JP5734602B2 - Red coloring composition, colored curable composition, color filter for solid-state imaging device, method for producing the same, and solid-state imaging device - Google Patents

Description

  The present invention relates to a red coloring composition, a colored curable composition, a color filter for a solid-state imaging device, a manufacturing method thereof, and a solid-state imaging device.

  As a color filter used for colorizing a solid-state imaging device or a liquid crystal display device, a color filter composed of a red filter layer, a green filter layer, and a blue filter layer formed adjacent to each other on the same plane on a substrate In addition, a color filter composed of a yellow filter layer, a magenta filter layer, and a cyan filter layer is known (in the present specification, the colored filter layers of the respective colors are also referred to as “colored patterns”).

In recent years, color filters are required to have finer pigments, thinner colored patterns, and reduced noise due to a spectral spectrum as the solid-state imaging device becomes finer.
In order to solve such problems, the use of dyes has been proposed (see, for example, Patent Document 1). For example, it is known that a red dye is used for a red filter array of a color filter (see, for example, Patent Document 2).

However, since the coloring pattern obtained with the dye does not have sufficient heat resistance and light resistance, a color filter using an organic pigment having excellent heat resistance and light resistance has been studied.
As organic pigments for color filters, the use of organic pigments with excellent heat resistance and light resistance such as anthraquinone, diketopyrrolopyrrole, quinacridone, isoindoline, perinone, perylene, and condensed azo has been studied. Yes.
Patent Document 3 proposes a red ink composition for a color filter containing a monoazo compound containing a naphthalene ring.

  However, there are no pigment dispersions containing conventional red pigments such as anthraquinone and diketopyrrolopyrrole that satisfy all the requirements for finer pigments, thinner colored patterns, and spectral spectra. .

  As a method for producing a color filter using an organic pigment, for example, a photolithography method (for example, performing a patterning process by exposing and developing a composition in which an organic pigment is dispersed in a photosensitive resin is repeated a required number of times. And Patent Document 4), offset printing using an ink containing an organic pigment, and printing methods such as inkjet printing.

JP-A-6-75375 Japanese Patent Laid-Open No. 5-5067 International Publication No. 05/052074 Pamphlet Japanese Patent Laid-Open No. 1-152449

A red composition used for a color filter for a solid-state imaging device or the like is desired to have a fine pigment, be a thin film, and be capable of forming a colored film exhibiting spectral characteristics capable of reducing noise.
However, according to the knowledge of the present inventors, particularly when an azo pigment is used as a red pigment, the microparticulation changes the spectral spectrum, and the dispersion stability of the pigment in the red composition is also improved. From the decrease, it became clear that it is difficult to reduce the thickness of the colored film formed by the curable composition using the red composition.

This invention is made | formed in view of said situation, and makes it a subject to achieve the following objectives.
That is, an object of the present invention is to provide a red composition capable of forming a red thin film having excellent spectral characteristics.
Another object of the present invention is to provide a colored curable composition that can form a fine red pattern having excellent spectral characteristics and suppresses development residue.
It is to provide.
Furthermore, the objective of this invention is providing the solid-state image sensor provided with the color filter for solid-state image sensors which has the fine red pattern excellent in the spectral characteristics, its manufacturing method, and this color filter.

Specific means for solving the above problems are as follows.
<1> A red coloring composition comprising (A) a red pigment, (B) a yellow pigment, and (C) a dispersant, wherein the (A) red pigment is an azo pigment represented by the following general formula (1) And (B) the yellow pigment is C.I. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, and 185, and (C) the dispersing agent is A polymer compound containing at least one repeating unit selected from repeating units represented by formula (I) and general formula (II), and having a film thickness of 0. A red colored composition that satisfies all of the following characteristics (1) to (5) when a colored permeable membrane of 6 μm is formed.
(1) The range of the wavelength of light from which 5% transmittance is obtained is 583 nm or more and less than 587 nm (2) The transmittance of light having a wavelength of 400 nm is 15% or less (3) The transmittance of light having a wavelength of 525 nm is 5% or less (4 ) The transmittance of light with a wavelength of 600 nm is 75% or more (5) The transmittance of light with a wavelength of 700 nm is 95% or more

<2> The red coloring composition according to <1>, wherein the (A) red pigment is an azo pigment represented by the following general formula (1).

[In one general formula (1), G represents a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group, R ₁ is amino group which may have a substituent, an aliphatic oxy group, an aliphatic Represents a group, an aryl group, or a heterocyclic group, and R ₂ represents a substituent.
A represents any of the groups represented by the following general formulas (A-1) to (A-32).
m represents an integer of 0 to 5, and n represents 1 .
Does not have an ionic hydrophilic groups in one general formula (1). ]

[In General Formulas (A-1) to (A-32), R _{51 to} R ₅₉ each independently represent a hydrogen atom or a substituent, and adjacent substituents are bonded to each other to form a 5- to 6-membered ring. May be formed. * Represents the bonding position with the azo group in the general formula (1). ]


[In General Formulas (I) and (II), R ^{1 to} R ⁶ each independently represent a hydrogen atom or a monovalent organic group, and X ¹ and X ² each independently represent —CO—, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group, L ¹ and L ² each independently represent a single bond or a divalent organic linking group. , A ¹ and A ² each independently represent a monovalent organic group, m and n each independently represents an integer of 2 to 8, and p and q each independently represents 1 to 100. Represents an integer. ]

< 2 > The red coloring composition according to < 1 >, wherein the azo pigment represented by the general formula (1) is an azo pigment represented by the following general formula (2).

In [general formula (2), R ₂₁ is an optionally substituted amino group, an aliphatic oxy group, an aliphatic group, an aryl group, or a heterocyclic group, R ₂₂ represents a substituent. R ₅₅ and R ₅₉ each independently represent a hydrogen atom or a substituent.
m represents an integer of 0 to 5, and n represents 1 .
Z represents an electron withdrawing group having a Hammett's σp value of 0.2 or more .
One general formula (2) it does not have an ionic hydrophilic group in. ]

< 3 > The <1> or <2>, wherein the azo pigment represented by the general formula (1) is a solvent salt milled azo pigment, and the particle size of the pigment after the solvent salt milling is 100 nm or less. Red coloring composition according to

< 4 > The yellow pigment (B) is C.I. Wherein an I Pigment Yellow 139 <1> to red colored composition according to any one of <3>.

