JP2005134758A - Dye-containing curable composition, and color filter and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stable dye-containing curable composition having good heat resistance and light resistance. <P>SOLUTION: The dye-containing curable composition contains at least (A) an alkali-soluble resin, (B) a phthalocyanine mixture represented by formula (1) and/or a phthalocyanine compound represented by formula (2) and (C) a photosensitive compound, wherein R<SP>1</SP>and R<SP>2</SP>are each unsubstituted alkyl, alkyl containing O in the form of an ether bond or the like, alkylcarbonyl or alkoxycarbonyl (R<SP>1</SP>and/or R<SP>2</SP>is alkyl containing O in the form of an ether bond or the like, alkylcarbonyl or alkoxycarbonyl); R<SP>3</SP>is H, unsubstituted alkyl or alkyl containing O in the form of an ether bond or the like; m=0.1-3.9, n=0.1-3.9 (m+n=1.0-4.0); m'=1-3, n'=1-3 (m'+n'=2-4); and Met is a metal atom or or an oxy-metal. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a dye-containing curable composition suitable for forming a colored image constituting a color filter used in a liquid crystal display device, a solid-state imaging device, etc., a color filter using the dye-containing curable composition, and a production thereof Regarding the method.

  As a method for producing a color filter generally used for a liquid crystal display element or a solid-state image sensor, a dyeing method, an electrodeposition method, a printing method, a pigment dispersion method, and the like are known.

  The above dyeing method is a method for producing a color filter by dyeing a dyed substrate made of a natural resin such as gelatin, mulled or casein or a synthetic resin such as amine-modified polyvinyl alcohol with a dye such as an acid dye. In this dyeing method, there is a problem in light resistance, heat resistance and moisture resistance due to the use of a dye, and color unevenness is likely to occur because it is difficult to uniformly control dyeing and fixing characteristics on a large screen. When dyeing, there is a problem that a dye-proof layer is required and the process is complicated.

  In the electrodeposition method, a transparent electrode is formed in a predetermined pattern in advance, a resin containing a pigment dissolved or dispersed in a solvent is ionized, a voltage is applied, and a colored image is formed in a pattern. This is a method for producing a filter. In this electrodeposition method, a transparent electrode for forming a color filter and a photolithography process including an etching process are required in addition to the transparent electrode for display. In this case, when there is a short circuit, a line defect occurs and the yield decreases. Further, in principle, it is difficult to apply to a mosaic arrangement other than the stripe arrangement, and further, it is difficult to manage the transparent electrode.

  The printing method is a simple method for producing a color filter by printing such as offset printing using an ink in which a pigment is dispersed in a thermosetting resin or an ultraviolet curable resin. However, since the ink that can be used is highly viscous, filtering is difficult, and defects due to dust, foreign matter, and the gelled portion of the ink binder are likely to occur. Position accuracy, line width accuracy, and planar smoothness associated with printing accuracy There is a problem.

  The pigment dispersion method is a method for producing a color filter by a photolithography method using a colored radiation-sensitive composition in which a pigment is dispersed in various photosensitive compositions. This method uses a pigment as a coloring material and is stable to light, heat, etc., and is patterned by a photolithographic method, so that it has excellent positional accuracy and is suitable for producing a color filter for a large screen and high-definition color display. .

  As a pigment dispersion method, a negative photosensitive composition in which a photopolymerizable monomer and a photopolymerization initiator are used in combination with an alkali-soluble resin is disclosed (for example, see Patent Document 1). However, in recent years, there has been a demand for higher definition in color filters for solid-state imaging devices, and the conventional pigment dispersion method essentially does not improve the resolution because the pigment exists in a particle state having a size. Further, there are problems such as color unevenness due to coarse particles of the pigment, and it is not suitable for applications requiring a fine pattern such as a solid-state imaging device.

  In response to the above demand for higher resolution, a technique using a dye as a colorant has been studied, and a positive curable composition containing a naphthoquinonediazide compound or the like as a dye-containing curable composition using a dye. There have been proposed two types of compositions (for example, see Patent Document 2) and negative curable compositions (for example, see Patent Document 3) using a photopolymerization initiator (in combination with a crosslinking agent) as a photosensitive material. . However, these dye-containing curable compositions have problems in terms of solvent solubility of the dye, and also have a problem that the heat resistance and light resistance of the dye are low.

Examples of dyes having excellent heat resistance and light resistance include phthalocyanine compounds, but phthalocyanine compounds have poor solvent solubility and have practical problems. Cause a problem of deterioration. On the other hand, a compound in which a sulfonic acid amide group is substituted is disclosed as a phthalocyanine compound with improved solvent solubility (see, for example, Patent Document 4). However, the required solubility is still insufficient.
Japanese Patent Laid-Open No. 1-102469 JP-A-2-127602 JP-A-6-75375 Japanese Patent Laid-Open No. 3-195833

  As described above, a dye having both solvent solubility and heat and light resistance is constituted as a colorant, and particularly a dye-containing curable composition or a color filter having good heat resistance and light resistance is still available. The current situation is that it has not been provided. This invention is made | formed in view of the above, and makes it a subject to achieve the following objective.

An object of the present invention is to provide a stable dye-containing curable composition containing a phthalocyanine dye having excellent solvent solubility and having good heat resistance and light resistance. In particular, it is suitable for cyan color because the transmittance on the long wave side with a wavelength of 600 nm or more is kept low, and as other dyes, for example, a blue color is combined with a violet dye, or a green color is combined with a yellow dye. Suitable for color.
In addition, the present invention is a color filter which is sharp and has a good hue, is particularly excellent in heat resistance and light resistance, and has a high resolution with a rectangular good pattern, and has heat resistance and light resistance. It aims at providing the manufacturing method of the color filter which can produce a filter.

  The present invention is excellent in solvent solubility by introducing a specific number of specific sulfonamide groups as substituents of the phthalocyanine skeleton constituting the dye, and a photosensitive ( This has been achieved based on the knowledge that the curable composition (especially for cyan color) exhibits particularly good heat resistance and light resistance. Hereinafter, specific means for solving the above problems will be described.

  <1> A dye-containing curable composition containing at least (A) an alkali-soluble resin, (B) a dye, and (C) a photosensitive compound, wherein the (B) dye is represented by the following general formula (1). It is a dye-containing curable composition characterized by including a phthalocyanine mixture.

In the general formula (1), R ¹ and R ² are each independently an unsubstituted alkyl group, an alkyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond and an ester bond, A group, an alkoxycarbonyl group, wherein at least one of R ¹ and R ² is an alkyl group, an alkylcarbonyl group, or an alkoxycarbonyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond, and an ester bond Represents. R ³ represents a hydrogen atom, an unsubstituted alkyl group, or an alkyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond, an ester bond, and a hydroxy group. However, the -R ³ and -CHR ¹ R ² is not to represent the same group at the same time. m represents a numerical value of 0.1 to 3.9, n represents a numerical value of 0.1 to 3.9, and m + n represents a numerical value of 1.0 to 4.0. Met represents a divalent metal atom, a trivalent monosubstituted metal atom, a tetravalent disubstituted metal atom, or an oxy metal.

<2> In the general formula (1), R ¹ and R ² are an unsubstituted alkyl group having 1 to 8 carbon atoms, and an oxygen atom is selected from an ether bond, a carbonyl bond, and an ester bond. Represents an alkyl group having 1 to 12 carbon atoms, an alkylcarbonyl group having 2 to 12 carbon atoms, or an alkoxycarbonyl group having 2 to 12 carbon atoms, wherein R ³ represents a hydrogen atom, 8 represents an unsubstituted alkyl group having 8 or 1 to 12 carbon atoms containing 1 to 4 oxygen atoms in at least one form selected from an ether bond, a carbonyl bond, an ester bond and a hydroxy group. > Is a curable composition containing a dye.

<3> In the general formula (1), m represents a numerical value of 0.5 to 3.5, n represents a numerical value of 0.5 to 3.5, and m + n represents a numerical value of 1.0 to 4.0. The dye-containing curable composition according to <1> or <2>.
<4> The dye-containing curable composition according to any one of <1> to <3>, wherein Met represents Cu, Co, Zn, Pd, VO, AlCl, or AlOH in the general formula (1). .
<5> A dye-containing curable composition containing at least (A) an alkali-soluble resin, (B) a dye, and (C) a photosensitive compound, wherein the (B) dye is represented by the following general formula (2). A curable composition containing a dye containing a phthalocyanine compound.

In the general formula (2), R ¹ and R ² are each independently an unsubstituted alkyl group, an alkyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond and an ester bond, A group, an alkoxycarbonyl group, wherein at least one of R ¹ and R ² is an alkyl group, an alkylcarbonyl group, or an alkoxycarbonyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond, and an ester bond Represents. R ³ represents a hydrogen atom, an unsubstituted alkyl group, or an alkyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond, an ester bond, and a hydroxy group. However, -R ³ and -CHR ¹ R ² is not to represent the same group at the same time. m ′ represents a numerical value of 1 to 3, n ′ represents a numerical value of 1 to 3, and m ′ + n ′ represents a numerical value of 2 to 4. Met represents a divalent metal atom, a trivalent monosubstituted metal atom, a tetravalent disubstituted metal atom, or an oxy metal.

<6> In the general formula (2), R ¹ and R ² are an unsubstituted alkyl group having 1 to 8 carbon atoms, and an oxygen atom is selected from an ether bond, a carbonyl bond, and an ester bond. Represents an alkyl group having 1 to 12 carbon atoms, an alkylcarbonyl group having 2 to 12 carbon atoms, or an alkoxycarbonyl group having 2 to 12 carbon atoms, wherein R ³ represents a hydrogen atom, 8 represents an unsubstituted alkyl group having 8 carbon atoms or an alkyl group having 1 to 12 carbon atoms containing 1 to 4 oxygen atoms in at least one form selected from an ether bond, a carbonyl bond, an ester bond and a hydroxy group. > Is a dye-containing curable composition described in

<7> The dye-containing curable composition according to <5> or <6>, wherein Met in the general formula (2) represents Cu, Co, Zn, Pd, VO, AlCl, or AlOH.
<8> (E) The dye-containing curable composition according to any one of <1> to <7>, further including a crosslinking agent.
<9> At least (A) an alkali-soluble resin and (B) a dye, and the (B) dye is represented by a phthalocyanine mixture represented by the following general formula (1) and the following general formula (2) A color filter comprising at least one selected from the group of phthalocyanine compounds.

