = CH-, -O-, -S. —, —C (═O) —, —CO ₂ —, —NR—, —CONR—, —O ₂ C—, —SO—, —SO ₂ — and a linkage formed by linking two or more thereof. Represents a group. Here, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.
In the general formula (A), DyeI represents a structure containing a halogenated phthalocyanine skeleton, that is, a partial structure derived from a halogenated phthalocyanine in a halogenated phthalocyanine multimer.
For details of the general formula (A), paragraphs 0138 to 0152 of JP 2013-29760 A can be referred to, and the contents thereof are incorporated in the present specification.

Structural unit represented by general formula (B)

In general formula (B), X ² has the same meaning as X ¹ in general formula (A). L ² has the same meaning as L ¹ in the general formula (A). Y ² represents a group capable of ionic bonding or coordination bonding with DyeII. DyeII represents a structure containing a halogenated phthalocyanine skeleton.

In general formula (B), X ² has the same meaning as X ² in general formula (A), and the preferred range is also the same. L ² has the same meaning as L ¹ in the general formula (A), and the preferred range is also the same. Y ² may be any group capable of ionic bonding or coordination bonding with Dye II, and may be either an anionic group or a cationic group. Examples of the anionic group include COO ⁻ , PO ₃ H ⁻ , SO ₃ ⁻ , —SO ₃ NH ⁻ , —SO ₃ N ^— CO—, and the like, with COO ⁻ , PO ₃ H ⁻ and SO ₃ ⁻ being preferred. .
Examples of the cationic group include substituted or unsubstituted onium cations (for example, ammonium, pyridinium, imidazolium, phosphonium and the like), and ammonium cations are particularly preferable.
Y ² can be bonded to an anion part (COO ⁻ , SO ₃ ⁻ , O ⁻ etc.) or a cation part (the onium cation, metal cation etc.) of DyeII.
For details of the general formula (B), paragraphs 0156 to 0161 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

Structural unit represented by general formula (C)

In general formula (C), L ³ represents a single bond or a divalent linking group. DyeIII represents a structure containing a halogenated phthalocyanine skeleton. m represents 0 or 1;

In the general formula (C), the divalent linking group represented by L ³ is a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 30 carbon atoms (for example, a methylene group, an ethylene group, Trimethylene group, propylene group, butylene group, etc.), substituted or unsubstituted arylene group having 6 to 30 carbon atoms (eg, phenylene group, naphthalene group, etc.), substituted or unsubstituted heterocyclic linking group, —CH═CH— , -O-, -S-, -NR- (R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group), -C (= O)-, -SO-, Preferable examples include —SO ₂ — and a linking group formed by linking two or more of these. m represents 0 or 1, but is preferably 1.

It describes a specific example which is suitably used as the divalent linking group represented by L ³ in the general formula (C) below, but not limited to as L ³ of the present invention.
For details of the general formula (C), paragraphs 0165 to 0167 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

Halogenated phthalocyanine multimer represented by the general formula (D)

(In General Formula (D), L ⁴ represents an n-valent linking group. N represents an integer of 2 to 20. When n is 2 or more, the structures of DyeIV may be the same or different. DyeIV represents a structure containing a halogenated phthalocyanine skeleton.)

In said general formula (D), n becomes like this. Preferably it is 3-15, Most preferably, it is 3-6.
In the general formula (D), when n is 2, the divalent linking group represented by L ⁴ is a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (for example, methylene group, ethylene group, trimethylene). Group, propylene group, butylene group, etc.), substituted or unsubstituted arylene group having 6 to 30 carbon atoms (eg, phenylene group, naphthalene group, etc.), substituted or unsubstituted heterocyclic linking group, —CH═CH—, —O—, —S—, —NR— (R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group), —C (═O) —, —SO—, — Preferable examples include SO ₂ — and a linking group formed by linking two or more of these.

  The n-valent linking group where n is 3 or more is a substituted or unsubstituted arylene group (1,3,5-phenylene group, 1,2,4-phenylene group, 1,4,5,8-naphthalene group, etc.) And a linking group formed by substituting the divalent linking group with a heterocycle linking group (for example, 1,3,5-triazine group, etc.), an alkylene linking group or the like as a central mother nucleus.

Specific examples of L ⁴ in the general formula (D) are shown below, but the present invention is not limited thereto.
For details of the general formula (D), paragraphs 0173 to 0178 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

  A halogenated phthalocyanine multimer having a structural unit represented by any one of general formula (A), general formula (B) and general formula (C), and a halogenated phthalocyanine large amount represented by general formula (D) The halogenated phthalocyanine multimer having a structural unit represented by general formula (A) and general formula (C) and the halogenated phthalocyanine multimer represented by general formula (D) are linked by a covalent bond. Therefore, the colored curable composition containing the halogenated phthalocyanine multimer is excellent in heat resistance, and when the colored curable composition is applied to the formation of a colored pattern of multiple colors, This is preferable because it is effective in suppressing color migration. In particular, the compound represented by the general formula (A) is preferable because the molecular weight of the halogenated phthalocyanine multimer is easily controlled.

The halogenated phthalocyanine multimer may have another functional group in the structural portion including the halogenated phthalocyanine skeleton of the above-described halogenated phthalocyanine multimer. Examples of other functional groups include polymerizable groups, acid groups, and alkali-soluble groups (for example, carboxylic acid, sulfonic acid, phosphoric acid, and phenolic hydroxyl group).
Moreover, the halogenated phthalocyanine multimer may contain other repeating units in addition to the repeating unit including the structure containing the halogenated phthalocyanine skeleton described above. Other repeating units may have a functional group. As another repeating unit, the repeating unit containing at least 1 sort (s) of a polymeric group, an acid group, and an alkali-soluble group is illustrated. That is, the halogenated phthalocyanine multimer may have other repeating units in addition to the repeating units represented by the general formulas (A) to (D). One type of other repeating unit may be contained in one halogenated phthalocyanine multimer, or two or more types may be contained.
Moreover, the halogenated phthalocyanine multimer may have another functional group in the halogenated phthalocyanine multimer represented by the general formulas (A) to (D).

The halogenated phthalocyanine multimer preferably contains a polymerizable group. One type of polymerizable group may be included, or two or more types may be included.
As for the polymerizable group, a structure containing a halogenated phthalocyanine skeleton may contain a polymerizable group, or may contain other parts. In the present invention, the structure containing a halogenated phthalocyanine skeleton preferably contains a polymerizable group.
Moreover, in this invention, the aspect in which other parts other than the structure containing a halogenated phthalocyanine skeleton contain a polymeric group is also preferable.
As the polymerizable group, a known polymerizable group that can be crosslinked by a radical, an acid, or heat can be used. Examples thereof include a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetane group), and a methylol group. In particular, a group containing an ethylenically unsaturated bond is preferable, a (meth) acryloyl group is more preferable, and a (meth) acryloyl group derived from glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate is more preferable.
The halogenated phthalocyanine multimer is preferably a polymer having a repeating unit derived from a halogenated phthalocyanine compound having one radical polymerizable group.

  It is also preferable that the halogenated phthalocyanine multimer has an epoxy group. Examples of the halogenated phthalocyanine multimer having an epoxy group include a repeating unit derived from a halogenated phthalocyanine compound having one radical polymerizable group and a radical polymerizable monomer having an epoxy group (for example, glycidyl acrylate, glycidyl methacrylate, etc.). Examples thereof include a polymer having a repeating unit derived therefrom.

As a method for introducing a polymerizable group, for example, paragraphs 0180 to 0188 in JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
For example, a method of obtaining a halogenated phthalocyanine multimer having an ethylenically unsaturated double bond is obtained by radicalizing a monomer mixture containing a halogenated phthalocyanine compound having one radical polymerizable group and a radical polymerizable monomer having a reactive group. The method of adding the compound which reacts with a reactive group and the compound which has an ethylenically unsaturated double bond with respect to the polymer obtained by superposition | polymerization is mentioned.
Examples of the reactive group include a carboxyl group and a hydroxy group. Examples of the radical polymerizable monomer having a reactive group include acrylic acid, methacrylic acid, hydroxyethyl acrylate, and hydroxyethyl methacrylate.
Examples of the group that reacts with the reactive group include an epoxy group and an isocyanate group.
Examples of the compound having an ethylenically unsaturated double bond include glycidyl acrylate, glycidyl methacrylate, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and the like.

  The polymerizable group amount of the halogenated phthalocyanine multimer is preferably 0.1 mmol to 2.0 mmol, more preferably 0.2 mmol to 1.5 mmol, and more preferably 0.3 mmol to 1. Particularly preferred is 0 mmol.

  The weight average molecular weight of the halogenated phthalocyanine multimer is preferably 2,000 to 20,000, more preferably 3,000 to 15,000, and most preferably 4,000 to 10,000. preferable. The ratio of the weight average molecular weight / number average molecular weight of the halogenated phthalocyanine multimer is preferably 1.0 to 3.0, more preferably 1.6 to 2.5, and more preferably 1.6 to 2 0.0 is most preferred. The weight average molecular weight and degree of dispersion of the polymer are defined as polystyrene conversion values by GPC measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer are, for example, HLC-8220 (manufactured by Tosoh Corporation) and TSKgel Super AWM-H (Tosoh Corporation) as a column. 6.0 mm ID × 15.0 cm can be obtained by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.

The blending amount of the halogenated phthalocyanine dye in the composition of the present invention is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, and more preferably 40 to 50% by mass with respect to the total solid content. % Is particularly preferred.
When the halogenated phthalocyanine dye is a multimer, the blending amount of the halogenated phthalocyanine dye multimer in the composition of the present invention is preferably 45 to 55% by mass with respect to the total solid content.
Moreover, it is preferable that the compounding quantity of halogenated phthalocyanine dye is 55-80 mass% among the coloring agents contained in the composition of this invention, and it is more preferable that it is 60-75 mass%.
Furthermore, the blending amount of the phthalocyanine compound containing no halogen atom (hereinafter sometimes referred to as “non-halogenated phthalocyanine compound”) in the composition of the present invention is 5% by mass or less based on the total solid content. Is preferable, and it is more preferable that it is 1 mass% or less. By setting it as such a range, the effect of this invention is exhibited more effectively.

<Other colorants>
The composition of the present invention may contain other colorants in addition to the halogenated phthalocyanine compound, and preferably contains other colorants. As other colorants, yellow pigments are preferably used, and dyes or pigments, mixed systems of dyes and pigments may be used, but a composition in a state where the composition is uniformly dissolved can be obtained without using a dispersant. From the viewpoint of being able to produce a dye, a dye is preferable.

  Examples of the pigment include conventionally known various inorganic pigments or organic pigments. Further, considering that it is preferable to have a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment having an average particle size as small as possible, and considering the handling properties, the average particle size of the pigment is 0.01 μm to 0.1 μm is preferable, and 0.01 μm to 0.05 μm is more preferable.

Examples of the pigment that can be preferably used in the present invention include the following. However, the present invention is not limited to these.
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214
These organic pigments can be used alone or in various combinations in order to increase color purity.

In the present invention, when the colorant is a dye, a colored curable composition in a state of being uniformly dissolved in the composition can be obtained. There is no restriction | limiting in particular as dye, A well-known dye can be used for conventional color filters.
Examples of the chemical structure include azo series (for example, CI solvent yellow 162) and methine series (CI solvent yellow 93).
As the methine dye, a monomethine dye is preferable, and a monomethine dye represented by the following general formula (5) is more preferable.
(In General Formula (5), R ¹¹ represents an alkyl group or a vinyl group, and R ¹² represents an aromatic ring group having a substituent.)
R ¹¹ is preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
R ¹² is preferably a phenyl group or a naphthyl group, and the substituent is preferably an alkylsulfonylamino group, a vinylsulfonylamino group, an arylsulfonylamino group, an alkylcarbonylamino group, a vinylcarbonylamino group, or an arylcarbonylamino group. Alkylsulfonylamino groups are preferred but preferred. The C 1-12 alkyl group may have an unsaturated bond, and examples of such a substituent include an allylsulfonylamino group.

Moreover, as a coloring agent, an acid dye and / or its derivative may be used suitably.
In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be used effectively.

  Specific examples of the acid dye are shown below, but are not limited thereto. For example, acid yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98,99,111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

  Direct Yellow 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129, 136, 138, 141 ;; Food Yellow 3; Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 50, 61, 62, 65; and these And derivatives of dyes.

  The yellow dye used in the present invention is particularly preferably an azo dye and / or a methine dye.