<6> The above-mentioned (C) the dispersant contains a polymer compound containing at least one repeating unit selected from repeating units represented by any one of the following general formula (I) and general formula (II) The red coloring composition in any one of <1>-<5>.

[In General Formulas (I) and (II), R ^{1 to} R ⁶ each independently represent a hydrogen atom or a monovalent organic group, and X ¹ and X ² each independently represent —CO—, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group, L ¹ and L ² each independently represent a single bond or a divalent organic linking group. , A ¹ and A ² each independently represent a monovalent organic group, m and n each independently represents an integer of 2 to 8, and p and q each independently represents 1 to 100. Represents an integer. ]

<5> The red colored composition according to any one of <1> to <4> , wherein the polymer compound has an acid group in a side chain in a range of 50 mgKOH / g to 200 mgKOH / g.

< 6 > A colored curable composition containing the red colored composition according to any one of <1> to < 5 >, a photopolymerization initiator, and a polymerizable compound.

< 7 > The colored curable composition according to < 6 >, wherein the photopolymerization initiator is an oxime photopolymerization initiator.

< 8 > A step of applying the colored curable composition according to < 6 > or < 7 > on the support to form a colored curable composition layer, and the colored curable composition layer as a mask. And a step of developing the colored curable composition layer after exposure to form a colored pattern, and a method for producing a color filter for a solid-state imaging device.

< 9 > A color filter for a solid-state imaging device manufactured by the method for manufacturing a color filter for a solid-state imaging device according to < 8 >.

<10> A solid-state imaging device comprising the color filter for a solid-state imaging device according to < 9 >.

ADVANTAGE OF THE INVENTION According to this invention, the red composition which can form the red thin film excellent in the spectral characteristics can be provided.
In addition, according to the present invention, it is possible to provide a colored curable composition in which a fine red pattern excellent in spectral characteristics can be formed and generation of development residues is suppressed.
In addition, according to the present invention, it is possible to provide a color filter for a solid-state imaging device having a fine red pattern with excellent spectral characteristics, a method for manufacturing the same, and a solid-state imaging device including the color filter.

[Red coloring composition]
The red coloring composition of the present invention is a red coloring composition containing (A) a red pigment, (B) a yellow pigment, and (C) a dispersant, which will be described in detail below , and using the red coloring composition. When the colored permeable membrane having a film thickness of 0.6 μm is formed using the red colored composition, the colored permeable membrane satisfies all the characteristics shown in the following (1) to (5) . Among them, the (A) red pigment is a red pigment in which n in the general formula (1) is 1 among the azo pigments represented by the general formula (1), and the (B) yellow pigment is C.I. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, and 185, and (C) the dispersant is generally It is a red coloring composition which is a high molecular compound containing the at least 1 sort (s) of repeating unit selected from the repeating unit represented by either formula (I) and general formula (II) .
(1) The range of the wavelength of light from which 5% transmittance is obtained is 583 nm or more and less than 587 nm (2) The transmittance of light having a wavelength of 400 nm is 15% or less (3) The transmittance of light having a wavelength of 525 nm is 5% or less (4 ) The transmittance of light with a wavelength of 600 nm is 75% or more (5) The transmittance of light with a wavelength of 700 nm is 95% or more

  When the red colored composition of the present invention is used to form a colored permeable film having a film thickness of 0.6 μm using the red colored composition, the colored permeable film has the following (1 ) To (5) are required to satisfy all the characteristics.

  Here, in this specification, solid content means including all the components except the solvent contained in a composition, and a liquid component etc. are also contained in solid content at normal temperature (25 degreeC). .

  In addition, the colored transmission film to be measured for transmittance is formed by spin coating a red colored composition on a glass substrate to form a coating film, and drying the coating film on a hot plate (100 ° C.). Make it.

  The transmittance in the present invention is a value measured using an instantaneous multi-photometry system (trade name: MCPD-3000) manufactured by Otsuka Electronics Co., Ltd. with the colored permeable membrane formed as described above as a measurement target.

  Examples of the method for controlling the red coloring composition of the present invention so as to satisfy all of the characteristics shown in the above (1) to (5) include, for example, the types, content ratios, and / or particle sizes of the red pigment and the yellow pigment. Adjustment and the like.

Hereinafter, each component which the red coloring composition containing the red coloring composition of this invention contains is demonstrated in detail.

(Pigment)
The red coloring composition of the present invention contains a pigment , and among the azo pigments represented by the general formula (1) which is a preferred embodiment of the red pigment (A) described later , the pigment is represented by the general formula. Among the red pigment in which n in (1) is 1 and (B) a yellow pigment , C.I. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, and 185 are included at least.
In this invention, a pigment can be used individually or in mixture of 2 or more types.

Here, the pigment will be described.
A pigment is used by being finely dispersed as solid particles such as a molecular aggregate in a solvent, unlike a dye used by being dissolved in water or an organic solvent in a molecular dispersion state.
More specifically, a pigment is a state in which molecules are firmly bonded to each other by cohesive energy due to strong interaction between dye molecules. In order to create this state, it is described in, for example, Journal of Imaging Society of Japan, Vol. 43, page 10 (2004) that van der Waals force between molecules and hydrogen bonding between molecules are necessary.
In order to increase the van der Waals force between molecules, introduction of an aromatic group, a polar group and / or a hetero atom into the molecule can be considered. In order to form an intermolecular hydrogen bond, introduction of a substituent containing a hydrogen atom bonded to a hetero atom and / or introduction of an electron donating substituent into the molecule can be considered. Further, it is considered preferable that the polarity of the whole molecule is high. For this purpose, for example, in the case of an azo pigment described later, it is considered that a shorter chain group such as an alkyl group is preferable, and a smaller molecular weight / azo group value is preferable.
From these viewpoints, the pigment molecule preferably contains an amide bond, a sulfonamide bond, an ether bond, a sulfone group, an oxycarbonyl group, an imide group, a carbamoylamino group, a hetero ring, a benzene ring and the like.

  The red coloring composition of the present invention preferably contains a red pigment as a main pigment. Here, the main pigment means that the pigment is contained in an amount of 60% by mass or more based on the total mass of the pigment pigmented in the red coloring composition.

  Further, the content ratio (A: B) of (A) the red pigment and (B) the yellow pigment is preferably 100: 50 to 100: 15, more preferably 100: 30 to 100: 15, based on mass. : 25-100: 15 is more preferable.