In the general formula (1), R ¹ and R ² are each independently an unsubstituted alkyl group, an alkyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond and an ester bond, A group, an alkoxycarbonyl group, wherein at least one of R ¹ and R ² is an alkyl group, an alkylcarbonyl group, or an alkoxycarbonyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond, and an ester bond Represents. R ³ represents a hydrogen atom, an unsubstituted alkyl group, or an alkyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond, an ester bond, and a hydroxy group. However, the -R ³ and -CHR ¹ R ² is not to represent the same group at the same time. m represents a numerical value of 0.1 to 3.9, n represents a numerical value of 0.1 to 3.9, and m + n represents a numerical value of 1.0 to 4.0. Met represents a divalent metal atom, a trivalent monosubstituted metal atom, a tetravalent disubstituted metal atom, or an oxy metal.

In the general formula (2), R ¹ and R ² are each independently an unsubstituted alkyl group, an alkyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond and an ester bond, A group, an alkoxycarbonyl group, wherein at least one of R ¹ and R ² is an alkyl group, an alkylcarbonyl group, or an alkoxycarbonyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond, and an ester bond Represents. R ³ represents a hydrogen atom, an unsubstituted alkyl group, or an alkyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond, an ester bond, and a hydroxy group. However, -R ³ and -CHR ¹ R ² is not to represent the same group at the same time. m ′ represents a numerical value of 1 to 3, n ′ represents a numerical value of 1 to 3, and m ′ + n ′ represents a numerical value of 2 to 4. Met represents a divalent metal atom, a trivalent monosubstituted metal atom, a tetravalent disubstituted metal atom, or an oxy metal.

<10> A step of coating the dye-containing curable composition according to any one of <1> to <8> on a support, exposing through a mask, and developing to form a pattern image. This is a method for manufacturing a color filter.
In the method for producing a color filter, when producing a color filter having a desired hue, the above steps are repeated according to the desired number of hues. Moreover, the aspect which has the process of hardening | curing the said pattern image by heating and / or exposure as needed is also suitable.

  As described above, the solubility of phthalocyanine dyes is generally very poor, and it has been difficult to prepare a color filter by a coating method, particularly a dye-containing curable composition containing a dye. When the composition was stored as a solution, the solubility was insufficient, so that the dye was deposited over time, resulting in poor storage and poor practicality. On the other hand, in the present invention, a stable dye-containing curable composition is obtained by increasing the solvent solubility of the dye, and precipitation of the dye from the dye-containing curable composition and from the coating film after coating are performed. Dye precipitation can be reduced. Furthermore, heat resistance and light resistance can be improved, and a high-performance color filter can be obtained.

According to the present invention, it is possible to provide a stable dye-containing curable composition (particularly a cyan dye-containing curable composition) containing a phthalocyanine dye excellent in solvent solubility and having good heat resistance and light resistance. . Also,
According to the present invention, a color filter which is sharp and has a good hue, is particularly excellent in heat resistance and light resistance, and has a high resolution with a rectangular good pattern and has heat resistance and light resistance. A method for manufacturing a color filter that can produce a filter can be provided.

  Hereinafter, the dye-containing curable composition of the present invention, a color filter (preferably using the dye-containing curable composition) and a method for producing the color filter will be described in detail.

  The dye-containing curable composition of the present invention comprises (A) an alkali-soluble resin, (B) a dye, and (C) a photosensitive compound, and generally comprises (D) a solvent. ) In particular, the dye comprises a phthalocyanine mixture represented by the following general formula (1) and / or a phthalocyanine compound represented by the general formula (2).

  The dye-containing curable composition of the present invention can be constituted as a positive type when it contains a naphthoquinonediazide compound as the photosensitive compound (C), and can be constituted as a negative type when it contains a photopolymerization initiator. In the case of constituting the negative type, generally, (E) a crosslinking agent can be further contained, and in the case of constituting the positive type, (E) a crosslinking agent can be further contained (preferably together with a photopolymerization initiator). In addition, other components may be included as necessary.

First, the dye that characterizes the present invention will be described in detail.
(B) Dye In the present invention, the dye contains at least one of the following phthalocyanine mixtures and / or phthalocyanine compounds. These are highly soluble in solvents, prevent dye precipitation when in the solution state or in the coated state after coating, and constitute a stable, heat- and light-resistant dye-containing curable composition. it can.

[Phthalocyanine mixture]
The phthalocyanine mixture according to the present invention is a mixture of phthalocyanine compounds in which at least one of two kinds of sulfonamide groups is introduced into a phthalocyanine skeleton, and is represented by the following general formula (1).

In the general formula (1), R ¹ and R ² are each independently an unsubstituted alkyl group, an alkyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond and an ester bond, A group, an alkoxycarbonyl group, wherein at least one of R ¹ and R ² is an alkyl group, an alkylcarbonyl group, or an alkoxycarbonyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond, and an ester bond Represents.

The unsubstituted alkyl group represented by R ¹ or R ² is preferably an unsubstituted alkyl group having 1 to 8 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, and an octyl group.

The “alkyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond and an ester bond” represented by R ¹ or R ² is an oxygen atom in the above at least one form in a range of 1 to 4 An alkyl group having 1 to 12 carbon atoms is preferred. Specific examples include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, acetylmethyl group, acetylethyl group, propionylmethyl group, propionylethyl group, tetrahydrofurfuryloxymethyl group, 2,2-dimethyl. -1,3-dioxolane-4-methoxymethyl group, 2- (1,3-dioxolane) ethoxymethyl group, 2- (1,3-dioxane) ethoxymethyl group, methoxycarbonylmethyl group, ethoxycarbonylethyl group, propoxy Preferred examples include carbonylethyl group, butoxycarbonylethyl group, and pentoxycarbonylbutyl group.

The alkylcarbonyl group or alkoxycarbonyl group represented by R ¹ or R ² is preferably an alkylcarbonyl group having 2 to 12 carbon atoms or an alkoxycarbonyl group having 2 to 12 carbon atoms. Specific examples include acetyl group, propionyl group, propylcarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group and pentoxycarbonyl group.

R ³ in the general formula (1) represents a hydrogen atom, an unsubstituted alkyl group, or an alkyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond, an ester bond, and a hydroxy group.

The unsubstituted alkyl group represented by R ³ is preferably an unsubstituted alkyl group having 1 to 8 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, and an octyl group.

As the “alkyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond, an ester bond and a hydroxy group” represented by R ³ , An alkyl group having 1 to 12 carbon atoms is preferred. Specific examples include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, hydroxyethyl, hydroxyethoxyethyl, acetylmethyl group, acetylethyl group, propionylmethyl group, propionylethyl group, tetrahydrofurfuryloxymethyl. Group, 2,2-dimethyl-1,3-dioxolane-4-methoxymethyl group, 2- (1,3-dioxolane) ethoxymethyl group, 2- (1,3-dioxane) ethoxymethyl group, methoxycarbonylmethyl group An ethoxycarbonylethyl group, a propoxycarbonylethyl group, a butoxycarbonylethyl group, and a pentoxycarbonylbutyl group are preferable.

In the above, —R ³ and —CHR ¹ R ^{2 in} formula (1) do not represent the same group at the same time.

  In the phthalocyanine mixture, the substitution positions of the two sulfonamide groups of the phthalocyanine skeleton may be any of α-position, only β-position, and a mixture of α-position and β-position. In the introduction of a sulfonamide group by chlorosulfonation of phthalocyanine, the α-position is usually mainly substituted. When 4-sulfophthalic acid is used as a starting material, a product substituted at the β-position is obtained. In addition, when 4-sulfophthalic acid and phthalic acid are mixed and used in phthalocyanination, and the resulting phthalocyani compound is further chlorosulfonated to introduce a sulfonamide group, it is mixed at the α-position and β-position. Thus, a substituted one can be obtained.

  In the general formula (1), m, which represents the number of sulfonamide groups bonded to the phthalocyanine skeleton, is a value of 0.1-3.9, n is a value of 0.1-3.9, and m + n is 1. The numerical value of 0.0-4.0 is represented. Among them, it is preferable that m is a numerical value of 0.5 to 3.5, n is a numerical value of 0.5 to 3.5, and m + n is a numerical value of 1.0 to 4.0.

  The phthalocyanine mixture represented by the general formula (1) is obtained as a mixture containing a plurality of phthalocyanine compounds having different kinds of substituents and different positions of the substituents. However, the numerical values of m and n must satisfy the above range, and the effects of the invention cannot be achieved outside this range.

  Met in the general formula (1) represents a divalent metal atom, a trivalent monosubstituted metal atom, a tetravalent disubstituted metal atom, or an oxy metal. As Met, any metal can be used as long as it is a metal that does not desorb during the reaction or during the treatment after the reaction. Among them, Cu, Co, Zn, Pd, VO, AlCl, or AlOH is preferable. Cu and Zn are particularly preferable.

As described above, the phthalocyanine mixture represented by the general formula (1) is a mixture of molecules (phthalocyanine compounds) in which at least one of two kinds of sulfonamide groups is introduced into the phthalocyanine skeleton. As a phthalocyanine compound having a sulfonamide group introduced,
A) Compound in which —SO ₂ NHCHR ¹ R ² is introduced as a substituent in the phthalocyanine molecule B) Compound in which —SO ₂ NHR ³ is introduced as a substituent in the phthalocyanine molecule C) —SO ₂ NHR as a substituent in the phthalocyanine molecule There are three types of compounds in which two kinds of ¹ R ² and —SO ₂ NHR ³ are introduced. As the form of the mixture, the mixture of A) and B), the mixture of A) and C), Any of the mixture of B) and C) and the mixture of A), B) and C) may be used.