<Pigment dispersion>
When a pigment is used for the preparation of the composition of the present invention, it is a preferable embodiment to prepare a pigment dispersion. From the viewpoint of improving the dispersibility of the pigment, it is preferable to further add a pigment dispersant.

Examples of pigment dispersants that can be used in the present invention include polymer dispersants [for example, polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, and modified poly (meth) acrylates. , (Meth) acrylic copolymers, naphthalenesulfonic acid formalin condensates], polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, pigment derivatives, and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.

The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures.
On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

  The pigment dispersant that can be used in the present invention is also available as a commercial product, and specific examples thereof include “Disperbyk-101 (polyamideamine phosphate), 107 (carboxylic acid ester)”, 110 (by BYK Chemie). Copolymer containing acid groups), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ) "EFKA 4047, 4050-4010-4165 (polyurethane)", EFKA 4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylic acid) Salt), 6220 (fatty acid polyester), 6745 Phthalocyanine derivatives), 6750 (azo pigment derivatives) ”,“ Ajispur PB821, PB822 ”manufactured by Ajinomoto Fan Techno Co.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co.,“ Polyflow No. 50E, No. 300 (acrylic) Copolymer) ”,“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, manufactured by Enomoto Kasei Co., Ltd. “DA-725”, “Demol RN, N (naphthalene sulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)”, “Homogenol L-18 (polymer) Polycarboxylic acid) "," Emulgen 920, 930, 935, 985 (polyoxyethylene) Nonylphenyl ether) ”,“ acetamine 86 (stearylamine acetate) ”,“ Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (end part) Polymer having functional part), 24000, 28000, 32000, 38500 (graft type polymer) "," Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) "manufactured by Nikko Chemicals Or the like.

  Moreover, the dispersing agent described in paragraph numbers 0028 to 0124 of JP 2011-070156 A and the dispersing agent described in JP 2007-277514 A are preferably used, and the contents thereof are incorporated in the present specification.

  These pigment dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant.

As content of the pigment dispersant in the composition of this invention, it is preferable that it is 1-80 mass parts with respect to 100 mass parts of pigments which are colorants, 5-70 mass parts is more preferable, 10-60 More preferably, it is part by mass.
Specifically, if a polymer dispersant is used, the amount used is preferably in the range of 5 to 100 parts by mass, and in the range of 10 to 80 parts by mass, with respect to 100 parts by mass of the pigment. It is more preferable that
Moreover, when using together a pigment derivative, it is preferable that it is in the range of 1-30 mass parts in conversion of mass as a usage-amount of a pigment derivative with respect to 100 mass parts of pigments, and exists in the range of 3-20 mass parts. Is more preferable, and is particularly preferably in the range of 5 to 15 parts by mass.

-Pigment derivative-
When a pigment is contained as a colorant, it is preferable to further contain a pigment derivative in order to increase the adsorptivity of the dispersion resin to the pigment. The pigment derivative is a compound having a structure in which a part of an organic pigment is substituted with an acidic group, a basic group or a phthalimidomethyl group. The pigment derivative preferably contains a pigment derivative having an acidic group or a basic group from the viewpoint of dispersibility and dispersion stability.

Examples of the organic pigment for constituting the pigment derivative include diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments , Isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, metal complex pigments, and the like.
Moreover, as an acidic group which a pigment derivative has, a sulfonic acid, carboxylic acid, and its quaternary ammonium salt are preferable, a carboxylic acid group and a sulfonic acid group are more preferable, and a sulfonic acid group is especially preferable. The basic group possessed by the pigment derivative is preferably an amino group, particularly preferably a tertiary amino group.

  As the pigment derivative, quinoline-based, benzimidazolone-based and isoindoline-based pigment derivatives are particularly preferable, and quinoline-based and benzimidazolone-based pigment derivatives are more preferable. In particular, a pigment derivative having the following structure is preferable.

In the general formula (P), A represents a partial structure selected from the following general formulas (PA-1) to (PA-3). B represents a single bond or a (t + 1) -valent linking group. C represents a single bond, -NH -, - CONH -, - CO 2 -, - SO 2 NH -, - O -, - S- or -SO ₂ - represents a. D represents a single bond, an alkylene group, a cycloalkylene group or an arylene group. E _{is, -SO 3 H, -SO 3 M} ( where M represents an alkali metal atom), - CO represents the ₂ H or -N (Rpa) (Rpb). Rpa and Rpb each independently represents an alkyl group or an aryl group, and Rpa and Rpb may be linked to each other to form a ring. t represents an integer of 1 to 5.

In general formulas (PA-1) and (PA-2), Rp1 represents an alkyl group having 1 to 5 carbon atoms or an aryl group. In General Formula (PA-3), Rp2 represents a hydrogen atom, a halogen atom, an alkyl group, or a hydroxyl group. s represents an integer of 1 to 4. When s is 2 or more, the plurality of Rp2s may be the same as or different from each other. In general formula (PA-1) and general formula (PA-3), Rp3 represents a single bond, —NH—, —CONH—, —CO ₂ —, —SO ₂ NH—, —O—, —S— or —SO ₂ — is represented. * Represents a connecting portion with B.

  In general formula (P), Rp1 is particularly preferably a methyl group or a phenyl group, and most preferably a methyl group. In general formula (PA-3), Rp2 is preferably a hydrogen atom or a halogen atom, and most preferably a hydrogen atom or a chlorine atom.

  In the general formula (P), examples of the (t + 1) -valent linking group represented by B include an alkylene group, a cycloalkylene group, an arylene group, and a heteroarylene group. Among these, the linking groups represented by the following structural formulas (PA-4) to (PA-9) are particularly preferable.

  Among structural formulas (PA-4) to (PA-9), in particular, a pigment derivative having a linking group represented by the structural formula (PA-5) or (PA-8) as B is more excellent in dispersibility. This is preferable.

  In the general formula (P), examples of the alkylene group, cycloalkylene group and arylene group represented by D include methylene, ethylene, propylene, butylene, pentylene, hexylene, decylene, cyclopropylene, cyclobutylene, cyclopentylene, Examples include cyclohexylene, cyclooctylene, cyclodecylene, phenylene, naphthylene, and the like. Among these, as D, an alkylene group is particularly preferable, and alkylene having 1 to 5 carbon atoms is most preferable.

  In the general formula (P), when E represents -N (Rpa) (Rpb), examples of the alkyl group and aryl group in Rpa and Rpb include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. , Sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, octyl group, decyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclodecyl group, phenyl Group, naphthyl group and the like. As Rpa and Rpb, an alkyl group is particularly preferable, and an alkyl group having 1 to 5 carbon atoms is most preferable. T is preferably 1 or 2.

  Specific examples of the pigment derivative are shown below, but the present invention is not limited thereto. In the following specific examples, M represents an alkali metal (Na, K, etc.).

  Among the pigment derivatives, (A-1), (A-2), (A-5), (A-9), (A-10), (A-11), (A-19), (A -20), (A-21), (A-22), (A-23), (A-24) and (A-25) are preferred, and (A-1), (A-2), (A -9), (A-10) and (A-23) are more preferable.

  1-30 mass% is preferable with respect to the total mass of a pigment, and, as for content of the pigment derivative in the colored curable composition of this invention, 3-20 mass% is more preferable. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.

-Solvent-
The solvent in the pigment dispersion is not particularly limited as long as it is an organic solvent used in general pigment dispersible compositions. For example, 1-methoxy-2-propyl acetate, 1-methoxy-2-propanol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethyl acetate, butyl acetate, ethyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, n-propanol , 2-propanol, n-butanol, cyclohexanol, ethylene glycol, diethylene glycol, toluene, xylene, and the like, and a plurality of these may be used together to adjust the melting point, viscosity, and pigment dispersibility. Is also possible.

The content of the solvent in the pigment dispersion is appropriately selected according to the use of the pigment dispersion.
When the pigment dispersion is used for the preparation of the colored curable composition described later, from the viewpoint of handleability, the sum of the pigment and the pigment dispersant is 5 to 5 based on the total mass excluding the pigment dispersion solvent. It can contain so that it may become 50 mass%.

  The content of the colorant can be used as long as the effect of the present invention is not impaired, and is preferably 10 to 55% by mass with respect to the total solid content of the colored curable composition of the present invention. More preferably, it is mass%. Further, it is preferably added to the colored curable composition so that the absorption intensity ratio (absorption at 450 nm / absorption at 650 nm) is in the range of 0.95 to 1.05.

<Thermosetting compound>
The composition of the present invention contains at least one thermosetting compound. Here, the thermosetting compound refers to a compound that can be cured by heating, and generally refers to a compound that is cured by heating at 180 ° C. or higher.
As the thermosetting compound used in the present invention, for example, a compound having a thermosetting functional group can be used. Examples of the thermosetting functional group include those having at least one group selected from an epoxy group, a methylol group, an alkoxymethyl group, an acyloxymethyl group, a (meth) acryloyl group, an isocyanate group, a vinyl group, and a mercapto group. preferable. As the thermosetting compound, those having two or more thermosetting functional groups in one molecule are more preferable, and compounds having two or more epoxy groups in one molecule are more preferable.
The thermosetting compound used in the present invention includes epoxy compounds, melamine compounds (for example, alkoxymethylated, acyloxymethylated melamine compounds), urea compounds (for example, alkoxymethylated, acyloxymethylated urea compounds), phenol compounds ( For example, a hydroxymethylated or alkoxymethylated phenol compound or resin, and an alkoxymethyl etherified phenol compound) are preferable examples. An epoxy compound and a melamine compound are more preferable, and an epoxy compound is more preferable.

  The thermosetting compound used in the present invention may be a low molecular compound (for example, a molecular weight of less than 2000, and further a molecular weight of less than 1000), or a high molecular compound (for example, a molecular weight of 1000 or more, in the case of a polymer, the weight average molecular weight is 1000 or more). In the present invention, those having a molecular weight of 1000 or more are preferred, and those having a molecular weight of 2000 to 100,000 are more preferred. In the present invention, a compound having 2 or more epoxy groups in one molecule and a molecular weight of 1000 or more is particularly preferable.

<Epoxy compound>
When the epoxy compound is a low molecular compound, a compound represented by the following general formula (EP1) can be mentioned.

In the formula (EP1), R ^{EP1 to} R ^EP3 each represent a hydrogen atom, a halogen atom, or an alkyl group, and the alkyl group may have a cyclic structure, and has a substituent. May be. R ^EP1 and R ^EP2 and R ^EP2 and R ^EP3 may be bonded to each other to form a ring structure. Examples of the substituent that the alkyl group may have include a hydroxyl group, a cyano group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, an alkylthio group, an alkylsulfone group, an alkylsulfonyl group, and an alkylamino group. Groups, alkylamide groups, and the like.
^QEP represents a single bond or an ^nEP- valent organic group. R ^EP1 to R ^EP3 combines with Q ^EP may form a ring structure.
n ^EP represents an integer of 2 or more, preferably 2 to 10, more preferably 2 to 6. However, n ^EP is 2 when Q ^EP is a single bond.

When Q ^EP is an n ^EP valent organic group, a chain or cyclic n ^EP valent saturated hydrocarbon group (preferably having 2 to 20 carbon atoms), n ^EP valent aromatic ring group (preferably having 6 to 30 carbon atoms) is preferred. ), Or a chain or cyclic saturated hydrocarbon or aromatic hydrocarbon such as an ether group, an ester group, an amide group, a sulfonamide group, an alkylene group (preferably having 1 to 4 carbon atoms, more preferably a methylene group), etc. A divalent linking group, a trivalent linking group such as —N (—) _2, or an n ^EP valent organic group having a structure in which a combination thereof is linked is preferable.

  Specific examples of the compound having an epoxy structure are illustrated below, but the present invention is not limited thereto.

The epoxy compound used in the present invention is also preferably an oligomer or polymer having an epoxy group in the side chain. Examples of such compounds include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type epoxy resin. And aliphatic epoxy resins.
These compounds may be used as commercial products or can be obtained by introducing an epoxy group into the side chain of the polymer.

  As a commercial product, for example, as bisphenol A type epoxy resin, JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (manufactured by DIC Corporation), etc., and bisphenol F type epoxy resin is JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835. (Above, manufactured by DIC Corporation), LCE-21, RE-602S (above, Nippon Kayaku) As a phenol novolac type epoxy resin, JER152, JER154, JER157S70, JER157S65 (manufactured by Japan Epoxy Resins Co., Ltd.), EPICLON N-740, EPICLON N-740, EPICLON N- 770, EPICLON N-775 (manufactured by DIC Corporation) and the like, and cresol novolac type epoxy resins include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N- 680, EPICLON N-690, EPICLON N-695 (manufactured by DIC Corporation), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), etc., and as an aliphatic epoxy resin, ADEK RESIN EP-4080S, EP-4085S, EP-4088S (above, manufactured by ADEKA) Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (above, Daicel Chemical Industries) (Manufactured by Nagase ChemteX Corporation), etc., Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Co., Ltd.), JER1031S (manufactured by Japan Epoxy Resin Co., Ltd.) and the like.