  The volume average particle diameter of the pigment (a pigment containing at least a red pigment and a yellow pigment) in the red coloring composition of the present invention is preferably 1 nm or more and 250 nm or less. The volume average particle diameter of the pigment particles refers to the particle diameter of the pigment itself or the particle diameter to which the additive has adhered when an additive such as a dispersant is attached to the pigment.

  In the present invention, a nanotrac UPA particle size analyzer (UPA-EX150; manufactured by Nikkiso Co., Ltd.) was used as a device for measuring the volume average particle diameter of the pigment in the red coloring composition. The measurement was performed according to a predetermined measurement method by placing 3 ml of the pigment dispersion composition in a measurement cell. As parameters to be input at the time of measurement, ink viscosity was used as the viscosity, and pigment density was used as the density of the dispersed particles.

  The preferable volume average particle diameter of the pigment contained in the red coloring composition of the present invention is 2 nm or more and 100 nm or less, and more preferably 2 nm or more and 50 nm or less. The particularly preferred volume average particle diameter of the pigment is 2 nm or more and 30 nm or less, and the most preferable volume average particle diameter is 2 nm or more and 15 nm or less from the viewpoint of obtaining good spectral characteristics.

  The total concentration of the pigments contained in the red coloring composition of the present invention is preferably in the range of 1 to 35% by mass, and more preferably in the range of 2 to 25% by mass. If it is the said range, it will be easy to adjust the physical-property values of dispersion, such as surface tension and a viscosity, and it is preferable.

<(A) Red pigment>
Examples of red pigments include C.I. among the compounds classified as Pigment in the Color Index (CI; issued by The Society of Dyers and Colorists). I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,270,272,279 etc. (C.I.) Other pigments are numbered, it is possible to apply the azo pigment represented by the general formula (1) described later.
Among these red pigments, the azo pigment represented by the general formula (1) is more preferable.

<< Azo pigments represented by general formula (1) >>
A preferred red pigment in the present invention is an azo pigment represented by the following general formula (1).

In General Formula (1), G represents a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group, and R ₁ represents an amino group, an aliphatic oxy group, or an aliphatic group that may have a substituent. Represents an aryl group or a heterocyclic group, and R ₂ represents a substituent.
A represents any of the groups represented by the following general formulas (A-1) to (A-32).
m represents an integer of 0 to 5, and n represents an integer of 1 to 4.
When n = 2, the general formula (1) represents a dimer via R ₁ , R ₂ , A or G.
In the case of n = 3, the general formula (1) represents a trimer via R ₁ , R ₂ , A or G.
When n = 4, the general formula (1) represents a tetramer through R ₁ , R ₂ , A or G.
There is no ionic hydrophilic group in the general formula (1).

In general formulas (A-1) to (A-32), R _{51 to} R ₅₉ each independently represent a hydrogen atom or a substituent, and adjacent substituents are bonded to each other to form a 5- to 6-membered ring. You may do it. * Represents a bonding position with the azo group of the general formula (1).

The compound represented by the general formula (1) can easily form an intermolecular interaction of dye molecules due to its specific structure, has low solubility in water or an organic solvent, and can be an azo pigment.
In addition, the azo pigment represented by the following general formula (1) has the above-described specific structure, thereby exhibiting excellent characteristics in color characteristics such as coloring power and hue, and light resistance, ozone resistance, and the like. The characteristic which was excellent also in durability of can be shown.
Specifically, the red pattern of the color filter formed using the red coloring composition of the present invention containing the azo pigment represented by the general formula (1) exhibits good spectral characteristics as red.

Hereinafter, the azo pigment represented by the general formula (1) will be described in detail.
First, the aliphatic group, aryl group, heterocyclic group, and substituent in general formula (1) will be described.

  The aliphatic moiety of the aliphatic group in the general formula (1) may be linear, branched or cyclic. Moreover, it may be saturated or unsaturated. Specific examples include an alkyl group, an alkenyl group, a cycloalkyl group, and a cycloalkenyl group. Furthermore, the aliphatic group may be unsubstituted or may have a substituent.

The aryl group in the general formula (1) may be a single ring or a condensed ring. The aryl group may be unsubstituted or may have a substituent.
The heterocyclic group in the general formula (1) only needs to have a hetero atom (for example, a nitrogen atom, a sulfur atom, or an oxygen atom) in the ring portion. It may be a ring. The heterocyclic moiety may be a single ring or a condensed ring. Furthermore, the heterocyclic group may be unsubstituted or may have a substituent.

  Moreover, the substituent in General formula (1) should just be a group which can be substituted, for example, an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, aryl Oxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy group, arylsulfonyl Oxy group, heterocyclic sulfonyloxy group, sulfamoyl group, aliphatic sulfonamide group, aryl sulfonamide group, heterocyclic sulfonamide group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxycarbonyl An amino group, an aryloxycarbonylamino group, Telocyclic oxycarbonylamino group, aliphatic sulfinyl group, arylsulfinyl group, aliphatic thio group, arylthio group, hydroxy group, cyano group, sulfo group, carboxy group, aliphatic oxyamino group, aryloxyamino group, carbamoylamino group Sulfamoylamino group, halogen atom, sulfamoylcarbamoyl group, carbamoylsulfamoyl group, dialiphatic oxyphosphinyl group, diaryloxyphosphinyl group and the like. These substituents may be further substituted, and examples of the further substituent include groups selected from the substituents described above.

  When the substituent is an acyl group, the acyl group may be an aliphatic carbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, or may have a substituent. As the group which may be substituted, any group can be used as long as it is a group which can be substituted with the groups described in the above-mentioned substituent group. For example, acetyl, propanoyl, benzoyl, 3-pyridinecarbonyl and the like can be mentioned.

  The azo pigment of the present invention does not contain an ionic hydrophilic group (for example, carboxyl group, sulfo group, phosphono group and quaternary ammonium group) as a substituent from the viewpoint of solubility. When it contains an ionic hydrophilic group, it is preferably a salt with a polyvalent metal cation (eg, magnesium, calcium, barium), more preferably a lake pigment.

  The azo pigment represented by the general formula (1) does not contain an ionic hydrophilic group (for example, carboxy group, sulfo group, phosphono group and quaternary ammonium group) as a substituent from the viewpoint of solubility.