  Hereinafter, specific examples (Exemplified Compounds 1-1 to 1-46) of the phthalocyanine mixture represented by the general formula (1) are shown. However, these specific examples do not limit the scope of the phthalocyanine mixture according to the present invention.

[Phthalocyanine compounds]
The phthalocyanine compound according to the present invention is a compound having a phthalocyanine skeleton in which at least one of each of two kinds of sulfonamide groups is introduced into one molecule, and is represented by the following general formula (2).

In the general formula (2), R ¹ and R ² are each independently an unsubstituted alkyl group, an alkyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond and an ester bond, and an alkylcarbonyl A group, an alkoxycarbonyl group, wherein at least one of R ¹ and R ² is an alkyl group, an alkylcarbonyl group, or an alkoxycarbonyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond, and an ester bond Represents.

The unsubstituted alkyl group represented by R ¹ or R ² is preferably an unsubstituted alkyl group having 1 to 8 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, and an octyl group.

The “alkyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond and an ester bond” represented by R ¹ or R ² is an oxygen atom in the above at least one form in a range of 1 to 4 An alkyl group having 1 to 12 carbon atoms is preferred. Specific examples include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, acetylmethyl group, acetylethyl group, propionylmethyl group, propionylethyl group, tetrahydrofurfuryloxymethyl group, 2,2-dimethyl. -1,3-dioxolane-4-methoxymethyl group, 2- (1,3-dioxolane) ethoxymethyl group, 2- (1,3-dioxane) ethoxymethyl group, methoxycarbonylmethyl group, ethoxycarbonylethyl group, propoxy Preferred examples include carbonylethyl group, butoxycarbonylethyl group, and pentoxycarbonylbutyl group.

The alkylcarbonyl group or alkoxycarbonyl group represented by R ¹ or R ² is preferably an alkylcarbonyl group having 2 to 12 carbon atoms or an alkoxycarbonyl group having 2 to 12 carbon atoms. Specific examples include acetyl group, propionyl group, propylcarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group and pentoxycarbonyl group.

R ³ in the general formula (1) represents a hydrogen atom, an unsubstituted alkyl group, or an alkyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond, an ester bond, and a hydroxy group.

The unsubstituted alkyl group represented by R ³ is preferably an unsubstituted alkyl group having 1 to 8 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, and an octyl group.

As the “alkyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond, an ester bond and a hydroxy group” represented by R ³ , An alkyl group having 1 to 12 carbon atoms is preferred. Specific examples include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, hydroxyethyl, hydroxyethoxyethyl, acetylmethyl group, acetylethyl group, propionylmethyl group, propionylethyl group, tetrahydrofurfuryloxymethyl. Group, 2,2-dimethyl-1,3-dioxolane-4-methoxymethyl group, 2- (1,3-dioxolane) ethoxymethyl group, 2- (1,3-dioxane) ethoxymethyl group, methoxycarbonylmethyl group An ethoxycarbonylethyl group, a propoxycarbonylethyl group, a butoxycarbonylethyl group, and a pentoxycarbonylbutyl group are preferable.

In the above, —R ³ and —CHR ¹ R ^{2 in} formula (2) do not represent the same group at the same time.

  In the phthalocyanine compound represented by the general formula (2), the substitution positions of the two sulfonamide groups of the phthalocyanine skeleton are any one of α-position, only β-position, and a mixture of α-position and β-position. Also good. In the introduction of a sulfonamide group by chlorosulfonation of phthalocyanine, the α-position is usually mainly substituted. When 4-sulfophthalic acid is used as a starting material, a product substituted at the β-position is obtained. In addition, when 4-sulfophthalic acid and phthalic acid are mixed and used in phthalocyanination, and the resulting phthalocyani compound is further chlorosulfonated to introduce a sulfonamide group, it is mixed at the α-position and β-position. Thus, a substituted one can be obtained.

  In the general formula (2), m ′ represents a numerical value of 1 to 3, n ′ represents a numerical value of 1 to 3, and m ′ + n ′ represents a numerical value of 2 to 4.

  Met in the general formula (2) represents a divalent metal atom, a trivalent mono-substituted metal atom, a tetravalent di-substituted metal atom, or an oxy metal, and does not desorb during the reaction or after the reaction. Any metal can be used as long as it is a metal. Among these, Cu, Co, Zn, Pd, VO, AlCl or AlOH is preferable, and Cu is particularly preferable.

The phthalocyanine compound represented by the general formula (2) is structurally characterized in that at least one sulfonamide group is introduced into the same phthalocyanine molecule.
The phthalocyanine compound represented by the general formula (2) is obtained by converting a desired phthalocyanine compound from the phthalocyanine mixture represented by the general formula (1) described above using a purification method such as column chromatography or recrystallization. It can be obtained by separating.

  Hereinafter, specific examples (Exemplified Compounds 2-1 to 2-46) of the phthalocyanine compound represented by the general formula (2) are shown. However, these specific examples do not limit the scope of the phthalocyanine compound according to the present invention.

[Method for producing phthalocyanine mixture or compound]
The phthalocyanine mixture represented by the general formula (1) can be produced by various methods. An example of a typical manufacturing method is given below.
(1) An unsubstituted metal phthalocyanine compound as a raw material is prepared. As this, one synthesized by a known method can be used, or a commercially available product can be used.
(2) Next, the raw material is chlorosulfonylated.
(3) Furthermore, the resulting chlorosulfonylated product is amidated by reacting two amines corresponding to the above general formula to obtain a desired phthalocyanine mixture.

The method for producing the phthalocyanine mixture will be described in more detail.
An unsubstituted metal phthalocyanine compound is added little by little so as to keep 20 ° C. or less in 5 to 10 times mass of chlorosulfonic acid. After stirring at the same temperature for 1 hour, the temperature is raised at a rate of 0.5 to 1 ° C./min and reacted at 130 to 135 ° C. for 4 hours. Subsequently, the mixture is cooled to 80 ° C., and thionyl chloride corresponding to 2 to 5 times the mass of the unsubstituted metal phthalocyanine compound is dropped over 1 to 2 hours while maintaining the temperature at 70 to 80 ° C. Thereafter, the mixture is stirred at the same temperature for 4 to 10 hours, cooled to 15 to 20 ° C., and stirred at this temperature for 12 hours. The obtained reaction mixture was discharged little by little into ice water corresponding to 50 to 200 times the mass of the phthalocyanine mixture, and then the precipitate was filtered off, washed with ice water until neutral and washed with metal phthalocyanine tetrasulfonyl chloride. obtain.

  The above reaction conditions are mainly those for obtaining metal phthalocyanine tetrasulfonyl chloride, but when obtaining mono-, di- or tri-substituted sulfonyl chlorides, it is possible to make the reaction conditions in chlorosulfonic acid more gentle. Become. That is, it can be achieved by lowering the reaction temperature or shortening the reaction time.

  Next, the metal phthalocyanine sulfonyl chloride obtained above is used as two kinds of amines to be introduced or ammonium salts thereof (total mass of 1 to 4 equivalents of 0.1: 3.9 to 3.9: 0.1). Ratio), or by sequentially reacting each of two kinds of amines or ammonium salts thereof. Further, as the deoxidizer, an amine to be introduced, a tertiary amine such as triethylamine, or an inorganic base such as caustic soda or sodium carbonate can be used. The amine and the deoxidizer are added so as to keep the temperature at 15 ° C. or lower, and the reaction is completed by stirring at 20-30 ° C. for 15-24 hours. The desired metal phthalocyanine sulfonic acid amide mixture (phthalocyanine mixture represented by the general formula (1)) can be obtained by filtering, washing with water and drying.

  In addition, as described above, the phthalocyanine compound represented by the general formula (2) is obtained by the above-described method. The phthalocyanine mixture represented by the general formula (1) is recrystallized, silica gel chromatography or the like. It can be obtained by separation and isolation by a purification method.

  Next, the above exemplary compounds (1-2, 1-7, 1-15, 2-2, 2-7, 2-15, 1-46, 2-46) and sulfonamides not included in the above general formula Examples (Synthesis Examples 1 to 8 and Comparative Synthesis Examples 1 to 3) specifically synthesized with respect to the mono-substituted group (Comparative Compounds 1 to 3) are shown. However, the present invention is not limited by these. The structural formulas of the phthalocyanine mixture and the phthalocyanine compound synthesized in the synthesis example here, and comparative compounds are shown in Tables 1 and 2 below. Each synthesis example shows the result of measuring the solubility of each.

[Synthesis Example 1]
120.0 g of copper phthalocyanine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 880.0 g of chlorosulfonic acid at 20 ° C. or less in small portions over 30 minutes. Next, the temperature was raised to 70 to 80 ° C., stirred for 1 hour at the same temperature, further raised to 130 to 135 ° C. over 2 hours, reacted for 4 hours at the same temperature, and then cooled to 80 ° C. Further, 352.0 g of thionyl chloride was added dropwise over 1 hour while keeping at 70 to 80 ° C., then stirred at 70 to 80 ° C. for 4 hours and 30 minutes, cooled to 15 to 20 ° C., and at the same temperature for 12 hours. Stir. The obtained reaction solution was discharged into 9000 g of ice water little by little, and then the precipitate was separated by filtration and washed with ice water until neutrality to obtain 587.2 g of an intermediate copper phthalocyanine tetrasulfonyl chloride blue filter cake. .

  After adding 300 g of ice water to 97.9 g of the blue filter cake of the intermediate copper phthalocyanine tetrasulfonyl chloride obtained from the above, the mixture was dispersed and stirred at 10 ° C. or lower for 20 minutes, and then methylamine hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) 4 7 g (2 equivalents) was added, and then a mixture of 7.2 g (2 equivalents) of 2-amino-1-methoxybutane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 14.1 g (4 equivalents) of triethylamine for 40 minutes Over the course of 15 ° C. Subsequently, the temperature was raised to 20 ° C. to 30 ° C., and after stirring for 18 hours at this temperature, the product was separated by filtration, dispersed in 300 g of water and filtered twice, and then dried at 60 ° C. for 16 hours. As a result, 34.9 g of blue powder was obtained. This was further recrystallized with ethyl acetate to obtain 28.4 g of a phthalocyanine mixture (Exemplary Compound 1-2) as a blue powder. As a result of fluorescent X-ray analysis of the obtained mixture, the atomic ratio of copper and sulfur was 1.0: 4.0.