In the case of synthesizing by introducing into a polymer side chain, for example, the introduction reaction includes tertiary amines such as triethylamine and benzylmethylamine, quaternary ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, pyridine, The reaction can be carried out in an organic solvent at a reaction temperature of 50 to 150 ° C. for several to several tens of hours using triphenylphosphine or the like as a catalyst. The introduction amount of the alicyclic epoxy unsaturated compound is preferably controlled so that the acid value of the obtained polymer is in a range satisfying 5 to 200 KOH · mg / g. Further, the molecular weight is preferably 500 to 5000000, more preferably 1000 to 500000 in terms of weight average.
As the epoxy unsaturated compound, those having a glycidyl group as an epoxy group such as glycidyl (meth) acrylate and allyl glycidyl ether can be used, but preferred are unsaturated compounds having an alicyclic epoxy group. Examples of such compounds include the following compounds.

<Melamine compounds, urea compounds, other thermosetting compounds>
As the thermosetting compound used in the present invention, compounds having the following N-hydroxymethyl group, N-alkoxymethyl group, or N-acyloxymethyl group are also preferable. Such a compound is usually provided as a melamine compound or a urea compound.

  As a compound having an N-hydroxymethyl group, an N-alkoxymethyl group, or an N-acyloxymethyl group, two or more (more preferably 2 to 8) partial structures represented by the following general formula (CLNM-1) are used. ) Is preferred.

In General Formula (CLNM-1), R ^NM1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an oxoalkyl group.

In general formula (CLNM-1), the alkyl group represented by R ^NM1 is preferably a linear or branched alkyl group having 1 to 6 carbon atoms. The cycloalkyl group represented by R ^NM1 is preferably a cycloalkyl group having 5 to 6 carbon atoms. The oxoalkyl group of R ^NM1 is preferably an oxoalkyl group having 3 to 6 carbon atoms, and examples thereof include a β-oxopropyl group, a β-oxobutyl group, a β-oxopentyl group, and a β-oxohexyl group. it can.

  As a more preferable embodiment of the compound having two or more partial structures represented by the general formula (CLNM-1), a urea compound represented by the following general formula (CLNM-2), represented by the following general formula (CLNM-3) And an alkylene urea compound represented by the following general formula (CLNM-4), and a melamine compound represented by the following general formula (CLNM-5).

In the general formula (CLNM-2), R ^NM1 are respectively those in formula (CLNM-1) at, the same as R ^NM1. R ^NM2 represents a hydrogen atom, an alkyl group (preferably having 1 to 6 carbon atoms), or a cycloalkyl group (preferably having 5 to 6 carbon atoms).

  Specific examples of the urea compound represented by the general formula (CLNM-2) include, for example, N, N-di (methoxymethyl) urea, N, N-di (ethoxymethyl) urea, N, N-di (propoxy). Methyl) urea, N, N-di (isopropoxymethyl) urea, N, N-di (butoxymethyl) urea, N, N-di (t-butoxymethyl) urea, N, N-di (cyclohexyloxymethyl) Examples include urea, N, N-di (cyclopentyloxymethyl) urea, N, N-di (adamantyloxymethyl) urea, N, N-di (norbornyloxymethyl) urea and the like.

In the general formula (CLNM-3), R ^NM1 are respectively those in formula (CLNM-1) at, the same as R ^NM1. R ^NM3 is a hydrogen atom, a hydroxyl group, a linear or branched alkyl group (preferably having 1 to 6 carbon atoms), a cycloalkyl group (preferably having 5 to 6 carbon atoms), an oxoalkyl group (having 1 to 6 carbon atoms). 6 is preferable), an alkoxy group (preferably having 1 to 6 carbon atoms) or an oxoalkoxy group (preferably having 1 to 6 carbon atoms).
G represents a single bond, an oxygen atom, a sulfur atom, an alkylene group (preferably having 1 to 3 carbon atoms) or a carbonyl group. More specifically, a methylene group, ethylene group, propylene group, 1-methylethylene group, hydroxymethylene group, cyanomethylene group and the like can be mentioned.

  Specific examples of the alkylene urea compound represented by the general formula (CLNM-3) include, for example, N, N-di (methoxymethyl) -4,5-di (methoxymethyl) ethylene urea, N, N-di ( Ethoxymethyl) -4,5-di (ethoxymethyl) ethyleneurea, N, N-di (propoxymethyl) -4,5-di (propoxymethyl) ethyleneurea, N, N-di (isopropoxymethyl) -4 , 5-Di (isopropoxymethyl) ethyleneurea, N, N-di (butoxymethyl) -4,5-di (butoxymethyl) ethyleneurea, N, N-di (t-butoxymethyl) -4,5- Di (t-butoxymethyl) ethyleneurea, N, N-di (cyclohexyloxymethyl) -4,5-di (cyclohexyloxymethyl) ethyleneurea, N, N-di (cyclope Tiloxymethyl) -4,5-di (cyclopentyloxymethyl) ethyleneurea, N, N-di (adamantyloxymethyl) -4,5-di (adamantyloxymethyl) ethyleneurea, N, N-di (norbol) Nyloxymethyl) -4,5-di (norbornyloxymethyl) ethyleneurea and the like.

In the general formula (CLNM-4),
R ^NM1 are respectively those in formula (CLNM-1) at, the same as R ^NM1.
R ^NM4 represents a hydrogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, or an alkoxy group, respectively.

R ^NM4 alkyl group (preferably having 1 to 6 carbon atoms), cycloalkyl group (preferably having 5 to 6 carbon atoms), alkoxy group (preferably having 1 to 6 carbon atoms), more specifically, methyl group, Examples include an ethyl group, a butyl group, a cyclopentyl group, a cyclohexyl group, a methoxy group, an ethoxy group, and a butoxy group.

  Specific examples of the glycoluril compound represented by the general formula (CLNM-4) include, for example, N, N, N, N-tetra (methoxymethyl) glycoluril, N, N, N, N-tetra (ethoxymethyl). ) Glycoluril, N, N, N, N-tetra (propoxymethyl) glycoluril, N, N, N, N-tetra (isopropoxymethyl) glycoluril, N, N, N, N-tetra (butoxymethyl) Glycoluril, N, N, N, N-tetra (t-butoxymethyl) glycoluril, N, N, N, N-tetra (cyclohexyloxymethyl) glycoluril, N, N, N, N-tetra (cyclopentyloxy) Methyl) glycoluril, N, N, N, N-tetra (adamantyloxymethyl) glycoluril, N, N, N, N-te La (norbornyloxymethyl) glycoluril, and the like.

In the general formula (CLNM-5), R ^NM1 are respectively those in formula (CLNM-1) at, the same as R ^NM1. R ^NM5 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an atomic group represented by the following general formula (CLNM-5 ′). R ^NM6 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an atomic group represented by the following general formula (CLNM-5 ″).

In formula (CLNM-5'), R ^NM1 are those in formula (CLNM-1) at, the same as R ^NM1. In formula (CLNM-5''), R ^NM1 is in formula (CLNM-1), is similar to the R ^NM1, R ^NM5 is in formula (CLNM-5) R ^It is the same as ^NM5 .

Alkyl group R ^NM5 and R ^NM6 (1 to 6 carbon atoms is preferred), cycloalkyl groups (5 to 6 carbon atoms is preferred), an aryl group (having 6 to 10 carbon atoms is preferred), and more specifically, Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a phenyl group, and a naphthyl group.

  Examples of the melamine compound represented by the general formula (CLNM-5) include N, N, N, N, N, N-hexa (methoxymethyl) melamine, N, N, N, N, N, N-hexa. (Ethoxymethyl) melamine, N, N, N, N, N, N-hexa (propoxymethyl) melamine, N, N, N, N, N, N-hexa (isopropoxymethyl) melamine, N, N, N , N, N, N-hexa (butoxymethyl) melamine, N, N, N, N, N, N-hexa (t-butoxymethyl) melamine, N, N, N, N, N, N-hexa (cyclohexyl) Oxymethyl) melamine, N, N, N, N, N, N-hexa (cyclopentyloxymethyl) melamine, N, N, N, N, N, N-hexa (adamantyloxymethyl) melamine, N, N, N , N, N, N-hexa Bornyloxymethyl) melamine, N, N, N, N, N, N-hexa (methoxymethyl) acetoguanamine, N, N, N, N, N, N-hexa (ethoxymethyl) acetoguanamine, N, N , N, N, N, N-hexa (propoxymethyl) acetoguanamine, N, N, N, N, N, N-hexa (isopropoxymethyl) acetoguanamine, N, N, N, N, N, N- Hexa (butoxymethyl) acetoguanamine, N, N, N, N, N, N-hexa (t-butoxymethyl) acetoguanamine, N, N, N, N, N, N-hexa (methoxymethyl) benzoguanamine, N , N, N, N, N, N-hexa (ethoxymethyl) benzoguanamine, N, N, N, N, N, N-hexa (propoxymethyl) benzoguanamine, N, N, N, N, N, N- Oxa (isopropoxymethyl) benzoguanamine, N, N, N, N, N, N-hexa (butoxymethyl) benzoguanamine, N, N, N, N, N, N-hexa (t-butoxymethyl) benzoguanamine, etc. Can be mentioned.

The groups represented by R ^{NM1 to} R ^NM6 in formulas (CLNM-1) to (CLNM-5) may further have a substituent. Examples of the substituent that R ^{NM1 to} R ^NM6 may have include, for example, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a cycloalkyl group (preferably having 3 to 20 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), alkoxy group (preferably 1 to 20 carbon atoms), cycloalkoxy group (preferably 3 to 20 carbon atoms), acyl group (preferably 2 to 20 carbon atoms), acyloxy group (preferably carbon 2-20) etc. can be mentioned.
Specific examples of the compound having two or more partial structures represented by the general formula (CLNM-1) are illustrated below, but the present invention is not limited thereto. In addition to the compounds shown below, compounds from Sanwa Chemical Co., Ltd. and Nicarac series which are not exemplified below can also be preferably used.

<Phenol compound>
The phenol compound contains 3 to 5 benzene rings in the molecule, and further has two or more hydroxymethyl groups or alkoxymethyl groups, and the hydroxymethyl group or alkoxymethyl group is attached to at least one of the benzene rings. Mention may be made of phenolic compounds which are concentrated or distributed and combined. As the alkoxymethyl group bonded to the benzene ring, those having 6 or less carbon atoms are preferable. Specifically, a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an i-propoxymethyl group, an n-butoxymethyl group, an i-butoxymethyl group, a sec-butoxymethyl group, and a t-butoxymethyl group are preferable. Further, alkoxy-substituted alkoxy groups such as 2-methoxyethoxy group and 2-methoxy-1-propoxy group are also preferable.
The thermosetting compound is more preferably a phenol compound having two or more benzene rings in the molecule, and is preferably a phenol compound containing no nitrogen atom.
The thermosetting compound is preferably a phenol compound having 2 to 8 thermosetting functional groups per molecule, and more preferably 3 to 6 thermosetting functional groups.

Among these phenol compounds, particularly preferable ones are listed below. In the formula, L ^{1 to} L ⁸ represent a thermosetting functional group such as an alkoxymethyl group and may be the same or different, and the thermosetting functional group is preferably a hydroxymethyl group, a methoxymethyl group or An ethoxymethyl group is shown.

As the thermosetting compound, a commercially available one can be used, or it can be synthesized by a known method. For example, a phenol compound having a hydroxymethyl group is obtained by reacting a phenol compound not having a corresponding hydroxymethyl group (a compound in which L ^{1 to} L ⁸ are hydrogen atoms in the above formula) with formaldehyde in the presence of a base catalyst. be able to. At this time, in order to prevent resinification or gelation, the reaction temperature is preferably 60 ° C. or lower. Specifically, it can be synthesized by the methods described in JP-A-6-282067, JP-A-7-64285 and the like.