  In the general formula (1), the aliphatic group represented by G may have a substituent and may be saturated or unsaturated. The substituent may be any group as long as it is a group described in the above-mentioned substituent group and can be substituted for the aliphatic group represented by G. Preferred substituents include a hydroxy group and an aliphatic group. An oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, and a carbamoylamino group. The aliphatic group represented by G is preferably an aliphatic group having 1 to 8 carbon atoms in total, more preferably an alkyl group having 1 to 4 carbon atoms in total, such as methyl, ethyl, vinyl, cyclohexyl. , Carbamoylmethyl and the like.

  In general formula (1), the aryl group represented by G may be condensed or may have a substituent. The substituent may be any group as long as it is a group described in the above-mentioned substituent group and can be substituted for the aryl group represented by G. Preferred substituents include a nitro group, a halogen atom, An aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, and a carbamoylamino group. The aryl group represented by G is preferably an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms, such as phenyl, 4-nitrophenyl, 4-acetylamino. Phenyl, 4-methanesulfonylphenyl and the like.

  In the general formula (1), the heterocyclic group represented by G may have a substituent, may be saturated or unsaturated, and may be condensed. As the substituent, any group can be used as long as it is a group described in the above-mentioned substituent group and can be substituted with the heterocyclic group represented by G. Preferred substituents include a halogen atom, a hydroxy group, An aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, and a carbamoylamino group. The heterocyclic group represented by G is preferably a heterocyclic group bonded with carbon atoms having 2 to 12 carbon atoms in total, more preferably 5 to 6 having 2 to 10 carbon atoms bonded with carbon atoms. It is a membered heterocycle, and examples thereof include 2-tetrahydrofuryl and 2-pyrimidyl.

  G is preferably a hydrogen atom. This is because it is easy to form an intramolecular hydrogen bond or an intramolecular cross hydrogen bond.

The amino group represented by R ₁ may have a substituent. The substituent may be any group as long as it is a group described in the above-mentioned substituent group and can be substituted with the amino group represented by R _1. Preferred substituents include aliphatic groups, aryl Group, heterocyclic group, and the like.
These substituents may further have a substituent, and the substituent is preferably a substituent having an aliphatic group, a hydroxy group, an amide bond, an ether bond, an oxycarbonyl bond, a thioether bond, and the like. A substituent having a bond between a hetero atom and a hydrogen atom is more preferable from the viewpoint of facilitating intermolecular interaction such as intermolecular hydrogen bonding.
The amino group which may have a substituent represented by R ₁ is preferably an unsubstituted amino group, an alkylamino group having 1 to 10 carbon atoms in total, a dialkylamino group having 2 to 10 carbon atoms in total ( Dialkyl groups may be bonded to each other to form a 5- to 6-membered ring), an arylamino group having 6 to 12 carbon atoms in total, saturated even if having 2 to 12 carbon atoms in total, A heterocyclic amino group which may be present, more preferably an unsubstituted amino group, an alkylamino group having 1 to 8 carbon atoms in total, a dialkylamino group having 2 to 8 carbon atoms in total, and 6 carbon atoms in total. -10 arylamino group, a heterocyclic amino group which may be saturated or unsaturated having 2 to 12 carbon atoms in total, such as methylamino, N, N-dimethylamino, N-phenylamino N- (2-pyrimidyl) a Mino etc. are mentioned.
More preferably, the arylamino group having 6 to 13 carbon atoms which may have a substituent and the saturated or unsaturated group having 2 to 12 total carbon atoms which may have a substituent A heterocyclic amino group which may be

When R ₁ is an arylamino group, the substituent on the aryl group preferably has a substituent at the para position from the bonding position with the amino group, and most preferably has a substituent only at the para position. As the substituent, any group can be used as long as it is a group described in the above-mentioned substituent group and can be substituted on the arylamino group represented by R ₁ , and preferably has 1 to 7 carbon atoms in total. More preferably an aliphatic group optionally having a substituent having 1 to 4 carbon atoms (for example, methyl, ethyl, allyl, (i) -propyl, (t) -butyl, etc.), the total number of carbon atoms 1 to 7 optionally substituted aliphatic oxy groups (for example, methoxy, ethoxy, (i) -propyloxy, allyloxy, etc.), halogen atoms (for example, fluorine, chlorine, bromine, etc.), total carbon A carbamoyl group (for example, carbamoyl, N-phenylcarbamoyl, N-methylcarbamoyl, etc.) which may have a substituent of 1 to 7 atoms, 1 to 7 total carbon atoms, more preferably 1 total carbon atoms With ~ 4 substituents Ureido group (for example, ureido, N-methylureido, N, N-dimethylureido, N-4-pyridylureido, N-phenylureido, etc.), nitro group, aryl having 1 to 7 carbon atoms in total A heterocyclic ring condensed with a group (e.g., imidazolone), a hydroxy group, an aliphatic thio group (e.g., having a substituent having 1 to 7 carbon atoms in total, more preferably 1 to 4 carbon atoms in total) , Methylthio, ethylthio, (i) -propylthio, allylthio, (t) -butylthio, etc.), acylamino which may have a substituent having 2 to 7 total carbon atoms, more preferably 2 to 4 total carbon atoms A group (for example, acetamino, propionylamino, pivaloylamino, benzoylamino, etc.) having a substituent of 2 to 7 carbon atoms, more preferably 2 to 4 carbon atoms in total. May have an aliphatic oxycarbonylamino group (for example, methoxycarbonylamino, propyloxycarbonylamino, etc.), a substituent having 2 to 7 carbon atoms in total, more preferably 2 to 4 carbon atoms in total. A good aliphatic oxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl, etc.), an acyl group (aliphatic group) which may have a substituent having 2 to 7 total carbon atoms, more preferably 2 to 4 total carbon atoms It may be a carbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, or may have a substituent, and the substituent is described in the above-mentioned substituents section. Any acyl group having 2 to 7 carbon atoms in total, more preferably an acyl group having 2 to 4 carbon atoms in total, may be used as long as it is a group that can be substituted on the acyl group. There, for example, acetyl, propanoyl, benzoyl, 3-pyridine carbonyl, and the like. ) And the like.

  When the substituent on the aryl group of the arylamino group is substituted from the bonding position with the amino group to the para position, the substituent is located at the end of the molecule, so intermolecular interactions such as intermolecular hydrogen bonding are likely to occur. Because of this, the hue becomes sharper. When the substituent on the aryl group further has a substituent, a substituent having an aliphatic group, a hydroxy group, an amide bond, an ether bond, an oxycarbonyl bond, a thioether bond or the like is preferable, and a bond between a hetero atom and a hydrogen atom Is more preferable from the viewpoint of facilitating intermolecular interaction such as intermolecular hydrogen bonding.