[Synthesis Example 2]
25.0 g of copper phthalocyanine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 183.3 g of chlorosulfonic acid at 20 ° C. or less in small portions over 30 minutes. Next, the temperature was raised to 75 to 80 ° C., stirred at the same temperature for 1 hour, heated to 124 to 126 ° C. over 1 hour and 30 minutes, reacted at the same temperature for 4 hours, and then cooled to 80 ° C. Further, 62.0 g of thionyl chloride was added dropwise over 1 hour while maintaining the temperature at 77 to 81 ° C., followed by stirring at 70 to 80 ° C. for 4 hours and 30 minutes, and then cooling to 15 to 20 ° C. Stir for 11 hours. The obtained reaction solution was discharged into 2200 g of ice water little by little, and then the precipitate was separated by filtration and washed with ice water until neutrality to obtain 115.2 g of an intermediate copper phthalocyanine tetrasulfonyl chloride blue filter cake. .

  The blue filter cake obtained as described above was transferred to a flask, 800 g of ice water was added, and after dispersion and stirring at 10 ° C. or lower for 20 minutes, 1.93 g (0.5%) of 2-ethoxyethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.). Equivalent) and 14.0 g (2.0 equivalents) of 2-amino-1 (2-ethoxyethoxy) butane and 11.0 g (2.5 equivalents) of triethylamine so as to keep the temperature at 15 ° C. or lower over 40 minutes. It was dripped in. Subsequently, the temperature was raised to 20 to 30 ° C., and after stirring for 18 hours at the same temperature, the product was separated by filtration, dispersed in 800 g of water and filtered twice, and then dried at 60 ° C. for 16 hours. Thus, 47.6 g of a blue powder phthalocyanine mixture (Exemplary Compound 1-7) was obtained. As a result of fluorescent X-ray analysis of the obtained mixture, the atomic ratio of copper and sulfur was 1.0: 2.5.

[Synthesis Example 3]
300 g of ice water was added to 97.9 g of the blue filter cake of the intermediate copper phthalocyanine tetrasulfonyl chloride obtained in Synthesis Example 1, and the mixture was dispersed and stirred at 10 ° C. or lower for 20 minutes, and then L-valine methyl hydrochloride (Tokyo Kasei Co., Ltd.). 11.6 g (2.0 equivalents) was further added, followed by 4.24 g (2.0 equivalents) of 2-aminoethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 14.1 g (4.0 equivalents) of triethylamine. ) Was added dropwise over 40 minutes while maintaining the temperature at 15 ° C. or lower. Subsequently, the temperature was raised to 20 to 30 ° C., and after stirring for 18 hours at the same temperature, the product was separated by filtration, dispersed in 300 g of water and filtered twice, and then dried at 60 ° C. for 16 hours. As a result, 38.2 g of blue powder was obtained. This was further recrystallized with ethyl acetate to obtain 31.9 g of a phthalocyanine mixture (Exemplary Compound 1-15) as a blue powder. As a result of fluorescent X-ray analysis of the obtained mixture, the atomic ratio of copper and sulfur was 1.0: 4.0.

[Synthesis Example 4]
The main component was separated and purified from 25.0 g of Exemplified Compound 1-2 (phthalocyanine mixture) synthesized in Synthesis Example 1 above by silica gel chromatography, and this was further recrystallized from ethyl acetate to give Exemplified Compound 2-2 (phthalocyanine compound) 3.1 g was obtained. As a result of fluorescent X-ray analysis of the obtained compound, the atomic ratio of copper and sulfur was 1.0: 4.0. The elemental analysis values of this phthalocyanine compound were as follows.
Elemental analysis _{(C 44 H 44 CuN 12 O} 10 S 4): Mw = 1092.71
Theoretical value (%): C 48.36, H 4.06, N 15.38
Found (%): C 48.41, H 4.11, N 15.34.
Moreover, as a result of performing FD-Mass analysis of the obtained phthalocyanine compound, it corresponded with the molecular weight peak of the target object.

[Synthesis Example 5]
After recrystallizing 45.0 g of Example Compound 1-7 (phthalocyanine mixture) obtained in Synthesis Example 2 above with ethyl acetate, the main component was separated and purified by silica gel chromatography, and this was further recrystallized with ethyl acetate. 3.9 g of exemplary compound 2-7 (phthalocyanine compound) was obtained. As a result of fluorescent X-ray analysis of the obtained compound, the atomic ratio of copper and sulfur was 1.0: 3.0. The elemental analysis values of this phthalocyanine compound were as follows.
Elemental analysis _{(C 52 H 59 CuN 11 O} 11 S 3): Mw = 1173.84
Theoretical value (%): C 53.21, H 5.07, N 13.13
Found (%): C 53.16, H 5.14, N 13.47
Moreover, as a result of performing FD-Mass analysis of the obtained phthalocyanine compound, it corresponded with the molecular weight peak of the target object.

  Using the obtained phthalocyanine compound (Exemplary Compound 1-7), a pigment resin of 0.5 g of this phthalocyanine compound, 0.5 g of an acrylic resin (Delpet 80N, manufactured by Asahi Kasei Co., Ltd.) and 9.5 g of ethyl acetate A solution was prepared, applied to a glass plate by a spin coating method, dried at 60 ° C. for 1 hour, and then measured for a transmission spectrum. This transmission spectrum is shown in FIG.

[Synthesis Example 6]
The main component of 28.0 g of the phthalocyanine mixture of Exemplified Compound 1-15 obtained in Synthesis Example 3 above was separated and purified by silica gel chromatography, and this was further recrystallized from ethyl acetate to give Exemplified Compound 2-15 (Phthalocyanine Compound) ) 6.2 g was obtained. As a result of fluorescent X-ray analysis of the obtained compound, the atomic ratio of copper and sulfur was 1.0: 4.0. The elemental analysis values of this phthalocyanine compound were as follows.
Elemental analysis _{(C 48 H 48 CuN 12 O} 14 S 4): MW = 1208.78
Theoretical value (%): C 47.69, H 4.00, N 13.91
Found (%): C 48.59, H 4.02, N 13.97
Moreover, as a result of performing FD-Mass analysis of the obtained phthalocyanine compound, it corresponded with the molecular weight peak of the target object.

[Synthesis Example 7]
25.0 g of zinc phthalocyanine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 194.6 g of chlorosulfonic acid at 20 ° C. or less in small portions over 30 minutes. Next, the temperature was raised to 75-80 ° C., stirred at the same temperature for 1 hour, heated to 110-120 ° C. over 1 hour 30 minutes, reacted at this temperature for 3 hours, and then cooled to 75 ° C. Further, 77.9 g of thionyl chloride was added dropwise over 1 hour while maintaining at 75 to 80 ° C., followed by stirring at 75 to 80 ° C. for 2 hours, cooling to 15 to 20 ° C., and stirring at the same temperature for 11 hours. . The obtained reaction solution was discharged into 2200 g of ice water little by little, and then the precipitate was separated by filtration and washed with ice water until neutrality to obtain 118.3 g of a blue filter cake of an intermediate copper phthalocyanine tetrasulfonyl chloride. .

  The blue filter cake obtained as described above was transferred to a flask, added with 800 g of ice water, dispersed and stirred at 10 ° C. or lower for 20 minutes, and then 6.50 g (2.0%) of 2-methoxyethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.). Equivalent) and 6.98 g (1.0 equivalent) of 2-amino-1 (2-ethoxyethoxy) butane and 13.1 g (3.0 equivalent) of triethylamine so as to keep the temperature at 15 ° C. or lower over 40 minutes. It was dripped in. Subsequently, the temperature was raised to 20 to 30 ° C., and after stirring for 18 hours at the same temperature, the product was separated by filtration, dispersed in 800 g of water and filtered twice, and then dried at 60 ° C. for 16 hours. 42.3 g of a phthalocyanine mixture (Exemplary Compound 1-46) as a blue powder was obtained. As a result of fluorescent X-ray analysis of the obtained mixture, the atomic ratio of zinc to sulfur was 1.0: 3.0.

[Synthesis Example 8]
After recrystallizing 40.0 g of Exemplified Compound 1-46 (phthalocyanine mixture) obtained in Synthesis Example 7 with ethyl acetate, the main component was separated and purified by silica gel chromatography, and this was further recrystallized with ethyl acetate. 4.1 g of exemplary compound 2-46 (phthalocyanine compound) was obtained. As a result of fluorescent X-ray analysis of the obtained compound, the atomic ratio of zinc to sulfur was 1.0: 3.0. The elemental analysis values of this phthalocyanine compound were as follows.
Elemental analysis _{(C 52 H 59 CuN 11 O} 11 S 3): Mw = 1075.52
Theoretical value (%): C 51.37, H 4.40, N 14.33
Found (%): C 51.44, H 4.31, N 14.39
Moreover, as a result of performing FD-Mass analysis of the obtained phthalocyanine compound, it corresponded with the molecular weight peak of the target object.

[Comparative Synthesis Example 1]
73.4 g of a blue filter cake of an intermediate copper phthalocyanine tetrasulfonyl chloride obtained in Synthesis Example 1 above was added to 150 g of ice water, dispersed and stirred at 10 ° C. or lower for 30 minutes, and then added with 2-ethoxyethylamine (Tokyo Kasei). 20.9 g (manufactured by Co., Ltd.) was added dropwise so as to maintain the temperature at 15 ° C. or lower over 20 minutes. Subsequently, the temperature was raised to 20 to 30 ° C., and after stirring for 18 hours at the same temperature, the product was separated by filtration, dispersed in 300 g of water and filtered twice, and then dried at 60 ° C. for 16 hours. As a result, 27.6 g of a blue powder was obtained. This was recrystallized with ethyl acetate to obtain a comparative compound 1 (19.7 g) as a blue powder. The elemental analysis values of this comparative compound were as follows.
Elemental analysis _{(C 48 H 52 CuN 12 O} 12 S 4): Mw = 1180.81
Theoretical value (%): C 48.82, H 4.44, N 14.23
Found (%): C 48.88, H 4.48, N 14.31.