  A phenol compound having an alkoxymethyl group can be obtained by reacting a corresponding phenol compound having a hydroxymethyl group with an alcohol in the presence of an acid catalyst. At this time, in order to prevent resinification and gelation, the reaction temperature is preferably 100 ° C. or lower. Specifically, it can be synthesized by the method described in EP632003A1 and the like. A phenol compound having a hydroxymethyl group or an alkoxymethyl group synthesized in this manner is preferable from the viewpoint of stability during storage, but a phenol compound having an alkoxymethyl group is particularly preferable from the viewpoint of stability during storage. Such a phenol compound having two or more hydroxymethyl groups or alkoxymethyl groups in total and concentrated on any benzene ring or distributed and bonded may be used alone or in combination of two kinds. A combination of the above may also be used.

  In this invention, a thermosetting compound may be used independently and may be used in combination of 2 or more type.

  Although the total content of the thermosetting compound in the composition of the present invention varies depending on the material, it is preferably 5 to 40% by mass, and preferably 7 to 35% with respect to the total solid content (mass) of the colored curable composition. The mass% is more preferable, and 10 to 30% is particularly preferable. In this invention, the effect that the cured film excellent in chemical-resistance can be obtained by setting it as the compounding quantity of such a thermosetting compound is acquired.

<Solvent>
The colored curable composition of the present invention contains a solvent (usually an organic solvent) that dissolves at least the halogenated phthalocyanine dye and the thermosetting compound.
Examples of organic solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate. , Alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-oxypropionate Esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.) )), 2- Xylpropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy) Propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg 2-methoxy-2- Methyl methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. And as ethers For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like and ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone and aromatic hydrocarbons such as toluene, Xylene and the like are preferred.

  These solvents are also preferably in a form of mixing two or more kinds from the viewpoint of improving the coated surface. In this case, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl It is a mixed solution composed of two or more selected from carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

  The content of the solvent in the colored curable composition is preferably such that the total solid concentration of the composition is 5 to 30% by mass, more preferably 7 to 25% by mass, from the viewpoint of applicability. 10-20 mass% is especially preferable.

<Various additives>
The colored curable composition of the present invention has various additives as required, for example, surfactants, acid anhydrides, curing agents, curing catalysts, fillers, adhesion promoters, as long as the effects of the present invention are not impaired. An agent, an antioxidant, an ultraviolet absorber, an aggregation inhibitor and the like can be blended.
On the other hand, in the colored curable composition of the present invention, the amount of the photopolymerizable compound is preferably 1% by mass or less, more preferably 0.5% by mass or less, based on the total solid content. Is more preferable.

(Surfactant)
Various colored surfactants may be added to the colored curable composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

In particular, the colored curable composition of the present invention contains a fluorosurfactant, so that the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, so that the coating thickness is uniform. And the liquid-saving property can be further improved.
That is, when a film is formed using a coating liquid to which a colored curable composition containing a fluorosurfactant is applied, by reducing the interfacial tension between the coated surface and the coating liquid, The wettability is improved, and the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

  The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. A fluorine-based surfactant having a fluorine content in this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in a colored curable composition.

  Examples of the fluorine-based surfactant include Megafac F781 (manufactured by DIC Corporation).

  Only one type of surfactant may be used, or two or more types may be combined.

  The colored curable composition may or may not contain a surfactant, but when it is contained, the addition amount of the surfactant is 0.001% by mass relative to the total mass of the colored curable composition. -2.0 mass% is preferable, More preferably, it is 0.005 mass%-1.0 mass%.

  When the surfactant is a polymer compound (that is, a resin), the solid content acid value of the polymer compound is 80 mgKOH / g or less.

<Acid anhydride>
The colored curable composition of the present invention may contain an acid anhydride. By containing an acid anhydride, it is possible to improve the crosslinkability of the thermosetting compound, particularly the epoxy compound, by thermosetting.

  Examples of the acid anhydride include phthalic anhydride, nadic anhydride, maleic anhydride, succinic anhydride, and the like. Among these, phthalic anhydride is preferable because the acid anhydride has little influence on pigment dispersion. An amine compound is generally used as an epoxy curing agent, but has advantages such as a relatively long pot life.

  As content in the colored curable composition of an acid anhydride, the range of 10-40 mass% is preferable with respect to content of a thermosetting compound (especially epoxy compound), and the range of 15-30 mass% is preferable. More preferred. When the content of the acid anhydride is 10% by mass or more, the crosslinking density of the thermosetting compound, particularly epoxy, can be improved, and the mechanical strength can be increased. Curing components are suppressed, which is advantageous for increasing the concentration of the coloring material.

(Curing agent)
When using an epoxy resin as the thermosetting compound, it is preferable to add a curing agent. There are many types of curing agents for epoxy resins, and their properties, pot life with resin and curing agent mixture, viscosity, curing temperature, curing time, heat generation, etc. vary greatly depending on the type of curing agent used. An appropriate curing agent must be selected according to the purpose of use, use conditions, working conditions, and the like. The curing agent is explained in detail in Chapter 5 of Hiroshi Kakiuchi “Epoxy resin (Shojodo)”. Examples of curing agents are shown below.

  Those that act catalytically include tertiary amines, boron trifluoride-amine complexes, those that react stoichiometrically with functional groups of epoxy resins, polyamines, acid anhydrides, etc .; Examples include diethylenetriamine, polyamide resin, and medium temperature curing examples such as diethylaminopropylamine and tris (dimethylaminomethyl) phenol; examples of high temperature curing include phthalic anhydride and metaphenylenediamine. In terms of chemical structure, for amines, diethylenetriamine as an aliphatic polyamine; metaphenylenediamine as an aromatic polyamine; tris (dimethylaminomethyl) phenol as a tertiary amine; phthalic anhydride as an acid anhydride; polyamide resin Polysulfide resin, boron trifluoride-monoethylamine complex; Synthetic resin initial condensate includes phenol resin, dicyandiamide and the like.

  These curing agents react with an epoxy group by heating and polymerize to increase the crosslinking density and cure. For thinning, both the binder and the curing agent are preferably as small as possible. In particular, the curing agent is 35% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less with respect to the thermosetting compound. It is preferable that

(Curing catalyst)
In order to realize a composition having a high colorant concentration, curing by reaction between epoxy groups is effective in addition to curing by reaction with a curing agent. For this reason, a curing catalyst can be used without using a curing agent. The addition amount of the curing catalyst is about 1/10 to 1/1000, preferably about 1/20 to 1/500, more preferably 1/30, based on the mass of the epoxy resin having an epoxy equivalent of about 150 to 200. It can be cured with a slight amount of about 1/250.

<Preparation method of colored curable composition>
A preferred method for preparing the colored curable composition of the present invention will be described. However, the present invention is not limited to this.

  When the colorant is a dye, it is dissolved in a suitable solvent together with the thermosetting compound. When a pigment is included as a colorant, it is usually blended after adjusting as a pigment dispersion as described above.

  In particular, when the thermosetting compound is an epoxy compound, a thermosetting compound and a curing catalyst or a curing agent are added to the pigment dispersion or dye solution thus obtained, or the binder is already thermosetting. In the case of a compound, it is preferable to prepare the colored curable composition in the present invention by adding a curing catalyst or a curing agent to impart a thermosetting function, and adding a solvent as necessary.

<Filter filtration>
The colored curable composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances and reducing defects.
As a filter used for filter filtration, if it is a filter conventionally used for the filtration use etc., it can use without being specifically limited.
Examples of the filter material include: a fluororesin such as PTFE (polytetrafluoroethylene); a polyamide resin such as nylon-6 and nylon-6, 6; a polyolefin resin such as polyethylene and polypropylene (PP) (high density, Including ultra high molecular weight); Among these materials, polypropylene (including high density polypropylene) is preferable.

The pore size of the filter is not particularly limited, but is, for example, about 0.01 to 20.0 μm, preferably about 0.01 to 5 μm, and more preferably about 0.01 to 2.0 μm.
By setting the pore size of the filter within the above range, fine particles can be more effectively removed and turbidity can be further reduced.
Here, the pore size of the filter can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (former Nihon Microlith Co., Ltd.), or Kitz Micro Filter Co., Ltd. .

In the filter filtration, two or more filters may be used in combination.
For example, the filtration can be performed first using a first filter and then using a second filter having a pore diameter different from that of the first filter.
At that time, the filtering by the first filter and the filtering by the second filter may be performed only once or may be performed twice or more, respectively.
As the second filter, a filter formed of the same material as the first filter described above can be used.

<Application>
The colored curable composition of the present invention is cured and preferably used as a cured film. The layer obtained by curing the colored curable composition of the present invention can be preferably used as a colored layer of a color filter. In particular, it can be preferably used as a colored curable composition for dry etching.

<Color filter and manufacturing method thereof>
In the color filter of the present invention, at least one of the patterns constituting the color filter is a colored pattern formed from the above-described colored curable composition of the present invention. The color filter of the present invention is not particularly limited as long as at least one pattern is a colored pattern formed from the above-described colored curable composition of the present invention, but preferably the color of the present invention shown below. The filter is manufactured by a manufacturing method.

  As an example of the method for producing the color filter of the present invention, a step of forming a colored layer using the colored curable composition of the present invention, a step of forming a photoresist layer on the colored layer, exposure and development Patterning the photoresist layer to obtain a resist pattern, and dry etching the colored layer using the resist pattern as an etching mask.

In the method for producing a color filter of the present invention, the first colored layer is formed using the above-described colored curable composition of the present invention (also referred to as the first colored curable composition).
Here, since the 1st colored layer is formed with the colored curable composition of this invention, as above-mentioned, it is excellent in solvent resistance and alkali developing solution resistance.
As a result, a developer used when forming a resist pattern (patterned photoresist layer) as an etching mask on the first colored layer, which will be described in detail later, or a second on the first colored layer. In the step of forming the second colored radiation-sensitive layer with the colored radiation-sensitive composition and the step of forming the third colored radiation-sensitive layer with the third colored radiation-sensitive composition on the first colored layer, The first colored layer exposes the organic solvent in the second or third colored radiation-sensitive composition and the second or third colored radiation-sensitive layer formed by the second or third colored radiation-sensitive composition, When dissolved in the developer used for development, the color component in the first colored layer may be eluted into the solvent or developer, or the color component in the second or third colored radiation-sensitive composition is May be mixed into the first colored layer It can be suppressed. As a result, it is possible to suppress the occurrence of color fading in the first colored layer and the occurrence of overlapping regions in which a plurality of colors overlap each other, so that the performance of the finally obtained color filter can be improved.
In particular, for a solid-state imaging device in which a minute size is required such that the thickness is 0.1 to 1.0 μm and / or the pixel pattern size (one side in a square pattern) is 2 μm or less (for example, 0.5 to 2.0 μm). It is effective for producing a color filter.

Here, the solid-state imaging device will be briefly described with reference to FIG. 1 as an example.
As shown in FIG. 1, the solid-state imaging device 10 includes a light receiving element (photodiode) 42 provided on a silicon substrate, a color filter 13, a planarizing film 14, a microlens 15, and the like. In the present invention, the planarizing film 14 is not necessarily provided. In FIG. 1, in order to clarify each part, the ratios of the thicknesses and widths are disregarded and some of them are exaggerated.

  The support is not particularly limited as long as it is used for a color filter in addition to a silicon substrate. For example, soda glass, borosilicate glass, quartz glass, and a transparent conductive film attached to these are used for liquid crystal display elements. And a photoelectric conversion element substrate used for a solid-state imaging device, such as an oxide film or silicon nitride. Further, an intermediate layer or the like may be provided between the support and the color filter 13 as long as the present invention is not impaired.

  A P well 41 is provided on the silicon substrate, and a photodiode 42 is provided on a part of the surface of the P well. The photodiode 42 is formed by performing heat treatment after ion-implanting N-type impurities such as P and As into a part of the surface of the P-well. In addition, an impurity diffusion layer 43 having an N-type impurity concentration higher than that of the photodiode 42 is provided in a region different from the above portion on the surface of the P well 41 of the silicon substrate. The impurity diffusion layer 43 is formed by ion implantation of N-type impurities such as P and As and then performing heat treatment, and the role of the floating diffusion layer that transfers charges generated when the photodiode 42 receives incident light. Fulfill. In addition to the well 41 being a P-type impurity layer and the photodiode 42 and the impurity diffusion layer 43 being an N-type impurity layer, the well 41 is an N-type impurity layer, and the photodiode 42 and the impurity diffusion layer 43 being a P-type impurity layer. You can also

An insulating film 47 such as SiO ₂ or SiO ₂ / SiN / SiO ₂ is provided on the P well 41, the photodiode 42, and the impurity diffusion layer 43. Poly Si, tungsten, An electrode 44 made of tungsten silicide, Al, Cu or the like is provided. The electrode 44 serves as the gate of the gate MOS transistor, and can serve as a transfer gate for transferring charges generated in the photodiode 42 to the impurity diffusion layer 43. Further, a wiring layer 45 is formed above the electrode 44. Above the wiring layer 45, a BPSG film 46 and a P-SiN film 48 are provided. The interface between the BPSG film 46 and the P-SiN film 48 is formed so as to curve downward above the photodiode 42, and serves as an in-layer lens for efficiently guiding incident light to the photodiode 42. Fulfill. On the BPSG film 46, a planarizing film layer 49 is formed for the purpose of planarizing the surface of the P-SiN film 48 or the uneven portions other than the pixel region.