When R ₁ is a heterocyclic amino group, the substituent is the group described in the above-mentioned substituent group, and can be any group that can be substituted for the heterocyclic amino group represented by R _1. Any substituent may be used, and the same substituent as in the case of the arylamino group is preferable. However, when the substituent on the heterocyclic group further has a substituent, an aliphatic group, a hydroxy group, an amide bond, an ether bond, an oxycarbonyl bond In addition, a substituent having a thioether bond or the like is preferable, and a substituent having a bond between a hetero atom and a hydrogen atom is more preferable from the viewpoint of facilitating intermolecular interaction such as intermolecular hydrogen bonding.

More preferable substituents when R ₁ is an arylamino group or a heterocyclic amino group include an aliphatic group, an aliphatic oxy group, a halogen atom, a carbamoyl group, a heterocyclic ring condensed with the aryl group, It is an aliphatic oxycarbonyl group. More preferably, the substituent is preferably an aliphatic group having 1 to 4 carbon atoms, an aliphatic oxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a carbamoyl group having 1 to 4 carbon atoms, or a total carbon atom. It is an aliphatic oxycarbonyl group having 2 to 4 atoms.

The aliphatic oxy group represented by R ₁ may have a substituent, and the substituent is the group described in the above-mentioned substituent group, and the aliphatic oxy group represented by R ₁ Any group can be used as long as it can be substituted with an aliphatic oxy group. Preferred substituents include a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, An acylamino group and a carbamoylamino group. The aliphatic oxy group represented by R ₁ is preferably an alkoxy group having 1 to 8 carbon atoms in total, more preferably an alkoxy group having 1 to 4 carbon atoms in total, such as methoxy, ethoxy, ( t) -butoxy, methoxyethoxy, carbamoylmethoxy and the like.

The aliphatic group represented by R ₁ may have a substituent, and the substituent is the group described in the above-mentioned substituent group, and the aliphatic group represented by R _1. Any substituent can be used as long as the group can be substituted. Preferred substituents include a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, and an acylamino group , A carbamoylamino group. The aliphatic group represented by R ₁ is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, (s) -Butyl, methoxyethyl, carbamoylmethyl and the like.

The aryl group represented by R ₁ may have a substituent, and the substituent is the group described in the above-mentioned substituent group, and includes the aryl group represented by R _1. Any substituent can be used, and preferred substituents include an aliphatic group, an aliphatic oxy group, a halogen atom, a carbamoyl group, a heterocycle condensed with the aryl group, and an aliphatic oxycarbonyl group. The aryl group represented by R ₁ is preferably an aryl group having 6 to 12 carbon atoms in total, more preferably an aryl group having 6 to 10 carbon atoms in total, such as phenyl, 4-methylphenyl, 3-chlorophenyl and the like can be mentioned.

The heterocyclic group represented by R ₁ may be a saturated heterocyclic ring, an unsaturated heterocyclic group, or may have a substituent. The substituent may be any group as long as it is the group described in the above-mentioned substituent group and can be substituted on the heterocyclic group represented by R _1. Preferred substituents include aliphatic groups, An aliphatic oxy group, a carbamoyl group, a hetero ring condensed with the hetero group, and an aliphatic oxycarbonyl group. The heterocyclic group represented by R ₁ is preferably a heterocyclic group having 2 to 10 carbon atoms in total, more preferably a 5- to 6-membered non-ring bonded with a nitrogen atom having 2 to 8 carbon atoms in total. An aromatic heterocyclic group such as 1-piperidyl, 4-morpholinyl, 1-quinoyl, 2-pyrimidyl, 4-pyridyl and the like.

R ₁ is preferably an amino group which may have a substituent, an aliphatic oxy group, or a 5- to 6-membered non-aromatic heterocyclic group bonded by a nitrogen atom, more preferably a substituted group. An amino group which may have a group, an aliphatic oxy group, and more preferably an amino group which may have a substituent.

R ₁ is more preferably an amino group which may have a substituent.

The substituent represented by R ₂ may be any group as long as it is a group that can be substituted as R ₂ , and is preferably an aliphatic group, an aryl group, or a heterocyclic group. A group, an aliphatic oxycarbonyl group, a carboxy group, an optionally substituted carbamoyl group, an acylamino group, a sulfonamide group, an optionally substituted carbamoylamino group, and a substituent. A sulfamoyl group, an aliphatic oxy group, an aliphatic thio group, a cyano group, and a halogen atom, more preferably an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, an acylamino group, and a substituent. A carbamoylamino group, an aliphatic oxy group, or a halogen atom, which may have an aliphatic group, most preferably an aliphatic oxy group.
When these substituents further have a substituent, a substituent having an aliphatic group, a hydroxy group, an amide bond, an ether bond, an oxycarbonyl bond, a thioether bond, or the like is preferable, and a substituent having a heteroatom-hydrogen atom bond is preferable. The group is more preferable from the viewpoint of facilitating intermolecular interaction such as intermolecular hydrogen bonding.

m is preferably 0 to 3, more preferably 0 to 1, and even more preferably 0.
n is preferably 1 or 2. The red coloring composition of the present invention includes those in which n is 1.

The aliphatic group represented by R ₂ may have a substituent and may be saturated or unsaturated. The substituent may be any group as long as it is a group described in the above-mentioned substituent group and can be substituted for the aliphatic group represented by R ₂ . The aliphatic group represented by R ₂ is preferably an alkyl group having 1 to 8 carbon atoms in total, more preferably an alkyl group having 1 to 6 carbon atoms in total, such as methyl, ethyl, i- And propyl, cyclohexyl, t-butyl and the like.

The aryl group represented by R ₂ may have a substituent. As the substituent, any group can be used as long as it is the group described in the above-mentioned substituent group and can be substituted for the aryl group represented by R ₂ . The aryl group represented by R ₂ is preferably an aryl group having 6 to 12 carbon atoms in total, more preferably an aryl group having 6 to 10 carbon atoms in total, such as phenyl, 3-methoxyphenyl, 4-carbamoylphenyl and the like can be mentioned.