[Comparative Synthesis Example 2]
73.4 g of a blue filter cake of the intermediate copper phthalocyanine tetrasulfonyl chloride obtained in Synthesis Example 1 above was added to 150 g of ice water, dispersed and stirred at 10 ° C. or lower for 30 minutes, and then DL-2-amino-1- 20.9 g of butanol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise so as to keep the temperature at 15 ° C. or less over 20 minutes. Subsequently, the temperature was raised to 20 to 30 ° C., and after stirring for 17 hours at the same temperature, the product was separated by filtration, dispersed in 300 g of water and filtered twice, and then dried at 60 ° C. for 16 hours. 27.0 g of blue powder was obtained. This was recrystallized from methanol to obtain a comparative compound 2 (19.1 g) as a blue powder. The elemental analysis values of this comparative compound were as follows.
Elemental analysis _{(C 48 H 52 CuN 12 O} 12 S 4): Mw = 1180.81
Theoretical value (%): C 48.82, H 4.44, N 14.23
Found (%): C 48.86, H 4.35, N 14.27

[Comparative Synthesis Example 3]
150 g of ice water was added to 73.9 g of the blue filter cake of the intermediate copper phthalocyanine tetrasulfonyl chloride obtained in Synthesis Example 1, and the mixture was dispersed and stirred at 10 ° C. or lower for 30 minutes, followed by isobutylamine (Tokyo Kasei Co., Ltd.). (Made) 17.1g was dripped so that 15 degrees C or less might be maintained over 20 minutes. Subsequently, the temperature was raised to 20 to 30 ° C., and after stirring for 18 hours at the same temperature, the product was separated by filtration, dispersed in 300 g of water and filtered twice, and then dried at 60 ° C. for 16 hours. As a result, 25.8 g of blue powder was obtained. This was recrystallized with toluene to obtain a comparative compound 3 (18.1 g) as a blue powder. The elemental analysis values of this comparative compound were as follows.
Elemental analysis _{(C 48 H 52 CuN 12 O} 8 S 4): Mw = 1116.81
Theoretical value (%): C 51.62, H 4.69, N 15.05
Found (%): C 51.57, H 4.71, N 15.15

[Measurement of solubility]
The solubility of the synthesized products in Synthesis Examples 1 to 8 and Comparative Synthesis Examples 1 to 3 in ethyl acetate was measured. The solubility here represents the amount (g) dissolved in 100 g of ethyl acetate at 25 ° C. The results are shown in Table 3 below.

  In the dye-containing curable composition of the present invention, as the (B) dye, in addition to using the phthalocyanine mixture represented by the general formula (1) and the phthalocyanine compound represented by the general formula (2), respectively, A plurality of phthalocyanine mixtures or a plurality of phthalocyanine compounds may be used in combination, or at least one of these phthalocyanine mixtures and at least one of phthalocyanine compounds may be used in combination.

  Furthermore, conventionally well-known dye can also be used together with the phthalocyanine mixture represented by said general formula (1) and / or the phthalocyanine compound represented by General formula (2). The conventionally known dye can be appropriately selected from organic solvent-soluble dyes according to the required spectral absorption. Examples of the dye species include an acid dye, a basic dye, a reaction product of a disperse dye and a basic compound of an acid dye, a reaction product of a basic dye and an acid compound, and soluble in an organic solvent. Furthermore, as an oil-soluble dye, C.I. I. The dye mentioned as Solvent Dye can also be selected suitably.

  When using conventionally known dyes together, it must have a desirable spectrum as a color filter, and must be dissolved in the necessary concentration in a solution containing a solvent or alkali-soluble resin, which will be described later, without causing precipitation or aggregation over time. It is. These dyes include C.I. described in the Color Index. I. It can select suitably from Solvent Color etc. in the range which does not impair the effect of this invention. Further, a dye having a solvent solubility and a spectrum suitable can be selected from oil-soluble dyes, acid dyes, disperse dyes, reactive dyes, and direct dyes. Here, the solvent solubility of the dye means one that dissolves in a solvent at a mass percentage of 1% or more.

  Total content of the phthalocyanine mixture represented by the above general formula (1) and / or the phthalocyanine compound represented by the general formula (2) (and a conventionally known dye if necessary) in the dye-containing curable composition. Is preferably 1 to 80% by mass, more preferably 3 to 50% by mass, and particularly preferably 5 to 30% by mass with respect to the total solid content (mass) of the composition. If the spectral characteristics can be satisfied, the smaller the dye content ratio, the better from the viewpoints of sensitivity and developability.

Next, other structural components (A) and (C) to (E) and other components of the dye-containing curable composition of the present invention will be described in detail.
(A) Alkali-soluble resin The alkali-soluble resin is preferably a linear organic polymer, soluble in an organic solvent, and developable with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, as described in JP-A-59-53836 and JP-A-59-71048. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.

In addition to the above, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone and polyethylene oxide, Polyvinyl alcohol, etc. are also useful.
Moreover, you may copolymerize the monomer which has hydrophilic property, As an example, alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, Secondary or tertiary alkylacrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate Branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like.

  In addition, monomers having a tetrahydrofurfuryl group, phosphoric acid, phosphoric acid ester, quaternary ammonium salt, ethyleneoxy chain, propyleneoxy chain, sulfonic acid and its salt, morpholinoethyl group, etc. as the above-mentioned hydrophilic monomer Useful.

  In order to improve the crosslinking efficiency, a polymerizable group may be included in the side chain, and a polymer containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is also useful. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  Among these various alkali-soluble resins, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control. Are preferably acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins.

  The acrylic resin is preferably a copolymer composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, allyl (meth) acrylate, and the like.

  Alkali-soluble phenol resins are also useful. That is, examples of the alkali-soluble resin having a phenolic hydroxyl group include polyhydroxystyrene resins. Specifically, p-hydroxystyrene resin, m-hydroxystyrene resin, o-hydroxystyrene resin, and copolymers thereof, copolymer of hydroxystyrene and styrene, copolymer of hydroxystyrene and acetoxystyrene And a copolymer of hydroxystyrene and the above (meth) acrylic monomer.

Moreover, novolak resins or vinyl polymers are also included.
Examples of the novolac resin include those obtained by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of phenols include phenol, cresol, ethylphenol, propylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, bisphenol A, and the like. These phenols can be used alone or in combination of two or more. Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and the like.
Specific examples of the novolak resin include a condensation product of metacresol, paracresol or a mixture thereof and formalin.

As the alkali-soluble resin, a polymer having a number average molecular weight Mn (polystyrene conversion value measured by GPC method) of 1000 to 2 × 10 ⁵ is preferable, a polymer of 2000 to 1 × 10 ⁵ is more preferable, and 4000 to A 5 × 10 ⁴ polymer is particularly preferred.

  Further, the molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn) of the alkali-soluble resin is preferably 1.6 to 1.05 in that the rectangularity of the image profile after development can be maintained. 1.4 to 1.1 is more preferable. In order to obtain a molecular weight distribution in the above range, it is preferable to directly synthesize a resin having a narrow molecular weight distribution by applying a known polymerization method (for example, living anion polymerization method, living cation polymerization method, living radical polymerization method). In addition, solvent fractionation (a method in which a resin is dissolved in a good solvent and then mixed with a poor solvent to precipitate only a high molecular weight component to obtain a resin having a narrow molecular weight distribution), molecular weight fractionation using column chromatography, A method such as fractionation using a supercritical fluid can be applied.

  As content in the dye containing curable composition of the said alkali-soluble resin, 10-90 mass% is preferable with respect to the total solid (mass) of this composition, 20-80 mass% is more preferable, 30- 70% by mass is particularly preferred.

(C) Photosensitive compound As the photosensitive compound according to the present invention, a naphthoquinonediazide compound is preferable when the dye-containing curable composition is constituted as a positive type, and photopolymerization is initiated when it is constituted as a negative type. Agents are preferred.

-Naphthoquinonediazide compound-
In order to obtain a positive type dye-containing curable composition, a naphthoquinonediazide compound used for a g-line and i-line sensitive semiconductor photoresist is preferable. Examples of the naphthoquinone diazide compound include o-naphthoquinone diazide-5-sulfonic acid ester, o-naphthoquinone diazide-5-sulfonic acid amide, o-naphthoquinone diazide-4-sulfonic acid ester, o-naphthoquinone diazide-4-sulfone. And acid amides. These esters or amides can be produced by a known method using, for example, a phenol compound described as general formula (I) in JP-A-2-84650 and JP-A-3-49437. .

  As a phenol compound, having at least two, preferably three or more phenolic hydroxyl groups in one molecule gives sufficient alkali developer resistance before exposure and high developability after exposure. It is preferably selected in terms of possible. Also, it is preferable from the viewpoint of improving sensitivity and solubility in a solvent that all hydroxyl groups in the molecule are not converted to naphthoquinonediazide sulfonic acid ester, and some hydroxyl groups are left.

  The above alkali-soluble resin and naphthoquinone diazide compound can usually be dissolved in a solvent at a ratio of about 2 to 35% by mass with respect to the mass of the solvent.

-Photopolymerization initiator-
When constituting a negative dye-containing curable composition, a photopolymerization initiator is an essential component. Moreover, it can further contain in the positive type containing said naphthoquinone diazide compound. In this case, the degree of curing of the pattern can be further promoted after the pattern is formed.

  The photopolymerization initiator is not particularly limited as long as it can initiate the crosslinking reaction or polymerization reaction of the crosslinking agent by exposure, but is selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, safety, and the like. It is preferable. For example, at least one active halogen compound selected from halomethyloxadiazole compounds and halomethyl-s-triazine compounds, 3-aryl-substituted coumarin compounds, lophine dimers, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene -A benzene-iron complex and its salt, an oxime compound, etc. are mentioned.