  The color filter 13 is formed on the planarizing film layer 49. In the following description, a colored film (so-called solid film) formed on a silicon substrate without dividing the region is referred to as a “colored (colored radiation sensitive) layer”, and is formed by dividing the region into a pattern. A colored film (for example, a film patterned in a stripe shape) is referred to as a “colored pattern”. In addition, among the colored patterns, a colored pattern that is an element constituting the color filter 13 (for example, a colored pattern patterned into a square or a rectangle) is referred to as a “colored (red, green, blue) pixel”.

  The color filter 13 includes a plurality of two-dimensionally arranged green pixels (first color pixels) 20G, red pixels (second color pixels) 20R, and blue pixels (third color pixels) 20B. Each of the colored pixels 20R, 20G, and 20B is formed above the light receiving element 42. The green pixels 20G are formed in a checkered pattern, and the blue pixels 20B and the red pixels 20R are formed between the green pixels 20G. In FIG. 1, in order to explain that the color filter 13 is composed of pixels of three colors, the colored pixels 20R, 20G, and 20B are displayed in a line.

  The planarization film 14 is formed so as to cover the upper surface of the color filter 13 and planarizes the color filter surface.

  The microlens 15 is a condensing lens arranged with the convex surface facing upward, and is provided above the planarizing film 14 (or a color filter when no planarizing film is provided) and above the light receiving element 42. Each microlens 15 efficiently guides light from the subject to each light receiving element 42.

Next, the manufacturing method of the color filter which concerns on embodiment of this invention is demonstrated.
In the method for producing a color filter according to the embodiment of the present invention, first, as shown in the schematic cross-sectional view of FIG. 2, the first colored layer 11 is formed from the first colored curable composition (step (a)). . Here, the first colored curable composition is the colored curable composition of the present invention described above.

  The first colored layer 11 can be formed by applying a colored curable composition on a support by a coating method such as spin coating, slit coating or spray coating, and drying to form a colored layer.

  As thickness of the 1st colored layer 11 here, the range of 0.3-1.0 micrometer is preferable, The range of 0.35-0.8 micrometer is more preferable, The range of 0.35-0.7 micrometer is more preferable. .

  When the 1st colored curable composition contains the thermosetting compound, it is preferable to heat and harden the 1st colored layer 11 with heating apparatuses, such as a hotplate and oven. The heating temperature is preferably 120 ° C to 250 ° C, and more preferably 160 ° C to 230 ° C. The heating time varies depending on the heating means, but is usually about 3 to 30 minutes when heated on a hot plate, and usually about 30 to 90 minutes when heated in an oven.

  Next, patterning is performed by dry etching so that a group of through holes is formed in the first colored layer 11 (step (a)). Thereby, a first colored pattern is formed. According to this technique, a through-hole having a desired shape is formed as compared with the case where a first colored layer is formed from a colored radiation-sensitive composition and the first colored layer is exposed and developed to provide a group of through-holes. A group can be provided more reliably. This is because, in a colored radiation-sensitive composition in which the content of the colorant with respect to the total solid content of the composition is 50% by mass or more, there is limited room for adding a component that contributes to developability to the composition. This is because reliable patterning becomes difficult.

  The first coloring pattern may be a coloring pattern provided as the first color on the support, or depending on the case, for example, a coloring provided as a second color pattern or a pattern after the third color on the support having the existing pattern. It may be a pattern.

  The dry etching can be performed using the etching gas using the patterned photoresist layer as a mask for the first colored layer 11. For example, as shown in the schematic cross-sectional view of FIG. 3, first, a photoresist layer 51 is formed on the first colored layer 11.

  Specifically, a positive or negative radiation-sensitive composition is applied (preferably applied) on the colored layer, and dried to form a photoresist layer. In forming the photoresist layer 51, it is preferable to further perform a pre-bake treatment. In particular, as a process for forming a photoresist, a mode in which heat treatment after exposure (PEB) and heat treatment after development (post-bake treatment) are desirable.

As the photoresist, for example, a positive type radiation sensitive composition is used. As this positive type radiation sensitive composition, positive type photo sensitive to radiation such as ultraviolet rays (g rays, h rays, i rays), deep ultraviolet rays including excimer lasers, electron beams, ion beams and X rays. A positive resist composition suitable for resist can be used. Of the radiation, g-line, h-line and i-line are preferable, and i-line is particularly preferable.
Specifically, as the positive radiation sensitive composition, a composition containing a quinonediazide compound and an alkali-soluble resin is preferable. The positive-type radiation-sensitive composition containing a quinonediazide compound and an alkali-soluble resin indicates that a quinonediazide group is decomposed by irradiation with light having a wavelength of 500 nm or less to generate a carboxyl group, resulting in alkali-solubility from an alkali-insoluble state. It is what you use. Since this positive photoresist has remarkably excellent resolution, it is used for manufacturing integrated circuits such as ICs and LSIs. Examples of the quinonediazide compound include a naphthoquinonediazide compound.

  As thickness of the photoresist layer 51, 0.1-3 micrometers is preferable, 0.2-2.5 micrometers is preferable, and 0.3-2 micrometers is still more preferable. The application of the photoresist layer 51 can be suitably performed using the application method for the first colored layer 11 described above.

Next, as shown in the schematic cross-sectional view of FIG. 4, the photoresist layer 51 is exposed and developed to form a resist pattern (patterned photoresist layer) 52 provided with a resist through-hole group 51A.
The formation of the resist pattern 52 is not particularly limited, and can be performed by appropriately optimizing a conventionally known photolithography technique. By providing the resist through hole group 51 </ b> A in the photoresist layer 51 by exposure and development, a resist pattern 52 as an etching mask used in the next etching is provided on the first colored layer 11.

  The exposure of the photoresist layer 51 is performed by exposing the positive or negative radiation sensitive composition with g-line, h-line, i-line, etc., preferably i-line, through a predetermined mask pattern. be able to. After the exposure, the photoresist is removed in accordance with a region where a colored pattern is to be formed by developing with a developer.

  Any developer can be used as long as it dissolves the exposed portion of the positive resist and the uncured portion of the negative resist without affecting the first colored layer containing the colorant. A combination of these organic solvents or an alkaline aqueous solution can be used. As the alkaline aqueous solution, an alkaline aqueous solution prepared by dissolving an alkaline compound so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 5% by mass is suitable. Alkaline compounds include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropyl Ammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene and the like can be mentioned. In addition, when alkaline aqueous solution is used as a developing solution, generally a washing process is performed with water after development.

Next, as shown in the schematic cross-sectional view of FIG. 5, patterning is performed by dry etching so that the through hole group 120 is formed in the first colored layer 11 using the resist pattern 52 as an etching mask. Thereby, the 1st coloring pattern 12 is formed. Here, the through-hole group 120 has a first through-hole part group 121 and a second through-hole part group 122.
The through-hole group 120 is provided in a checkered pattern in the first colored layer 11. Therefore, the 1st coloring pattern 12 by which the through-hole group 120 is provided in the 1st coloring layer 11 has a some square-shaped 1st coloring pixel in checkered form.

  Specifically, in the dry etching, the first colored layer 11 is dry etched using the resist pattern 52 as an etching mask. Representative examples of dry etching include JP-A-59-126506, JP-A-59-46628, JP-A-58-9108, JP-A-58-2809, JP-A-57-148706, JP-A-61-41102, and the like. There is a method described in this publication.

Dry etching is preferably performed in the following manner from the viewpoint of forming a pattern cross section closer to a rectangle and reducing damage to the support.
Using a mixed gas of fluorine-based gas and oxygen gas (O ₂ ), the first stage etching is performed up to a region (depth) where the support is not exposed, and after this first stage etching, nitrogen gas ( N ₂ ) and oxygen gas (O ₂ ), and a second stage etching is preferably performed to the vicinity of the region (depth) where the support is exposed, and over-etching is performed after the support is exposed. The form containing these is preferable. Hereinafter, a specific method of dry etching and the first stage etching, second stage etching, and over-etching will be described.

Dry etching is performed by obtaining etching conditions in advance by the following method.
(1) The etching rate (nm / min) in the first stage etching and the etching rate (nm / min) in the second stage etching are calculated respectively.
(2) The time for etching the desired thickness in the first stage etching and the time for etching the desired thickness in the second stage etching are respectively calculated.
(3) The first stage etching is performed according to the etching time calculated in (2) above.
(4) The second stage etching is performed according to the etching time calculated in (2) above. Alternatively, the etching time may be determined by endpoint detection, and the second stage etching may be performed according to the determined etching time.
(5) Overetching time is calculated with respect to the total time of (3) and (4) above, and overetching is performed.

The mixed gas used in the first-stage etching process preferably contains a fluorine-based gas and an oxygen gas (O ₂ ) from the viewpoint of processing the organic material that is the film to be etched into a rectangular shape. In addition, the first stage etching process can avoid damage to the support body by etching to a region where the support body is not exposed.
The second etching step and the over-etching step may be performed by etching the substrate to a region where the support is not exposed by the mixed gas of fluorine-based gas and oxygen gas in the first etching step. From the viewpoint of avoidance, it is preferable to perform the etching process using a mixed gas of nitrogen gas and oxygen gas.

  It is important to determine the ratio between the etching amount in the first stage etching process and the etching amount in the second stage etching process so as not to impair the rectangularity due to the etching process in the first stage etching process. It is. The latter ratio in the total etching amount (the sum of the etching amount in the first-stage etching process and the etching amount in the second-stage etching process) is preferably in the range of more than 0% and not more than 50%. 10 to 20% is more preferable. The etching amount refers to the remaining film thickness of the film to be etched.

  Etching preferably includes an over-etching process. The overetching process is preferably performed by setting an overetching ratio. Moreover, it is preferable to calculate the overetching ratio from the etching process time to be performed first. The over-etching ratio can be arbitrarily set, but it is preferably 30% or less of the etching processing time in the etching process, and 5 to 25% in terms of maintaining the etching resistance of the photoresist and the rectangularity of the pattern to be etched. Is more preferable, and 10 to 15% is particularly preferable.

  Next, as shown in the schematic cross-sectional view of FIG. 6, the resist pattern (that is, etching mask) 52 remaining after the etching is removed. The removal of the resist pattern 52 includes a step of applying a stripping solution or a solvent to the resist pattern 52 so that the resist pattern 52 can be removed, and a step of removing the resist pattern 52 using cleaning water. Is preferred.

  As a process of applying a stripping solution or solvent on the resist pattern 52 to make the resist pattern 52 removable, for example, a stripping solution or solvent is applied on at least the resist pattern 52 and is stagnated for a predetermined time. A step of developing can be mentioned. Although there is no restriction | limiting in particular as time to make stripping solution or a solvent stagnant, It is preferable that it is several dozen seconds to several minutes.

  Examples of the step of removing the resist pattern 52 using cleaning water include a step of removing the resist pattern 52 by spraying cleaning water onto the resist pattern 52 from a spray type or shower type spray nozzle. it can. As the washing water, pure water can be preferably used. Further, examples of the injection nozzle include an injection nozzle in which the entire support is included in the injection range, and an injection nozzle that is a movable injection nozzle and in which the movable range includes the entire support. When the spray nozzle is movable, the resist pattern 52 is more effectively moved by spraying the cleaning water by moving from the support center to the support end twice or more during the step of removing the resist pattern 52. Can be removed.

  The stripping solution generally contains an organic solvent, but may further contain an inorganic solvent. Examples of organic solvents include 1) hydrocarbon compounds, 2) halogenated hydrocarbon compounds, 3) alcohol compounds, 4) ether or acetal compounds, 5) ketones or aldehyde compounds, and 6) ester compounds. 7) polyhydric alcohol compounds, 8) carboxylic acids or acid anhydride compounds thereof, 9) phenol compounds, 10) nitrogen compounds, 11) sulfur compounds, and 12) fluorine compounds. The stripping solution preferably contains a nitrogen-containing compound, and more preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound.