The heterocyclic group represented by R ₂ may have a substituent, may be saturated or unsaturated, and may be condensed. As the substituent, any group can be used as long as it is a group described in the above-mentioned substituent group and can be substituted for the heterocyclic group represented by R ₂ . The heterocyclic group represented by R ₂ is preferably a heterocyclic group having 2 to 16 carbon atoms in total, more preferably a 5 to 6-membered heterocyclic group having 2 to 12 carbon atoms in total, For example, 1-pyrrolidinyl, 4-morpholinyl, 2-pyridyl, 1-pyrrolyl, 1-imidazolyl, 1-benzoimidazolyl and the like can be mentioned.

The aliphatic oxycarbonyl group represented by R ₂ may have a substituent and may be saturated or unsaturated. As the substituent, any group can be used as long as it is the group described in the above-mentioned substituent group and can be substituted for the aliphatic oxycarbonyl group represented by R ₂ . The aliphatic oxycarbonyl group represented by R ₂ is preferably an alkoxycarbonyl group having 1 to 8 carbon atoms in total, more preferably an alkoxycarbonyl group having 1 to 6 carbon atoms in total, such as methoxycarbonyl , I-propyloxycarbonyl, carbamoylmethoxycarbonyl and the like.

The carbamoyl group represented by R ₂ may have a substituent. The substituent may be any group as long as it is a group described in the above-mentioned substituent group and can be substituted for the carbamoyl group represented by R ₂ , and is preferably an aliphatic group, an aryl group, a hetero group. A cyclic group and the like. The carbamoyl group optionally having a substituent represented by R ₂ is preferably a carbamoyl group, an alkylcarbamoyl group having 2 to 9 carbon atoms in total, a dialkylcarbamoyl group having 3 to 10 carbon atoms, or a total carbon atom. An arylcarbamoyl group having 7 to 13 atoms and a heterocyclic carbamoyl group having 3 to 12 carbon atoms, more preferably a carbamoyl group, an alkylcarbamoyl group having 2 to 7 carbon atoms, and 3 to 6 carbon atoms. Dialkylcarbamoyl group, arylcarbamoyl group having 7 to 11 carbon atoms in total, and heterocyclic carbamoyl group having 3 to 10 carbon atoms in total, such as carbamoyl, methylcarbamoyl, dimethylcarbamoyl, phenylcarbamoyl, 4-pyridinecarbamoyl, etc. Is mentioned.

The acylamino group represented by R ₂ may have a substituent, and may be aliphatic, aromatic, or heterocyclic. As the substituent, any group can be used as long as it is the group described in the above-mentioned substituent section and can be substituted with the acylamino group represented by R ₂ . The acylamino group represented by R ₂ is preferably an acylamino group having 2 to 12 carbon atoms, more preferably an acylamino group having 1 to 8 carbon atoms, and still more preferably 1 to 1 carbon atoms. 8 alkylcarbonylamino group, and examples thereof include acetylamino, benzoylamino, 2-pyridinecarbonylamino, propanoylamino and the like.

The sulfonamide group represented by R ₂ may have a substituent, and may be aliphatic, aromatic, or heterocyclic. The substituent is any group as long as it is a group described in the above-mentioned substituent group and can be substituted for the sulfonamide group represented by R ₂ . The sulfonamide group of R ₂ is preferably a sulfonamide group having 1 to 12 carbon atoms in total, more preferably a sulfonamide group having 1 to 8 carbon atoms in total, and still more preferably 1 to 1 carbon atoms in total. 8 alkylsulfonamide groups such as methanesulfonamide, benzenesulfonamide, 2-pyridinesulfonamide and the like.

The carbamoylamino group represented by R ₂ may have a substituent. The substituent may be any group as long as it is a group described in the above-mentioned substituent group and can be substituted on the carbamoylamino group represented by R ₂ , and is preferably an aliphatic group, an aryl group, A heterocyclic group or the like; The carbamoylamino group optionally having a substituent for R ₂ is preferably a carbamoylamino group, an alkylcarbamoylamino group having 2 to 9 carbon atoms in total, a dialkylcarbamoylamino group having 3 to 10 carbon atoms in total, An arylcarbamoylamino group having 7 to 13 carbon atoms and a heterocyclic carbamoylamino group having 3 to 12 carbon atoms, more preferably a carbamoylamino group, an alkylcarbamoylamino group having 2 to 7 carbon atoms, and a total carbon A dialkylcarbamoylamino group having 3 to 6 atoms, an arylcarbamoylamino group having 7 to 11 carbon atoms, and a heterocyclic carbamoylamino group having 3 to 10 carbon atoms, such as carbamoylamino, methylcarbamoylamino, N , N-dimethylcarbamoylamino, phenylcarbamoylamino And 4-pyridinecarbamoylamino.

The sulfamoyl group represented by R ₂ may have a substituent. The substituent may be any group as long as it is a group described in the above-mentioned substituent group and can be substituted on the sulfamoyl group represented by R ₂ , and is preferably an aliphatic group, an aryl group, a hetero group. A cyclic group and the like. The sulfamoyl group optionally having a substituent for R ₂ is preferably a sulfamoyl group, an alkylsulfamoyl group having 1 to 9 carbon atoms in total, a dialkylsulfamoyl group having 2 to 10 carbon atoms in total, An arylsulfamoyl group having 7 to 13 carbon atoms and a heterocyclic sulfamoyl group having 2 to 12 carbon atoms, more preferably a sulfamoyl group, an alkylsulfamoyl group having 1 to 7 carbon atoms, and a total carbon A dialkylsulfamoyl group having 3 to 6 atoms, an arylsulfamoyl group having 6 to 11 carbon atoms, and a heterocyclic sulfamoyl group having 2 to 10 carbon atoms, such as sulfamoyl, methylsulfamoyl, N, N-dimethylsulfamoyl, phenylsulfamoyl, 4-pyridinesulfamoyl and the like can be mentioned.

The aliphatic oxy group represented by R ₂ may have a substituent, and may be saturated or unsaturated. The substituent may be any group as long as it is a group described in the above-mentioned substituent group and can be substituted for the aliphatic oxy group represented by R ₂ . The aliphatic oxy group represented by R ₂ is preferably an alkoxy group having 1 to 8 carbon atoms in total, more preferably an alkoxy group having 1 to 6 carbon atoms in total, such as methoxy, ethoxy, i -Propyloxy, cyclohexyloxy, methoxyethoxy and the like.