  Examples of the active halogen compound which is a halomethyloxadiazole compound include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds described in JP-B-57-6096, 2-trichloromethyl- 5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) ) -1,3,4-oxadiazole.

  Examples of the active halogen compound which is a halomethyl-s-triazine compound include vinyl-halomethyl-s-triazine compounds described in JP-B-59-1281 and 2- (naphtho-) described in JP-A-53-133428. 1-yl) -4,6-bis-halomethyl-s-triazine compound and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compound.

  Specific examples include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,6-bis (trichloromethyl) -4- (3,4-methylenedioxyphenyl)- 1,3,5-triazine, 2,6-bis (trichloromethyl) -4- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (1- p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, 2- (naphth-1-yl) -4,6 -Bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-yl) ) -4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2- Methoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine,

2- [4- (2-Ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5- Methyl-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2 -(5-Methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl -S-triazine, 2- 6-Ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s -Triazine,

4- [pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonyl) Methyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [p-N, -Di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine ,

4- [pN- (p-methoxyphenyl) carbonylaminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [mN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s- Triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) Minophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl)- s-triazine,

4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N- Di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloro Methyl) -s-triazine, 4- [o-fluoro-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-p -N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2, 6-di (trick Romechiru) -s- triazine,

4- [m-Fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylamino) Phenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 -(M-Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloro) Methyl) -s-triazine,

4- (o-Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro -PN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) ) -S-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloro) Ethylamino) -2,6-di (trichloromethyl) -s-triazine.

  In addition, TAZ series (for example, TAZ-104, TAZ-107, TAZ-109, TAZ-110, TAZ-113, TAZ-123, TAZ-140, TAZ-204) manufactured by Midori Chemical, T manufactured by PANCHIM Series (eg, T-OMS, T-BMP, TR, TB), Irgacure series (eg, Irgacure 149, Irgacure 184, Irgacure 261, Irgacure 500, Irgacure 651, Irgacure 819, Irgacure, manufactured by Ciba Geigy 1000), Darocur series (eg Darocur 1173), 4,4′-bis (diethylamino) -benzophenone, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione 2-benzyl-2-dimethyl Arylamino-4-morpholinobutyrophenone Ciro acetophenone, 2,2-dimethoxy-2-phenylacetophenone,

2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5 -Diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2, 4-Dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer, benzoin isopropyl ether, and the like are also useful.

A sensitizer and a light stabilizer can be used in combination with these photopolymerization initiators.
Specific examples thereof include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, and 2-ethyl-9-anthrone. 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2- Methoxyxanthone, 2-ethoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzylacetone, p- (dimethylamino) phenylstyryl ketone, p- (dimethylamino) ) Phenyl-p-methylstyryl ketone Examples include benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, benzothiazole compounds described in JP-B-51-48516, and tinuvin 1130 and 400. Can be mentioned.

  The dye-containing curable composition of the present invention may contain other known initiators in addition to the photopolymerization initiator. Specifically, the vicinal polykettle aldonyl compound disclosed in US Pat. No. 2,367,660, disclosed in US Pat. Nos. 2,367,661 and 2,367,670. Substituted α-carbonyl compounds, acyloin ethers disclosed in US Pat. No. 2,448,828, α-hydrocarbons disclosed in US Pat. No. 2,722,512 Aromatic acyloin compounds, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, disclosed in US Pat. No. 3,549,367. Triarylimidazole dimer / p-aminophenyl ketone combination, benzothiazole compound / trihalome disclosed in Japanese Patent Publication No. 51-48516 Examples thereof include a teal-s-triazine compound.

  As the total content of the photopolymerization initiator (and known initiator), the polymerization rate and the solid content (mass) of the polymerizable monomer component (for example, the polymerizable monomer compound mentioned as a crosslinking agent described later) From the viewpoint of improving the film strength, 0.01 to 50 mass% is preferable, 1 to 30 mass% is more preferable, and 1 to 20 mass% is particularly preferable.

(D) Solvent The dye-containing curable composition of the present invention may contain a solvent. The solvent is basically not particularly limited as long as the solubility of each component and the coating property of the dye-containing curable composition are satisfied, but it is particularly selected in consideration of the solubility, coating property, and safety of the dye and the alkali-soluble resin. It is preferable that

  Examples of the solvent 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, alkyl esters, and methyl lactate. , Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .;

3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, etc .; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, such as methyl 2-methoxypropionate, 2-methoxypropion Acid ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy- 2-methylpropio Methyl acid, 2-ethoxy-2-methylpropionic acid ethyl, etc; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .;

Ethers such as 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 methyl ether, propylene glycol methyl Ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, ethyl carbitol acetate, butyl carbitol acetate, etc .;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone are preferred; aromatic hydrocarbons such as toluene and xylene are preferred.

  Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate Butyl carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate and the like are more preferable.

  These solvents may be used in combination of two or more from the viewpoints of solubility of dyes and alkali-soluble resins, improvement of the coating surface, and the like. In particular, the above methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate , Ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate A mixed solution composed of two or more kinds is preferably used.

(E) Cross-linking agent The cross-linking agent is activated by an acid or radical generated from the photopolymerization initiator upon irradiation with light or radiation, reacts with the alkali-soluble resin to cause cross-linking, or the cross-linking agent itself binds to each other. Alternatively, it is used for the purpose of obtaining an image by reducing the solubility of an exposed portion in an alkali developer by causing crosslinking by polymerization. If necessary, a crosslinking agent is also useful for the purpose of sufficiently curing the pattern by heating after image formation.

  Accordingly, the crosslinking agent in the present invention is not particularly limited as long as it can cure the film by crosslinking or polymerization reaction. For example, (a) epoxy resin, (b) methylol group, alkoxymethyl group, and acyloxy At least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, which is substituted with at least one substituent selected from a methyl group; And a phenol compound, a naphthol compound or a hydroxyanthracene compound substituted with a group, and (d) a polymerizable monomer compound.

  The (a) epoxy resin may be any epoxy resin as long as it has an epoxy group and has crosslinkability, for example, bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether. , Hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diphthalic acid diglycidyl ester, N, N-diglycidyl aniline and other divalent glycidyl group-containing low molecular weight compounds, as well as trimethylolpropane triglycidyl ether, Trivalent glycidyl group-containing low molecular weight compounds represented by methylolphenol triglycidyl ether, TrisP-PA triglycidyl ether, etc., as well as pentaerythritol tetraglycidyl ether, tetramethylol vinyl Tetravalent glycidyl group-containing low molecular weight compounds typified by phenol A tetraglycidyl ether, polyvalent glycidyl group-containing low molecular weight compounds such as dipentaerythritol pentaglycidyl ether, dipentaerythritol hexaglycidyl ether, polyglycidyl ( And glycidyl group-containing polymer compounds represented by 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and the like. .

The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups substituted in the crosslinking agent (b) is 2 to 6 for melamine compounds, 2 for glycoluril compounds, guanamine compounds, and urea compounds. Although it is -4, Preferably it is 5-6 in the case of a melamine compound, and is 3-4 in the case of a glycoluril compound, a guanamine compound, and a urea compound.
Hereinafter, the melamine compound, guanamine compound, glycoluril compound, and urea compound of (b) are collectively referred to as a compound (methylol group-containing compound, alkoxymethyl group-containing compound, or acyloxymethyl group-containing compound) according to (b).

  The methylol group-containing compound according to the above (b) can be obtained by heating an alkoxymethyl group-containing compound in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like. The acyloxymethyl group-containing compound according to (b) above can be obtained by mixing and stirring a methylol group-containing compound with acyl chloride in the presence of a basic catalyst.

Hereinafter, specific examples of the compound according to (b) having the above-described substituent are given.
Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 5 methylol groups of hexamethylol melamine are methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, hexamethylol. Examples thereof include compounds in which 1 to 5 methylol groups of melamine are acyloxymethylated, or mixtures thereof.

  Examples of the guanamine compound include, for example, tetramethylolguanamine, tetramethoxymethylguanamine, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolguanamine, or a mixture thereof, tetramethoxyethylguanamine, tetraacyloxymethylguanamine, tetramethylol. Examples thereof include compounds obtained by acyloxymethylating 1 to 3 methylol groups of guanamine or a mixture thereof.

  Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxymethyl glycoluril, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol glycoluril, or a mixture thereof, or a methylol group of tetramethylol glycoluril. Examples thereof include compounds in which 1 to 3 are acyloxymethylated or a mixture thereof.

Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol urea, a mixture thereof, and tetramethoxyethyl urea.
These compounds according to (b) may be used alone or in combination.

  The crosslinking agent (c), that is, a phenol compound, a naphthol compound, or a hydroxyanthracene compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group is the crosslinking agent (b As in the case of), intermixing with the overcoated photoresist is suppressed by thermal crosslinking, and the film strength is further increased. Hereinafter, these compounds may be collectively referred to as a compound according to (c) (a methylol group-containing compound, an alkoxymethyl group-containing compound, or an acyloxymethyl group-containing compound).

  The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the cross-linking agent (c) is at least two per molecule, and from the viewpoint of thermal crosslinkability and storage stability, phenol as a skeleton Compounds in which the 2nd and 4th positions of the compound are all substituted are preferred. In addition, the naphthol compound and hydroxyanthracene compound as the skeleton are preferably compounds in which all of the ortho-position and para-position of the OH group are substituted. In addition, the 3-position or 5-position of the phenol compound may be unsubstituted or may have a substituent. In the naphthol compound, any substituent other than the ortho position of the OH group may be substituted. You may have.

  The methylol group-containing compound according to the above (c) is a phenolic OH group-containing compound in which the 2-position or 4-position of the phenolic OH group is a hydrogen atom as a raw material, and this is used as sodium hydroxide, potassium hydroxide, ammonia, It can be obtained by reacting with formalin in the presence of a basic catalyst such as tetraalkylammonium hydroxide. The alkoxymethyl group-containing compound according to (c) is obtained by heating the methylol group-containing compound according to (c) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid or methanesulfonic acid. The acyloxymethyl group-containing compound according to (c) is obtained by reacting the methylol group-containing compound according to (c) with an acyl chloride in the presence of a basic catalyst.