The acyclic nitrogen-containing compound is preferably an acyclic nitrogen-containing compound having a hydroxyl group. Specifically, for example, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N, N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, diethanolamine, triethanolamine, etc. Preferably, they are monoethanolamine, diethanolamine, and triethanolamine, and more preferably monoethanolamine (H ₂ NCH ₂ CH ₂ OH). Examples of the cyclic nitrogen-containing compound include isoquinoline, imidazole, N-ethylmorpholine, ε-caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, α-picoline, β-picoline, γ-picoline, 2- Preferred examples include pipecoline, 3-pipecoline, 4-pipecoline, piperazine, piperidine, pyrazine, pyridine, pyrrolidine, N-methyl-2-pyrrolidone, N-phenylmorpholine, 2,4-lutidine, 2,6-lutidine and the like. Are N-methyl-2-pyrrolidone and N-ethylmorpholine, more preferably N-methyl-2-pyrrolidone (NMP).

  The stripping solution preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound. Among these, as the acyclic nitrogen-containing compound, at least one selected from monoethanolamine, diethanolamine, and triethanolamine, and cyclic The nitrogen-containing compound preferably contains at least one selected from N-methyl-2-pyrrolidone and N-ethylmorpholine, and more preferably contains monoethanolamine and N-methyl-2-pyrrolidone.

  When removing with the stripping solution, it is sufficient that the resist pattern 52 formed on the first colored pattern 12 is removed, and a deposit as an etching product adheres to the side wall of the first colored pattern 12 However, the deposit may not be completely removed. A deposit means an etching product deposited and deposited on the side wall of a colored layer.

  As the stripping solution, the content of the non-cyclic nitrogen-containing compound is 9 parts by weight or more and 11 parts by weight or less with respect to 100 parts by weight of the stripping solution, and the content of the cyclic nitrogen-containing compound is 100 parts by weight of the stripping solution. On the other hand, what is 65 to 70 mass parts is desirable. Further, the stripping solution is preferably obtained by diluting a mixture of an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound with pure water.

Next, as shown in the schematic cross-sectional view of FIG. 7, the second colored radiation-sensitive composition is embedded in each through-hole in the first through-hole portion group 121 and the second through-hole portion group 122 to obtain a plurality of The second colored radiation-sensitive composition is formed on the first colored layer (that is, the first colored pattern 12 in which the through-hole group 120 is formed in the first colored layer 11) so that the second colored pixel is formed. The second colored radiation-sensitive layer 21 is laminated (step (c)). Thereby, the 2nd coloring pattern 22 which has a some 2nd coloring pixel in the through-hole group 120 of the 1st coloring layer 11 is formed. Here, the second colored pixel is a square pixel. The second colored radiation sensitive layer 21 can be formed in the same manner as the method for forming the first colored layer 11 described above.
As thickness of the 2nd coloring radiation sensitive layer 21 here, the range of 0.3-1 micrometer is preferable, The range of 0.35-0.8 is more preferable, The range of 0.35-0.7 micrometer is more preferable.

  Then, the second colored radiation-sensitive layer 21 is exposed and developed at a position 21A corresponding to the first through-hole portion group 121 provided in the first colored layer 11 of the second colored radiation-sensitive layer 21. Then, the plurality of second colored pixels 22R provided inside each through hole of the second through hole portion group 122 are removed (step (D)) (see the schematic sectional view of FIG. 8).

Next, as shown in the schematic cross-sectional view of FIG. 9, a third colored radiation-sensitive composition is embedded in each through hole in the second through hole portion group 122 to form a plurality of third colored pixels. As described above, the third coloring radiation sensitive composition is used for the third coloring on the first coloring layer (that is, the first coloring pattern 12 in which the second coloring pattern 22 is formed in the first through-hole portion group 121). The radiation sensitive layer 31 is formed (process (e)). Thereby, the third colored pattern 32 having a plurality of third colored pixels is formed in the second through-hole portion group 122 of the first colored layer 11. Here, the third colored pixel is a square pixel. The third colored radiation-sensitive layer 31 can be formed in the same manner as the method for forming the first colored layer 11 described above.
As thickness of the 3rd coloring radiation sensitive layer 31 here, the range of 0.3-1 micrometer is preferable, The range of 0.35-0.8 is more preferable, The range of 0.35-0.7 micrometer is more preferable.

  Then, the third colored radiation-sensitive layer 31 is exposed and developed at a position 31A corresponding to the second through-hole portion group 122 provided in the first colored layer 11 of the third colored radiation-sensitive layer 31. As shown in the schematic sectional view of FIG. 10, the color filter 100 having the first colored pattern 12, the second colored pattern 22, and the third colored pattern 32 is manufactured. )).

  The second colored radiation-sensitive composition and the third colored radiation-sensitive composition described above each contain a colorant. Examples of the colorant include those described above in the colored curable composition of the present invention, but one of the second colored pixel and the third colored pixel is a red transmissive portion, and the other is a blue transmissive portion. Are preferably a red transmissive part or a blue transmissive part, respectively. The colorant contained in the colored curable composition for forming the red transmission part is C.I. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, And C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279 Species Preferably, the colorant contained in the colored curable composition for forming the blue transmission part is C.I. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, and C.I. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80 It is preferable.

  In each of the second colored radiation-sensitive composition and the third colored radiation-sensitive composition, the content of the colorant composition with respect to the total solid content is preferably 30% by mass or more, and 35% by mass. More preferably, it is more preferably 40% by mass or more. Moreover, content with respect to the total solid of the composition of a coloring agent is 90 mass% or less normally, and it is preferable that it is 80 mass% or less.

  Moreover, it is preferable that a negative radiation sensitive composition is respectively used for the 2nd colored radiation sensitive composition and the 3rd colored radiation sensitive composition. As this negative type radiation sensitive composition, there is a negative type feeling sensitive to radiation such as ultraviolet rays (g rays, h rays, i rays), deep ultraviolet rays including excimer lasers, electron beams, ion beams and X rays. A radiation composition can be used. Of the radiation, g-line, h-line and i-line are preferable, and i-line is particularly preferable.

  Specifically, the negative radiation-sensitive composition is preferably a composition containing a photopolymerization initiator, a polymerization component (polymerizable compound), a binder resin (alkali-soluble resin, etc.) and the like. Examples described in Paragraph Nos. [0017] to [0064] of Kaikai 2005-326453. Such a negative radiation sensitive composition utilizes the fact that the photopolymerization initiator initiates the polymerization reaction of the polymerizable compound upon irradiation with radiation, and as a result, the alkali soluble state becomes alkali insoluble. To do.

Exposure to the second colored radiation-sensitive layer 21 and the third colored radiation-sensitive layer 31 can be performed by exposing with g-line, h-line, i-line, etc., preferably i-line.
The development performed after exposure is usually performed by developing with a developer.
Examples of the developer include the same developers as those already described in the exposure and development of the photoresist layer 51.
When an alkaline aqueous solution is used as a developer, a washing treatment with water is generally performed after development.

  The length of one side of the first colored pixel, the second colored pixel, and the third colored pixel (the length of the short side when the pixel is a rectangle, and the length of one side when the pixel is a square) is From the viewpoint of image resolution, 0.5 to 1.7 μm is preferable, and 0.6 to 1.5 μm is more preferable.

According to the method for producing a color filter of the present invention described above, the first colored layer, and thus the first colored pixel, is formed of the colored curable composition having a high concentration of the colorant of the present invention. The thickness of one colored pixel can be extremely reduced (for example, 0.7 μm or less). Thereby, it can be set as the manufacturing method of the color filter which can manufacture the color filter by which crosstalk (color mixture of light) was suppressed.
Moreover, as described above, the first colored pixel formed by the colored curable composition of the present invention has excellent solvent resistance and alkali developer resistance. Thereby, generation | occurrence | production of the overlap area | region which overlaps with the color in another coloring layer and another coloring pattern can be reduced, As a result, a high performance color filter can be manufactured.

  The color filter obtained from the colored curable composition of the present invention can be suitably used for a liquid crystal display (LCD) or a solid-state imaging device (for example, CCD, CMOS, etc.). Moreover, it can use suitably also for image display devices, such as electronic paper and organic EL. In particular, the color filter of the present invention can be suitably used for a solid-state imaging device such as a CCD and a CMOS.

  The color filter of the present invention is also suitable as a color filter for a liquid crystal display device. A liquid crystal display device provided with such a color filter can display a high-quality image having a good display image color tone and excellent display characteristics.

  For the definition of display devices and details of each display device, refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issued in the first year). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

The color filter of the present invention is useful for a color TFT type liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS, a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can.
The color filter of the present invention can also be used for a bright and fine COA (Color-filter On Array) system.
The colored layer formed by the COA method has a rectangular shape with a side length of about 1 to 15 μm in order to connect the ITO electrode arranged on the colored layer and the terminal of the driving substrate below the colored layer. It is necessary to form a conduction path such as a through hole or a U-shaped depression, and the dimension of the conduction path (that is, the length of one side) is particularly preferably 5 μm or less, but by using the present invention, It is also possible to form a conduction path of 5 μm or less. These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-Technology and latest trends in the market (issued by Toray Research Center Research Division 2001)".

The liquid crystal display device of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film in addition to the color filter of the present invention. The color filter of the present invention can be applied to a liquid crystal display element composed of these known members. Regarding these materials, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima, CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
Regarding the backlight, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. Have been described.

  When the color filter of the present invention is used in a liquid crystal display device, a high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold-cathode tube. By using as a backlight, a liquid crystal display device having high luminance and high color purity and good color reproducibility can be provided.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” and “%” are based on mass.

Synthesis Example 1 Synthesis of Halogenated Phthalocyanine Dye A
(Synthesis of Intermediate A)
A flask was charged with tetrachlorophthalonitrile (15.0 g, 56.4 mmol), HO—C ₆ H ₄ —COOC ₂ H ₄ OCH ₃ (12.65 g, 56.4 mmol), and 75.0 g of acetonitrile, and a magnetic stirrer. After stirring for 30 minutes until the internal temperature was stabilized at 40 ° C., potassium carbonate (8.58 g, 62.1 mmol) was added and allowed to react for about 3 hours. After cooling, the solution obtained by suction filtration was concentrated under reduced pressure at 40 ° C. for 1 hour, and the solvent was distilled off. Furthermore, it vacuum-dried at 110 degreeC overnight, and about 23.0 g (89.9%) of intermediate body A was obtained.

(Synthesis of halogenated phthalocyanine dye A)
Intermediate A (2.13 g, 4.7 mmol) and 2.35 mL of benzonitrile were added to the flask, and about 1 hour until the internal temperature was stabilized at 150 ° C. using a magnetic stirrer under a nitrogen stream (10 mL / min). After stirring, 0.43 g (1.3 mmol) of zinc iodide was added and allowed to react for about 35 hours. 30 mL of methanol was added after cooling, and it was set as the crystallization solution by stirring at room temperature using a magnetic stirrer. The crystallization solution was decanted and the remaining residue was purified by silica gel column chromatography (chloroform / methanol). 20 mL of methanol was added to the obtained purified product, and the mixture was heated and stirred at 60 ° C. for 1 hour using a magnetic stirrer. After cooling, suction filtration was performed, 20 mL of methanol was added to the obtained crystals, and the mixture was heated and stirred at 60 ° C. for 1 hour using a magnetic stirrer. After cooling, suction filtration was performed, and the obtained crystal was blown and dried overnight at 40 ° C. to obtain about 1.95 g (88.2%).

<Synthesis Example 2-Synthesis of other phthalocyanine dyes>
According to Synthesis Example 1, another phthalocyanine dye was synthesized.

<Preparation of pigment dispersion>
The mixed solution containing the following compound was mixed for 3 hours with a bead mill (high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism) using zirconia beads having a diameter of 0.3 mm. Dispersed to prepare a pigment dispersion. The types of pigments were as described in Table 1 below, and the amounts of each component were blended so that the composition ratio in the finally obtained colored curable composition would be the ratio described in the following table.
・ Pigments (Pigments shown in the table below)
Derivative A
・ Dispersant A
・ Solvent: Propylene glycol monomethyl ether acetate (PGMEA)

<Preparation of colored curable composition>
Each component was mixed so that it might become a composition of the following table | surface, and it stirred and prepared the colored curable composition.
・ Phthalocyanine compounds (compounds shown in the table below)
・ Pigment dispersion (adjusted above)
・ Thermosetting compounds (compounds shown in the table below)
・ Surfactant (compound shown in the table below)
・ Solvent (solvent shown in the table below)

  In the said table | surface, () in the column of a phthalocyanine compound, another coloring agent, a derivative | guide_body, a dispersing agent, a thermosetting compound, and surfactant has shown the ratio with respect to the total solid of a colored curable composition.