The aliphatic thio group represented by R ₂ may have a substituent and may be saturated or unsaturated. As the substituent, any group can be used as long as it is the group described in the above-mentioned substituent section and can be substituted with the aliphatic thio group represented by R ₂ . The aliphatic thio group represented by R ₂ is preferably an alkylthio group having 1 to 8 carbon atoms in total, more preferably an alkylthio group having 1 to 6 carbon atoms in total, for example, methylthio, ethylthio, carbamoyl Examples thereof include methylthio and t-butylthio.

The halogen atom represented by R ₂ is preferably a fluorine atom, a chlorine atom, or a bromine atom, and more preferably a chlorine atom.
In view of the effect of the present invention, R ₂ is preferably an aliphatic oxycarbonyl group or a carbamoyl group which may have a substituent.

  General formulas (A-1) to (A-32) represented by A will be described. The site represented by the general formulas (A-1) to (A-32) preferably has 2 to 15 carbon atoms in total, and more preferably 2 to 12 carbon atoms in total.

As the substituent represented by R _{51 to} R ₅₄ , any group can be used as long as it is the group described in the above-mentioned substituent group and can be substituted as R _{51 to} R ₅₄ . As the substituent represented by R _{51 to} R ₅₄ , an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, an acylamino group, a sulfonamide group An aliphatic oxy group, an aliphatic thio group, a cyano group, etc., more preferably an aliphatic group, an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, an aliphatic oxy group, a cyano group, etc. It is.

In terms of the effects of the present invention, R _{51 to} R ₅₄ are a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, an acylamino group, Preferred is a sulfonamide group, an aliphatic oxy group, an aliphatic thio group, a cyano group, etc., a hydrogen atom, an aliphatic group, an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, an aliphatic group The case where it is an oxy group and a cyano group is more preferable.

As the substituent represented by R ₅₅ , any group can be used as long as it is the group described in the above-mentioned substituent section and can be substituted as R ₅₅ . The substituent represented by R _55, preferably an aliphatic group, an aryl group, a heterocyclic group, more preferably contains an aliphatic group, an aryl group, the nitrogen atom in the position adjacent to the position connected to the nitrogen atom It is an aromatic 5- to 6-membered heterocyclic group.

From the viewpoint of the effect of the present invention, R ₅₅ is preferably an aliphatic group, an aryl group, or a heterocyclic group, and contains a nitrogen atom adjacent to the bonding site with the aliphatic group, aryl group, or nitrogen atom. More preferably, it is an aromatic 5 to 6-membered heterocyclic group, and more preferably an aromatic 5 to 6-membered heterocyclic group containing a nitrogen atom at the position adjacent to the binding site with the nitrogen atom. _R55 is an aromatic 5- to 6-membered heterocyclic group containing a nitrogen atom adjacent to the binding site with the nitrogen atom, so that not only the intermolecular interaction of the dye molecule but also the intramolecular interaction is firmly formed. It becomes easy to do. This makes it easy to construct a pigment having a stable molecular arrangement, which is preferable in terms of showing good hue and high fastness (light resistance, gas, heat, water, etc.).

In terms of the effects of the present invention, the aromatic 5- to 6-membered heterocyclic group containing a nitrogen atom at the position adjacent to the binding site with the nitrogen atom, which is preferable as R ₅₅ , may have a substituent. The substituent may be any group as long as it is a group described in the above-mentioned substituent section and can be substituted on the aromatic 5- to 6-membered heterocyclic group. Preferred substituents include a hydroxy group, An aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, and a carbamoylamino group. Or an aromatic 5- to 6-membered heterocyclic group containing a nitrogen atom at the position adjacent to the binding site with the nitrogen atom having 2 to 12 carbon atoms in total. And more preferably an aromatic 5- to 6-membered heterocyclic group containing a nitrogen atom at the position adjacent to the binding site with the nitrogen atom having 2 to 10 carbon atoms in total. For example, 2-thiazolyl, 2-benzothiazolyl, 2-oxazolyl, 2-benzoxazolyl, 2-pyridyl, 2-pyrazinyl, 3-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 2-imidazolyl, 2-benzimidazolyl, 2-triazinyl and the like can be mentioned, and these heterocyclic groups may have a tautomeric structure together with a substituent.

In terms of the effects of the present invention, the aryl group preferable as R ₅₅ may have a substituent. The substituent may be any group as long as it is a group described in the above-mentioned substituent group and can be substituted for the aryl group. Preferred substituents include a hydroxy group, a nitro group, an aliphatic group, An aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, and a carbamoylamino group. The aryl group for R ₅₅ is preferably an aryl group having 6 to 12 carbon atoms in total, more preferably an aryl group having 6 to 10 carbon atoms in total, such as phenyl, 3-methoxyphenyl, 4-carbamoylphenyl. The phenyl group is preferable.

In terms of the effects of the present invention, the aliphatic group preferable as R ₅₅ may have a substituent. The substituent may be any group as long as it is a group described in the above-mentioned substituent group and can be substituted for the aliphatic group. Preferred substituents include a hydroxy group, a nitro group, and an aliphatic oxy group. A carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, and a carbamoylamino group.
Preferred aliphatic groups as R ₅₅ are preferably alkyl groups having 1 to 6 carbon atoms, more preferably aliphatic groups having 1 to 4 carbon atoms, such as methyl, ethyl, methoxyethyl, carbamoyl. Methyl etc. are mentioned, A methyl group is preferable.

In general formula (1), R ₅₅ is preferably any one of groups represented by the following general formulas (Y-1) to (Y-13), and has a structure that easily takes an intramolecular hydrogen bond structure. Therefore, it is more preferable that it is any of the groups represented by the following general formulas (Y-1) to (Y-6) which are 6-membered rings, and the following general formulas (Y-1) and (Y-3) ), (Y-4), and (Y-6) are more preferred, and the following (Y-1) or (Y-4) may be preferred. Particularly preferred.
* In the following general formulas (Y-1) to (Y-13) represents a binding site with the N atom of the pyrazole ring. Y _{1 to} Y ₁₁ represent a hydrogen atom or a substituent. G ₁₁ in the following general formula (Y-13) represents a nonmetallic atom group capable of constituting a 5- to 6-membered heterocycle, and the heterocycle represented by G ₁₁ is substituted even if the heterocycle is unsubstituted. The heterocycle may be monocyclic or condensed. General formulas (Y-1) to (Y-13) may have tautomeric structures together with substituents.