  Examples of the skeleton compound in the crosslinking agent (c) include phenol compounds, naphthols, hydroxyanthracene compounds, etc., in which the ortho-position or para-position of the phenolic OH group is unsubstituted. , 3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenols such as bisphenol A, 4,4'-bishydroxybiphenyl, TrisP-PA (Honshu Chemical Industry) Naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, etc. are used.

  Specific examples of the crosslinking agent (c) include, as a phenol compound or a naphthol compound, for example, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, tri (methoxymethyl) phenol, trimethylolphenol, Trimethylol-3-cresol, tri (methoxymethyl) -3-cresol, compounds obtained by methoxymethylating 1 to 2 methylol groups of trimethylol-3-cresol, 2,6-dimethylol-4-cresol and the like Methylol cresol, tetramethylol bisphenol A, tetramethoxymethyl bisphenol A, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethyl A compound obtained by methoxymethylating 1 to 5 methylol groups of cymethyl-4,4′-bishydroxybiphenyl, hexamethylol of TrisP-PA, hexamethoxymethyl of TrisP-PA, hexamethylol of TrisP-PA, Bishydroxymethyl naphthalene diol, etc. are mentioned.

  Examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene, and examples of the acyloxymethyl group-containing compound include, for example, a part of the methylol group of the methylol group-containing compound. Examples include compounds that are all acyloxymethylated.

Among these compounds, trimethylolphenol, bishydroxymethyl-p-cresol, tetramethylolbisphenol A, trisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) or a methylol group thereof is preferable. Examples thereof include an alkoxymethyl group and a phenol compound substituted with both a methylol group and an alkoxymethyl group.
These compounds according to (c) may be used alone or in combination.

Next, the (d) polymerizable monomer compound will be described. As the polymerizable monomer compound, a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure is preferable.
Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate,

Polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate After adding ethylene oxide or propylene oxide to polyfunctional alcohols such as hexanediol (meth) acrylate, trimethylylpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin or trimethylolethane (Meth) acrylated,

Urethane acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, can be mentioned as described in JP-B 52-30490. Furthermore, the Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 are introduced as photocurable monomers and oligomers.

  The total content of the crosslinking agents (a) to (d) in the dye-containing curable composition varies depending on the material, but is preferably 1 to 70% by mass with respect to the solid content of the composition, and 5 to 50 % By mass is more preferable, and 7 to 30% by mass is particularly preferable.

(F) Others-Thermal polymerization inhibitor-
In addition to the above, it is preferable to add a thermal polymerization inhibitor to the dye-containing curable composition of the present invention. For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2 ' -Methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, etc. are useful.

-Various additives-
In the dye-containing curable composition of the present invention, various additives such as a filler, a polymer compound other than the above, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an aggregation preventive agent are optionally added. An agent or the like can be blended. If necessary, an anti-fading agent for the dye can also be added.

  Specific examples of the various additives include fillers such as glass and alumina; polymer compounds other than binder resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; nonionic, cationic And anionic surfactants: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimetoki Adhesion promoters such as silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl- 6-t-butylphenol), 2,6-di-t-butylphenol and other antioxidants; 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, etc. And an anti-aggregation agent such as sodium polyacrylate.

Further, when the alkali solubility of the non-cured part is promoted to further improve the developability of the dye-containing curable composition of the present invention, the composition has an organic carboxylic acid, preferably a low molecular weight of 1000 or less. A molecular weight organic carboxylic acid can be added.
Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

  The dye-containing curable composition of the present invention is used for forming colored pixels such as color filters and electroluminescence color filters used in liquid crystal display devices and solid-state imaging devices (for example, CCD, CMOS, etc.), and for printing. It can be suitably used as a production application for ink, ink for inkjet, and paint.

<< Color filter and manufacturing method thereof >>
Next, the color filter of the present invention will be described in detail through its manufacturing method.
In the method for producing a color filter of the present invention, the aforementioned (A) alkali-soluble resin, (B) the dye represented by the general formula (1) or the general formula (2), and other dyes as necessary. A color filter can be produced by using at least the containing composition, preferably the dye-containing curable composition of the present invention.

  That is, the color filter of the present invention is composed of at least (A) an alkali-soluble resin, (B) a dye represented by the general formula (1) or the general formula (2), and other dyes as necessary. Preferably, it further comprises (C) a photosensitive compound and (D) a solvent. Furthermore, it can comprise using the thing similar to the component which can be contained in the dye containing curable composition of the above-mentioned this invention.

  When the dye-containing curable composition of the present invention is configured as a negative type, the negative type dye-containing curable composition is applied onto a support by a coating method such as spin coating, cast coating, roll coating or the like. A radiation-sensitive composition layer is formed, the layer is exposed through a predetermined mask pattern, and developed with a developer to form a negative colored pattern (image forming step). Moreover, the hardening process which hardens | cures the formed coloring pattern by heating and / or exposure as needed may be included.

  When the dye-containing curable composition of the present invention is configured as a positive type, the positive type dye-containing curable composition is applied onto a support by a coating method such as spin coating, cast coating, roll coating or the like. After forming a radiation-sensitive composition layer, exposing the layer through a predetermined mask pattern, and developing with a developer, a positive colored pattern is formed (image forming step), and then the formed colored pattern Is heated to cure (post-bake).

In the production of the color filter, in the case of the negative type, the image forming step (and the curing step if necessary) is repeated according to the desired number of hues, and in the case of the positive type, the image forming step and the post baking are performed. By repeating according to the desired number of hues, a color filter having a desired hue can be produced.
As light or radiation used at this time, ultraviolet rays such as g-line, h-line and i-line are particularly preferably used.

Examples of the support include, for example, soda glass, Pyrex (R) glass, quartz glass used for liquid crystal display elements and the like, and a transparent conductive film attached thereto, a photoelectric conversion element substrate used for an imaging element, For example, a silicon substrate, a complementary metal oxide semiconductor (CMOS), or the like can be given. These supports may be formed with black stripes that separate pixels.
In addition, an undercoat layer may be provided on these supports, if necessary, for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the support surface.

  Any developer can be used as long as it has a composition that dissolves the uncured portion of the dye-containing curable composition of the present invention but does not dissolve the cured portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. As said organic solvent, the above-mentioned solvent used when preparing the dye-containing curable composition of this invention is mentioned.

  Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide. , Choline, pyrrole, piperidine, alkaline compounds such as 1,8-diazabicyclo- [5.4.0] -7-undecene, the concentration is 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An alkaline aqueous solution obtained by dissolution is preferable. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

  The color filter of the present invention is suitable for liquid crystal display devices, solid-state imaging devices, and the like, especially for high-resolution CCD devices exceeding 1 million pixels, CMOS, electroluminescence, and the like. The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

  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” is based on mass.

(Example 1)
1) Preparation of resist solution-Propylene glycol monomethyl ether acetate 28.9 parts (PGMEA)
Ethyl lactate (EL) 28.9 parts Alkali-soluble resin 30.5 parts [Benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer (= 50/25/25 [molar ratio]) 40% EL solution]
Dipentaerythritol hexaacrylate 10.8 parts Polymerization inhibitor (p-methoxyphenol) 0.004 parts TAZ-107 (photopolymerization initiator; Midori Chemical Co., Ltd.) 0.55 parts mixed And dissolved to prepare a resist solution.

2) Preparation of glass substrate with undercoat layer A glass substrate (Corning 1737) was ultrasonically washed with 0.5% NaOH water, followed by washing with water and dehydration baking (200 ° C./20 minutes). Next, the resist solution obtained in the above 1) is applied onto a glass substrate after washing using a spin coater so as to have a film thickness of 2 μm, and dried by heating at 220 ° C. for 1 hour to form a cured film (undercoat layer). Formed.

3) Preparation of dye resist solution (negative dye-containing curable composition) 9.0 parts of the resist solution obtained in 1) above and the exemplified compound 1-2 [general formula (1) described above as the dye The phthalocyanine mixture represented] 1.0 part was mixed and dissolved to obtain a dye resist solution (a solution of the dye-containing curable composition of the present invention [negative type]).

4) Exposure and development of dye-containing curable composition (image forming process)
The dye resist solution obtained in 3) above was applied onto the undercoat layer of the glass substrate with an undercoat layer obtained in 2) above using a spin coater so as to have a film thickness of 1.0 μm. For 120 seconds.

Then, using an exposure apparatus, the coating film was irradiated with a mask pattern having a wavelength of 365 nm and a mask pattern of 20 μm square with an exposure dose of 500 mJ / cm ² . After the irradiation, development was performed at 25 ° C. for 40 seconds using a CD-2000 (Fuji Film Arch Co., Ltd.) developer. Next, after rinsing with running water for 30 seconds, spray drying was performed to obtain a cyan pattern image. Formation of the pattern image was confirmed by an ordinary method by observation with an optical microscope and SEM photograph. As a result, the pattern image showed a rectangular profile.

5) Evaluation The following evaluation was performed about the dye-containing curable composition and the pattern image, and the used dye. The evaluation results are shown in Table 4 below.
-Solubility-
The solubility of the dye (Exemplary Compound 1-2) used in “3) Preparation of Dye Resist Solution” is a mixed solvent (EL of 50 g of ethyl lactate (EL) and 50 g of propylene glycol monomethyl acetate (PGMEA) at 25 ° C. / PGMEA = 1/1 wt) was evaluated according to the following criteria.
[Standard]
○: The amount dissolved in 100 g of the mixed solvent was 3 g or more.
X: The amount dissolved in the mixed solvent was less than 3 g.

-Storage stability-
The degree of precipitation of foreign matters after the dye resist solution obtained in “3) Preparation of dye resist solution” was stored at room temperature for 1 month was visually evaluated according to the following criteria.
[Standard]
○: No precipitation of foreign matters was observed.
(Triangle | delta): Precipitation of the foreign material was recognized slightly.
X: Precipitation of foreign matters was observed remarkably.