<Phthalocyanine compound>
Halogenated phthalocyanine dye A:

Halogenated phthalocyanine dye B:

Halogenated phthalocyanine dye C:

Halogenated phthalocyanine dye D:

Halogenated phthalocyanine dye E:

Halogenated phthalocyanine dye F:

Halogenated phthalocyanine dye G:

Halogenated phthalocyanine multimer H (multimer of halogenated phthalocyanine dye E)
The halogenated phthalocyanine multimer H is a polymer in which glycidyl methacrylate is added to a polymer composed of a repeating unit derived from the following compound D and a repeating unit derived from methacrylic acid to give a polymerizable double bond group.
The synthesis was performed according to the following scheme.

(Synthesis of Compound A)
Tetrachlorophthalonitrile (15.0 g, 56.4 mmol), the above compound 1 (12.65 g, 56.4 mmol), and 75.0 g of acetonitrile were put into the flask and stirred for 30 minutes until the internal temperature was stabilized at 40 ° C. Then, potassium carbonate (8.58 g, 62.1 mmol) was added and allowed to react for about 3 hours. After cooling, the solution obtained by suction filtration was concentrated under reduced pressure at 40 ° C. for 1 hour, and the solvent was distilled off. Furthermore, it vacuum-dried at 110 degreeC overnight, and about 23.0g of compound A was obtained.

(Synthesis of Compound B)
The flask was charged with compound A (2.13 g, 4.7 mmol) and 2.35 mL of benzonitrile and stirred under a nitrogen stream (10 mL / min) for about 1 hour until the internal temperature was stabilized at 150 ° C. 0.43 g (1.3 mmol) was added and reacted for about 60 hours. After cooling, 30 mL of methanol was added and stirred at room temperature to obtain a crystallization solution. The crystallization solution was decanted and the remaining residue was purified by silica gel column chromatography (chloroform / methanol). 20 mL of methanol was added to the obtained purified product, and the mixture was heated and stirred at 60 ° C. for 1 hour. After cooling, suction filtration was performed, 20 mL of methanol was added to the obtained crystals, and the mixture was heated and stirred at 60 ° C. for 1 hour. After cooling, suction filtration was carried out, and the obtained solid was blown and dried overnight at 40 ° C. to obtain about 1.95 g of Compound B.

(Synthesis of Compound C)
Compound B (1.75 g, 1.06 mmol), DMF 20 mL, and 1 M aqueous sodium hydroxide solution 1.06 mL were added to the flask and stirred at an internal temperature of 60 ° C. for about 6 hours. After cooling, 10 mL of 1M hydrochloric acid was added. 50 mL of methanol was added to this solution and suction filtered, and the resulting solid was blown and dried overnight at 40 ° C. to obtain about 1.48 g of Compound C.

(Synthesis of Exemplified Compound G-1 (Compound D))
Compound C (1.5 g), 0.18 g of glycidyl methacrylate, 0.23 g of tetrabutylammonium bromide, 0.02 g of p-methoxyphenol, and 9.0 mL of propylene glycol monomethyl ether were added to the flask and stirred at 100 ° C. for about 8 hours. did. To this reaction liquid, 45 mL of methanol was added and suction filtered, and the resulting crystal was blown and dried overnight at 40 ° C. to obtain about 1.21 g of Compound D.

In a three-necked flask, compound D (24.2 g), methacrylic acid (1.08 g), dodecyl mercaptan (0.25 g), propylene glycol 1-monomethyl ether 2-acetate (hereinafter also referred to as “PGMEA”) (23. 3 g) was added and heated to 80 ° C. under a nitrogen atmosphere. To this solution, compound D (24.2 g), methacrylic acid (1.08 g), dodecyl mercaptan (0.25 g), 2,2′-azobis (isobutyric acid) dimethyl (0.58 g) [trade name: V601, Wako Pure Chemical Industries, Ltd.] and PGMEA (23.3 g) were added dropwise over 2 hours. Then, after stirring for 3 hours, the temperature was raised to 90 ° C., the mixture was heated and stirred for 2 hours, and then allowed to cool to obtain a PGMEA solution of a multimeric intermediate. Next, glycidyl methacrylate (1.42 g), tetrabutylammonium bromide (80 mg) and p-methoxyphenol (20 mg) are added and heated in an air atmosphere at 100 ° C. for 15 hours, and glycidyl methacrylate disappears. Confirmed. After cooling, it was added dropwise to a mixed solvent of methanol / ion-exchanged water = 100 mL / 10 mL and reprecipitated to obtain 47.6 g of halogenated phthalocyanine multimer H.
The weight average molecular weight (Mw) of the halogenated phthalocyanine multimer H confirmed by GPC measurement was 6,500, and the ratio of the weight average molecular weight / number average molecular weight (Mw / Mn) was 1.9.

Non-halogenated phthalocyanine dye A:
Halogenated phthalocyanine pigment A: (P.G58)

<Other colorants>
Methine pigment (dye) A: (Synthesis examples will be described later.)
Methine dye (dye) B: (OPLAS YELLOW 140, Orient Chemical Co., Ltd.)
Azo dye (pigment) A: P.I. Y150
Azo dye (pigment) B: P.I. Y155
Isoindoline dye (pigment) A: P.I. Y139

<Derivative>
Derivative A:

<Dispersant>
Dispersant A: (synthesized with reference to paragraph number 0334 of JP-A-2007-277514)
In the above, a is 2.0, b is 4.0, acid value is 10 mgKOH / g, and Mw20000.
Further, a and b in the dispersant A each represent the number of partial structures represented in parentheses and satisfy a + b = 6.

<Thermosetting compound>
Epoxy compound A: EHPE3150 (Daicel Chemical Industries, Ltd. molecular weight = 2234)
Epoxy compound B: (DIC Corporation, EPICLON HP-4032 molecular weight = 272)
Epoxy compound C: (DIC Corporation, EPICLON N-660, molecular weight = 3400)
Melamine compound A: Nicalak, Sanwa Chemical Co., Ltd. melamine compound B: 80% solution of a compound containing a structure represented by the following structural formula (manufactured by Sigma-Aldrich)

<Surfactant>
Surfactant A: F-781 (Fluorine type surfactant manufactured by DIC Corporation)

<Synthesis of methine pigment (dye) A>
Methine pigment (dye) A was synthesized according to the following scheme.

(Synthesis of Intermediate A)
A mixed solution of 100 parts by weight of the above compound (A) (synthesized by the method described in EP 0571959A2) and 390 ml of pyridine was cooled to 5 ° C., and 87 parts by weight of octanesulfonyl chloride was added dropwise at a reaction temperature of 25 ° C. or less. The reaction mixture was stirred at room temperature for 2 hours, 2 L of 4N aqueous hydrochloric acid solution was added, and the mixture was stirred at room temperature and collected by filtration. The crystals collected by filtration were washed with 500 ml of methanol and dried to obtain 153 g of intermediate A (yield 91%).
¹ H-NMR CDCl ₃ δ0.8 (t, 3H) 1.0-1.4 (m, 19), 1.6 (m, 2H) 3.2 (t, 2H) 5.6 (s, 1H) 7.3 (d, 2H) 7.9 (d , 2H) 10.2 (s, 1H) 12.9 (s, 1H)

(Synthesis of methine pigment (dye) A)
To a suspension of 110 g of Intermediate A and 650 ml of acetic acid, 68 g of ethyl orthoformate was added at room temperature, and the reaction solution was allowed to stir at 80 ° C. for 3 hours. Methanol 1.1L was added to the reaction liquid, and after cooling, it was filtered and washed with methanol to obtain 96 g (yield 88%) of methine dye (dye) A.
¹ H-NMR CDCl ₃ δ0.8 (t, 6H) 1.2-2.0 (m, 41H) 3.3 (t, 4H) 7.3 (d, 4H), 7.6 (br, 2H) 7.8 (d, 4H) 8.4 (s , 1H)

  The following evaluation was performed about the obtained composition.

<Spectroscopic characteristics (film thickness)>
The composition obtained above was applied onto a 7.5 cm × 7.5 cm glass substrate with a spin coater so as to form a coating film having a thickness of 0.6 μm, and then heated at 100 ° C. using a hot plate. The coating layer was heated and dried for 5 minutes, and further heated at 200 ° C. for 5 minutes to cure the coating film, thereby forming a colored layer.

The spectrum of the glass substrate obtained above was measured using MCPD-3000 (manufactured by Otsuka Corporation). The difference Δ% between the maximum transmittance and the minimum transmittance in the spectral spectrum of the colored layer obtained from each composition was evaluated according to the following categories. In addition, it means that it is excellent in spectral characteristics, so that (DELTA)% is large.
5: Δ% = 95 or more and 100 or less 4: Δ% = 90 or more and less than 95 3: Δ% = 85 or more and less than 90 2: Δ% = 80 or more and less than 85 1: Δ% = 0 or more and less than 80

<Chemical resistance>
A colored layer substrate prepared by the same method as described above from the composition obtained above was immersed in a propylene glycol monomethyl ether acetate solvent for 10 minutes, and then the spectrum obtained by rinsing with running water was measured.
The absorbance before and after immersion was compared, the color material remaining rate after immersion was calculated from the following formula, and evaluated according to the following categories. In addition, it means that it is excellent in chemical resistance, so that a color material residual rate is high.
Formula:
Residual ratio of coloring material (%) = maximum absorbance after immersion in solvent / maximum absorbance before immersion in solvent × 100
5: Color material remaining rate = 95% or more and 100% or less 4: Color material remaining rate = 80% or more and less than 95% 3: Color material remaining rate = 70% or more and less than 80% 2: Color material remaining rate = 40% or more and 70 Less than% 1: Color material remaining rate = 0% or more and less than 40%

<Heat resistance (diffusion of colorant by heat)>
Preparation of evaluation substrate (formation of colored layer)
After applying the above composition to a 0.6 μm-thick coating film on a 7.5 cm × 7.5 cm glass substrate with a spin coater, heat drying at 100 ° C. for 2 minutes using a hot plate Then, heating was performed at 200 ° C. for 5 minutes, and the coating film was cured to form a colored layer.

(Pattern formation)
((Applying mask resist))
A positive photoresist “FHi622BC” (manufactured by FUJIFILM Electronics Materials) was applied and pre-baked to form a 0.8 μm-thick photoresist layer.
Next, heat treatment was performed for 1 minute at a temperature at which the temperature of the photoresist layer or the ambient temperature was 90 ° C. Next, the i-line reduction projection exposure apparatus was used to irradiate the coating film at a wavelength of 365 nm through a checkered mask measuring 1 cm in length and 1 cm in width. Thereafter, development processing was performed for 1 minute with a developer “FHD-5” (manufactured by Fujifilm Electronics Materials), and further post-baking processing was performed at 110 ° C. for 1 minute.

(Dry etching)
Next, the obtained glass substrate was bonded to an 8-inch silicon wafer, and dry etching was performed according to the following procedure. RF power: 800 W, antenna bias: 400 W, wafer bias: 200 W, chamber internal pressure: 4.0 Pa, substrate temperature: 50 ° C., mixed gas with dry etching apparatus (Hitachi High Technologies, U-621) The first stage etching process was performed for 80 seconds with the gas type and flow rate being CF ₄ : 80 mL / min, O ₂ : 40 mL / min, and Ar: 800 mL / min.
Next, in the same etching chamber, RF power: 600 W, antenna bias: 100 W, wafer bias: 250 W, chamber internal pressure: 2.0 Pa, substrate temperature: 50 ° C., gas mixture type and flow rate of N ₂ : 500 mL / min, O ₂ : 50 mL / min, Ar: 500 mL / min (N ₂ / O ₂ / Ar = 10/1/10), and the second-stage etching treatment and over-etching treatment for 28 seconds were performed.
After performing dry etching under the above conditions, a resist stripping solution “MS230C” (manufactured by FUJIFILM Electronics Materials Co., Ltd.) is used for 120 seconds to remove the resist, and further cleaning with pure water. Spin drying was performed. Thereafter, a dehydration baking process was performed at 100 ° C. for 2 minutes. The colored layer pattern board | substrate was obtained by the above.