-Heat resistance-
A glass substrate with an undercoat layer coated with a dye resist solution is placed on a hot plate so as to be in contact with the substrate surface and heated at 200 ° C. for 1 hour, and then a chromaticity meter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.) Was used to measure the chromaticity change in the pattern image before and after placement, that is, the ΔEab value. The obtained ΔEab value was used as an index indicating the degree of heat resistance, and was evaluated based on the following criteria. A smaller ΔEab value indicates better heat resistance.
[Standard]
A: ΔEab value was 5 or less.
(Triangle | delta): (DELTA) Eab value was 5-10.
X: ΔEab value was 10 or more.

-Light resistance-
A glass substrate with an undercoat layer coated with a dye resist solution is irradiated with a xenon lamp at 50,000 lux for 20 hours (equivalent to 1 million lux · h), and then the chromaticity change in the pattern image before and after irradiation, that is, ΔEab value Was measured. The obtained color difference ΔEab value was used as an index indicating the degree of light resistance, and was evaluated based on the following criteria. A smaller ΔEab value indicates better light resistance.
[Standard]
A: ΔEab value was 3 or less.
(Triangle | delta): (DELTA) Eab value was 3-10.
X: ΔEab value was 10 or more.

(Examples 2 to 24, Comparative Examples 1 to 3)
In Example 1, except that the dye (Exemplary Compound 1-2) used in “3) Preparation of Colorant-Containing Resist Solution” was replaced with the dyes shown in Table 4 below, respectively, in the same manner as in Example 1, A dye resist solution was prepared to form a pattern image, and the same evaluation was performed. The evaluation results are shown in Table 4 below. In addition, the spectrum of the dye (Exemplary Compound 1-7) used in Example 2 is as shown in FIG.

As shown in Table 4 above, the phthalocyanine compound or mixture according to the present invention is particularly excellent in solvent solubility, and the dye-containing curable composition of the present invention containing the phthalocyanine compound or mixture according to the present invention as a colorant. The product showed good storage stability and was excellent in heat resistance and light resistance. Moreover, the formed pattern image showed a rectangular profile.
On the other hand, as in Comparative Examples 1 to 3, Comparative Compounds 1 to 3 which are sulfonamide group monosubstituted products are good in terms of heat resistance and light resistance, but have low solubility in a solvent and in a solution state. The storage stability was also inferior.

(Example 25)
1) Preparation of dye resist solution (positive dye-containing curable composition)-Ethyl lactate (EL) 20 parts-Propylene glycol monomethyl ether acetate 10 parts (PGMEA)
The following resin P-1: 3.0 parts The following naphthoquinone diazide compound N-1: 1.8 parts Hexamethoxymethylolated melamine (crosslinking agent): 0.6 parts TAZ-107 (manufactured by Midori Chemical Co .; light Acid generator) 1.2 parts ・ Fluorosurfactant 0.0005 parts (F-475, manufactured by Dainippon Ink & Chemicals, Inc.)
Dye: 1.5 parts (Exemplary compound 1-2; phthalocyanine mixture represented by general formula (1))
Were mixed and dissolved to obtain a dye resist solution (dye-containing curable composition [positive type] solution of the present invention).

-Synthesis of Resin P-1-
A three-necked flask was charged with 70.0 g of benzyl methacrylate, 13.0 g of methacrylic acid, 17.0 g of 2-hydroxyethyl methacrylate, 300 g of ethyl lactate, and 300 g of propylene glycol monomethyl ether acetate, and a stirrer, a reflux condenser, and a thermometer. A catalyst amount of polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) was added at 65 ° C. under a nitrogen stream and stirred for 10 hours. The obtained resin solution was added dropwise to 20 L of ion exchange water with vigorous stirring to obtain a white powder. The obtained white powder was vacuum-dried at 40 ° C. for 24 hours to obtain 145 g of resin P-1. When the molecular weight of this resin P-1 was measured by GPC, it was weight average molecular weight Mw = 28,000 and number average molecular weight Mn = 11,000.

-Synthesis of naphthoquinonediazide compound N-1-
Trisp-PA (manufactured by Honshu Chemical Co., Ltd.) 42.45 g, o-naphthoquinonediazide-5-sulfonyl chloride 61.80 g, and acetone 300 ml were charged into a three-necked flask, and 24.44 g of triethylamine was added dropwise at room temperature over 1 hour. did. After completion of the dropwise addition, the mixture was further stirred for 2 hours, and then the obtained reaction solution was poured into a large amount of water while stirring. The precipitated naphthoquinonediazide sulfonic acid ester was collected by suction filtration and vacuum dried at 40 ° C. for 24 hours to obtain naphthoquinonediazide compound N-1.

2) Exposure / development and evaluation of dye-containing curable composition and evaluation In the same manner as in Example 1, coating, pre-baking, irradiation, development, rinsing and drying were performed to obtain a cyan pattern image, and then the pattern image was 180. Heat at 5 ° C. for 5 minutes. The formed pattern image showed a rectangular profile. Moreover, when the storage stability of the dye-containing curable composition and the heat resistance and light resistance of the pattern image were evaluated in the same manner as in Example 1, all were excellent as shown in Table 5 below. I understood.

(Examples 26 to 39, Comparative Examples 4 to 6)
In Example 25, except that the dye (Exemplary Compound 1-2) used in “3) Preparation of Colorant-Containing Resist Solution” was replaced with the dye shown in Table 5 below, in the same manner as in Example 25, A dye resist solution was prepared to form a pattern image, and the same evaluation was performed. The evaluation results are shown in Table 5 below.

  Also in the results of Table 5 above, as in the case of the negative type, in the examples, the solvent solubility of the dye is particularly good, and the dye-containing curable composition of the present invention has good storage stability and heat resistance. And light resistance. The pattern image showed a rectangular profile. On the other hand, in the comparative example, the solvent solubility of the dye was low, and the storage stability in the solution state was particularly inferior.

(Examples 40 to 65)
A pattern image was formed by performing the same operation as in Examples 1 to 24 except that the glass substrate used in Examples 1 to 24 was replaced with a silicon wafer substrate. Next, a 2 μm square pattern was irradiated with an exposure amount of 500 mj / cm ² using an i-line reduction projection exposure apparatus, and after irradiation, a 60% CD-2000 (manufactured by FUJIFILM Arch Corporation) developer was used. Developed at 23 ° C. for 60 seconds. Then, after rinsing with running water for 30 seconds, spray drying was performed. As a result, a pattern suitable as a color filter for CCD having a square cross section was obtained.

FIG. 4 is a graph showing a spectral spectrum of Exemplified Compound 1-7 used in Example 2.

Claims (4)

(A) A dye-containing curable composition comprising at least an alkali-soluble resin, (B) a dye, and (C) a photosensitive compound, wherein the (B) dye is represented by the following general formula (1) A dye-containing curable composition comprising:

Wherein R ¹ and R ² are each independently an unsubstituted alkyl group, an alkyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond and an ester bond, an alkylcarbonyl group, an alkoxycarbonyl And at least one of R ¹ and R ² represents an alkyl group, an alkylcarbonyl group or an alkoxycarbonyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond and an ester bond. R ³ represents a hydrogen atom, an unsubstituted alkyl group, or an alkyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond, an ester bond, and a hydroxy group. However, the -R ³ and -CHR ¹ R ² is not to represent the same group at the same time. m represents a numerical value of 0.1 to 3.9, n represents a numerical value of 0.1 to 3.9, and m + n represents a numerical value of 1.0 to 4.0. Met represents a divalent metal atom, a trivalent monosubstituted metal atom, a tetravalent disubstituted metal atom, or an oxy metal. ] (A) A dye-containing curable composition containing at least an alkali-soluble resin, (B) a dye, and (C) a photosensitive compound, wherein the (B) dye is represented by the following general formula (2) A dye-containing curable composition comprising:

Wherein R ¹ and R ² are each independently an unsubstituted alkyl group, an alkyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond and an ester bond, an alkylcarbonyl group, an alkoxycarbonyl And at least one of R ¹ and R ² represents an alkyl group, an alkylcarbonyl group or an alkoxycarbonyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond and an ester bond. R ³ represents a hydrogen atom, an unsubstituted alkyl group, or an alkyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond, an ester bond, and a hydroxy group. However, -R ³ and -CHR ¹ R ² is not to represent the same group at the same time. m ′ represents a numerical value of 1 to 3, n ′ represents a numerical value of 1 to 3, and m ′ + n ′ represents a numerical value of 2 to 4. Met represents a divalent metal atom, a trivalent monosubstituted metal atom, a tetravalent disubstituted metal atom, or an oxy metal. ] At least (A) an alkali-soluble resin and (B) a dye, and the (B) dye is a phthalocyanine mixture represented by the following general formula (1) and a phthalocyanine compound represented by the following general formula (2) A color filter comprising at least one selected from the group consisting of:

[In general formula (1) or (2), R ¹ and R ² are each independently an unsubstituted alkyl group, an alkyl containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond and an ester bond A group, an alkylcarbonyl group, or an alkoxycarbonyl group, wherein at least one of R ¹ and R ² includes an oxygen atom in at least one form selected from an ether bond, a carbonyl bond, and an ester bond; Represents an alkoxycarbonyl group. R ³ represents a hydrogen atom, an unsubstituted alkyl group, or an alkyl group containing an oxygen atom in at least one form selected from an ether bond, a carbonyl bond, an ester bond, and a hydroxy group. However, the -R ³ and -CHR ¹ R ² is not to represent the same group at the same time. m represents a numerical value of 0.1 to 3.9, n represents a numerical value of 0.1 to 3.9, and m + n represents a numerical value of 1.0 to 4.0. m ′ represents a numerical value of 1 to 3, n ′ represents a numerical value of 1 to 3, and m ′ + n ′ represents a numerical value of 2 to 4. Met represents a divalent metal atom, a trivalent monosubstituted metal atom, a tetravalent disubstituted metal atom, or an oxy metal. ]   A method for producing a color filter, comprising: applying a dye-containing curable composition according to claim 1 or 2 onto a support, exposing through a mask, and developing to form a pattern image.

Images