A CT-2000L solution (manufactured by FUJIFILM Electronics Materials Co., Ltd .; base clearing agent) is applied to the colored pattern forming surface produced as described above so that the dry film thickness is 0.6 μm, and dried. 11 and FIG. 12, after forming a transparent film, a heat treatment was performed at 200 ° C. for 5 minutes. After heating, the absorbance of the transparent film part adjacent to the colored pattern was measured with MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.). The absorbance of the transparent film part before and after heating was compared, the color material diffusion amount was calculated from the following formula, and evaluated according to the following categories. In addition, it means that it is excellent in heat resistance, so that movement amount is small.
Formula:
Color material transfer amount = maximum absorbance of transparent film portion after heating / maximum absorbance of colored pattern portion before heating × 100
5: Color material movement amount = 0
4: Color material movement amount = 0 to more than 5 3: Color material movement amount = More than 5 to 10 or less 2: Color material movement amount = More than 10 to 20 or less 1: Color material movement amount = 20 to 100 or less

<Chemical resistance (mandatory conditions)>
A colored layer substrate prepared by the same method as described above from the composition obtained above was immersed in a propylene glycol monomethyl ether acetate solvent for 1 month, and then the spectrum obtained by rinsing with running water was measured.
The absorbance before and after immersion was compared, the color material remaining rate after immersion was calculated from the following formula, and evaluated according to the following categories. In addition, it means that it is excellent in chemical resistance, so that a color material residual rate is high.
Formula:
Residual ratio of coloring material (%) = maximum absorbance after immersion in solvent / maximum absorbance before immersion in solvent × 100
5: Color material remaining rate = 95% or more and 100% or less 4: Color material remaining rate = 80% or more and less than 95% 3: Color material remaining rate = 70% or more and less than 80% 2: Color material remaining rate = 40% or more and 70 Less than% 1: Color material remaining rate = 0% or more and less than 40%

As is apparent from the above table, it contains at least a colorant containing a halogenated phthalocyanine dye, a thermosetting compound, and a solvent for dissolving them, and the total content of the colorant is 60 to 90% by mass with respect to the total solid content. It can be seen that the colored layers (Examples 1 to 19) formed using the colored curable composition are excellent in spectral characteristics, chemical resistance and heat resistance. It was.
In particular, it has been found that when an epoxy resin is used as a thermosetting compound and when a methine dye or an azo dye is used as a yellow dye, a remarkable effect is obtained.
On the other hand, when the phthalocyanine dye does not contain a halogen (Comparative Example 1), when the phthalocyanine compound is a pigment (Comparative Example 2), when the blending amount of the colorant is small (Comparative Example 3), spectral characteristics, chemical resistance Only a colored layer inferior in any one or more of property and heat resistance was obtained.

  According to the present invention, a colored curable composition with an increased colorant concentration can be prepared, and it can be expected to be used for preparing a thin film color filter with good color separation. In the present invention, for example, it can be expected that excellent effects can be exhibited even when the thickness of the colored layer is 0.1 to 1.0 μm. In addition, the combined use of the colored curable composition of the present invention can improve the curability of the pixel and suppress color loss for chemicals (resist stripping solution, alkali developer and general solvent) exposed in various processes. Can be expected to do. In addition, it can be expected that thermal diffusion color mixing (heat resistance) to other pixels is suppressed at the time of stacking and a good device sensitivity is achieved.

DESCRIPTION OF SYMBOLS 10 Solid-state image sensor 11 1st colored layer 12 1st colored pattern 13,100 Color filter 14 Flattening film 15 Microlens 20G Green pixel (1st color pixel)
20R red pixel (second color pixel)
20B Blue pixel (third color pixel)
21 2nd coloring radiation sensitive layer 21A The position corresponding to the 1st through-hole part group 121 22 2nd coloring pattern 22R The some 2nd coloring pixel 31 provided in the inside of each through-hole of the 2nd through-hole part group 122 Third colored radiation-sensitive layer 31A Position corresponding to second through-hole portion group 32 Third colored pattern 41 P well 42 Light receiving element (photodiode)
43 Impurity diffusion layer 44 Electrode 45 Wiring layer 46 BPSG film 47 Insulating film 48 P-SiN film 49 Planarizing film layer 51 Photoresist layer 51A Resist through hole 52 Resist pattern (patterned photoresist layer)
120 through-hole group 121 first through-hole part group 122 second through-hole part group

Claims (14)

A colorant containing at least a halogenated phthalocyanine dye and a yellow pigment, a thermosetting compound, and a solvent that dissolves at least the halogenated phthalocyanine dye and the thermosetting compound, and the total content of the colorant is based on the total solid content 60 to 90% by weight of a colored curable composition,
The colorant contains 55 to 80% by mass of the halogenated phthalocyanine dye and 20 to 45% by mass of the yellow pigment,
The halogenated phthalocyanine dye or a compound represented by the following general formula (1), or, a halogenated phthalocyanine structures directly halogenating the carbon atoms of the phthalocyanine skeleton is a compound containing 2 or more the following general formula (A Is a halogenated phthalocyanine multimer comprising a structural unit represented by :
The yellow pigment is a monomethine dye represented by the following general formula (5), an azo yellow pigment, or an isoindoline yellow pigment,
The thermosetting compound, epoxy compound, melamine compound, at least one selected from urea compounds and phenolic compounds,
The said colored curable composition is a colored curable composition which contains the said thermosetting compound 4.5 to 40 mass% with respect to the total solid of the said colored curable composition.
General formula (1)
(In the general formula (1), Z ^{1 to} Z ¹⁶ are each a hydrogen atom , a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, a hydroxyl group, a cyano group, a nitro group, or an alkoxy group. , Aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, acyl group, Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, amino group, anilino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, sulfamoyla Group, azo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, sulfo group, phosphonyl group, phosphinoylamino group, the following general A group represented by the formula (1-1-2) or a group represented by the following general formula (1-5-1), wherein at least one of Z ^{1 to} Z ¹⁶ is a halogen atom; At least one of Z ^{1 to} Z ¹⁶ is a group represented by the following general formula (1-5-1), where M represents two hydrogen atoms, a metal atom, a metal oxide, or a metal halide. .)
General formula (1-1-2)
(In General Formula (1-1-2), X ¹ is an oxygen atom or a sulfur atom, and A ¹¹ is a phenyl group having 1 to 5 substituents R, or a naphthyl having 1 to 7 substituents R. The substituent R is a nitro group, COOR ¹ (R ¹ is a group represented by the general formula (1-3) or an alkyl group having 1 to 8 carbon atoms), OR ² (R ² is carbon. An alkyl group having 1 to 8 carbon atoms), a halogen atom, an aryl group, a cyano group, an alkyl group having 1 to 8 carbon atoms, a group represented by any one of the general formulas (4) to (6), or a general formula ( Represents a group selected from X).)
(In the general formula (4), R ⁴ is a hydrogen atom, an alkoxy group, an aryl group, an aryloxy group, an alkoxycarbonyl group, an alkylthio group, an arylthio group and an alkyl group which may have a substituent selected from a halogen atom, The aryl group which may have the substituent, the dialkylamino group which may have the substituent, the diarylamino group which may have the substituent, or the alkylaryl which may have the substituent Represents an amino group.
In the general formula (5), d represents an integer of 0 to 2, and when d is 0 or 1, R ⁵ represents an alkoxy group, an aryl group, an aryloxy group, an alkoxycarbonyl group, an alkylthio group, an arylthio group, and a halogen. An alkyl group which may have a substituent selected from atoms, or an aryl group which may have the substituent, and when d is 2, R ⁵ is an alkyl which may have the substituent A group, an aryl group that may have the substituent, a dialkylamino group that may have the substituent, a diarylamino group that may have the substituent, or the substituent. Represents an alkylarylamino group.
In general formula (6), R ⁶ and R ⁷ are each an alkyl optionally having a substituent selected from an alkoxy group, an aryl group, an aryloxy group, an alkoxycarbonyl group, an alkylthio group, an arylthio group, and a halogen atom. Group, aryl group optionally having substituent (s), alkylcarbonyl group optionally having substituent (s), arylcarbonyl group optionally having substituent (s), alkyl optionally having substituent (s) A sulfonyl group or an arylsulfonyl group which may have the above-described substituent is represented. )
General formula (1-3)
(In General Formula (1-3), R ³ represents an alkylene group having 1 to ³ carbon atoms, R ⁴ represents an alkyl group having 1 to 8 carbon atoms, and n represents an integer of 1 to 4).
(In general formula (X), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. N1 represents an integer of 1 to 3. When n1 is 2 or 3, a plurality of R ¹¹ are each Y ¹ is —O—, —S—, —NR ¹³ — (R ¹³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), —SO ₂ —, or -C (= O)-R ¹² represents an alkyl group, alkenyl group, aryl group, heterocyclic group, silyl group, hydroxyl group, cyano group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy Group, silyloxy group, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, acyl group, Coxycarbonyl group, aryloxycarbonyl group, carbamoyl group, amino group, anilino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, sulfo From famoylamino group, azo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, sulfo group, phosphonyl group and phosphinoylamino group An alkyl group which may have a substituent selected, an acyl group which may have the substituent, a sulfonyl group which may have the substituent, an alkoxy group which may have the substituent, or Alkylamino optionally having the substituent A representative.)
Formula (1-5-1)
(In the general formula (1-5-1), L ¹ represents —O— or —S— , Ar represents an arylene group, and A represents a group represented by the following general formula (1-5-2). * Represents the site of bonding to the phthalocyanine ring.)
Formula (1-5-2)
* -L ^2A- (Meth) acryloyloxy group (in the general formula (1-5-2), L ^2A represents -O-, -C (= O)-, -CH _2- , -CH (OH)- , —NR ^B — represents a group consisting of one or a combination of two or more, R ^B represents a hydrogen atom, an alkyl group, or an aryl group, * represents an Ar atom in the general formula (1-5-1) Represents the binding site.)
Formula (A)
(In General Formula (A), X ¹ represents a (meth) acrylic linking chain, L ¹ represents a single bond, or an alkylene group, an arylene group, a heterocyclic linking group, —CH═CH—, — O—, —S— , —C (═O) —, —CO ₂ —, —NR—, —CONR—, —O ₂ C— , —SO— , —SO ₂ — and two or more of these are linked. And each R independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and DyeI represents a partial structure derived from the compound represented by the general formula (1). Represents.)
General formula (5)
(In the general formula (5), R ¹¹ represents an alkyl group or a vinyl group, and R ¹² represents an alkylsulfonylamino group, a vinylsulfonylamino group, an arylsulfonylamino group, an alkylcarbonylamino group, a vinylcarbonyl, respectively. Represents an aromatic ring group having a substituent selected from an amino group and an arylcarbonylamino group.) The thermosetting compound is at least one selected from epoxy compounds and melamine compounds, colored curable composition according to claim 1.   The colored curable composition of Claim 1 or 2 whose content of the thermosetting compound in the said colored curable composition is 5-40 mass% with respect to the total solid.   The colored curable composition according to any one of claims 1 to 3, wherein the thermosetting compound is an epoxy compound.   The colored curable composition according to any one of claims 1 to 4, wherein the thermosetting compound has two or more epoxy groups in one molecule and has a molecular weight of 1,000 or more.   The colored curable composition according to any one of claims 1 to 5, wherein the yellow pigment is a monomethine dye represented by the general formula (5). In the general formula (1), of Z ¹ to Z ^16, 1 to 8 one is a group represented by any one of the following, the colored curable according to any one of claims 1 to 6 Composition.
The colored curable composition according to any one of claims 1 to 6, wherein the halogenated phthalocyanine dye is a compound represented by the following general formula (1-5).
Formula (1-5)
(In the general formula (1-5), Z ¹ to Z ¹⁶ each represent a hydrogen atom, a halogen atom, a group represented by the general formula (1-5-1), of Z ¹ to Z ¹⁶ , At least one represents a group represented by the general formula (1-5-1), and at least one is a halogen atom, M is two hydrogen atoms, a metal atom, a metal oxide or a metal halide. Represents.) The colored curable composition according to any one of claims 1 to 6, wherein the halogenated phthalocyanine dye is a halogenated phthalocyanine multimer comprising the structural unit represented by the general formula (A) .   A cured film obtained by curing the colored curable composition according to claim 1.   The color filter which has a colored layer using the colored curable composition of any one of Claims 1-9.   The color filter of Claim 11 whose thickness of a colored layer is 0.1-1.0 micrometer.   A step of forming a colored layer using the colored curable composition according to any one of claims 1 to 9, a step of forming a photoresist layer on the colored layer, exposure and development to form the photoresist. A method for producing a color filter, comprising: a step of patterning a layer to obtain a resist pattern; and a step of dry etching the colored layer using the resist pattern as an etching mask.   A liquid crystal display device, an organic electroluminescence element, or a solid-state imaging device having the color filter according to claim 11.