The substituents represented by Y ₁ to Y _11, a group described in the aforesaid paragraph on substituents may be any substitutable group as in Y ₁ to Y _11. The substituent represented by Y _{1 to} Y ₁₁ is preferably an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, an acylamino group, or a sulfonamide. Group, aliphatic oxy group, aliphatic thio group, cyano group and the like, more preferably aliphatic group, aliphatic oxy group, aliphatic thio group, cyano group and the like. In Y _{1 to} Y ₁₁ , two adjacent substituents may form a 5- to 6-membered ring.
In terms of the effect of the present invention, Y _{1 to} Y ₁₁ are each a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, an acylamino group, Preferred is a sulfonamide group, an aliphatic oxy group, an aliphatic thio group, a cyano group, etc., a hydrogen atom, an aliphatic group, an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, an aliphatic group In the case of an oxy group or a cyano group, it is more preferable.
From the viewpoint of the effect of the present invention, A is preferably a 5-membered heterocycle from the viewpoint of hue, more preferably a nitrogen-containing or sulfur-containing 5-membered heterocycle, and two or more heteroatoms. More preferably, it is a 5-membered heterocycle.

The substituent represented by R _{56 to} R ₅₇ and R ₅₉ may be any group as long as it is the group described in the above-mentioned substituent group and can be substituted as R _{56 to} R ₅₇ and R ₅₉ . As the substituent represented by R _{56 to} R ₅₇ and R ₅₉ , an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, and an acylamino group are preferable. , Sulfonamido group, aliphatic oxy group, aliphatic thio group, cyano group and the like, more preferably aliphatic group, aliphatic oxy group, aliphatic thio group, cyano group and the like.

In terms of the effects of the present invention, R _{56 to} R ₅₇ and R ₅₉ are an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, an acylamino group, A sulfonamide group, an aliphatic oxy group, an aliphatic thio group, a cyano group and the like are preferable, and an aliphatic group, an aliphatic oxy group, an aliphatic thio group, and a cyano group are more preferable.

As the substituent represented by R ₅₈ , any group can be used as long as it is the group described in the above-mentioned substituent section and can be substituted as R ₅₈ . In view of the effect of the present invention, R ₅₈ is preferably a heterocyclic group or an electron-withdrawing group having Hammett's substituent constant σp value of 0.2 or more, and σp value of 0.3 or more. It is preferably an attractive group. The upper limit is 1.0 or less electron withdrawing group.

Here, Hammett's substituent constant σp value used in this specification will be described.
Hammett's rule is a method described in 1935 in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Chemicals” special edition, 122, 96-103, 1979 (Nankodo) ing. In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, but this means that it is limited to only a substituent having a value known in the literature, which can be found in the above-mentioned book. Needless to say, even if the value is unknown, it includes a substituent that would be included in the range when measured based on Hammett's rule. Although the azo pigment represented by the general formula (1) in the present invention is not a benzene derivative, the σp value is used as a scale indicating the electronic effect of the substituent regardless of the substitution position. In the present invention, the σp value will be used in this sense.

Specific examples of R ₅₈ which is an electron-attracting group having a σp value of 0.2 or more include acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphonic group Group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, alkyl halide Groups, halogenated alkoxy groups, halogenated aryloxy groups, halogenated alkylamino groups, halogenated alkylthio groups, aryl groups substituted with other electron-withdrawing groups having a σp value of 0.20 or more, heterocyclic groups, Halogen atom, azo group, or selenoshi Include sulfonate groups.

From the viewpoint of the effects of the present invention, R ₅₈ is preferably a group represented by the general formulas (Y-1) to (Y-13), which makes it easy to take an intramolecular hydrogen bond structure. Therefore, it is more preferable that it is any of the groups represented by the following general formulas (Y-1) to (Y-6) of a 6-membered ring, and the general formulas (Y-1), (Y-3), The case represented by (Y-4) or (Y-6) is more preferred, and the case represented by the general formula (Y-1) or (Y-4) is preferred. Particularly preferred.
Among the heterocyclic groups represented by the general formulas (A-1) to (A-32) listed as A, if the atom adjacent to the carbon atom bonded to the azo group is a heteroatom, light and heat fastness It is preferable to use a pigment having such a structural characteristic in a color filter because a color filter exhibiting high contrast can be obtained.

In view of the effects of the present invention, the azo pigment represented by the general formula (1), G is a hydrogen atom, R ₁ is attached by an amino group which may have a substituent, or a nitrogen atom A saturated heterocyclic group, when m is 0 or 1 and m is 1, R ₂ is an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, or an aliphatic oxy group And A is represented by the general formulas (A-1), (A-10) to (A-17), (A-20) to (A-23), (A-27), (A-28). , (A-30) to (A-32), wherein n is preferably 1 or 2, G is a hydrogen atom, and R ₁ has a substituent. an amino group which may have, or a saturated heterocyclic group connected at the nitrogen atom, a m is 0 or 1, when m is 1, R ₂ is an aliphatic oxy A sulfonyl group, an optionally substituted carbamoyl group, or an aliphatic oxy group, wherein A is a group represented by the general formulas (A-1), (A-10), (A-11), (A- 13) to (A-17), (A-20), (A-22) to (A-23), (A-27), (A-28), (A-30) to (A-32) It is more preferable that n is 1 or 2, and G is a hydrogen atom, and R ₁ may have a substituent, or a nitrogen atom Embedded image wherein m is 0, and A is represented by formulas (A-10), (A-11), (A-13) to (A-17), (A- 20), any one of the groups represented by (A-22) to (A-23), (A-27), (A-28), (A-30) to (A-32), When n is 1 or 2 But more preferably, a G is a hydrogen atom, an amino group which may R ₁ is substituted, a m is 0, A is represented by the general formula (A-16) ~ (A -17), (A-20), (A-28), (A-32), wherein n is particularly preferably 1 or 2, and G is a hydrogen atom. R ₁ is an amino group which may have a substituent, m is 0, A is a group represented by the general formula (A-16), and n is 1 or Most preferred is 2.

From the viewpoint of the effect of the present invention, the azo pigment represented by the general formula (1) is more preferably an azo pigment represented by the following general formula (2). The azo pigment represented by the general formula (2) includes tautomers, salts or hydrates thereof.
The azo pigment represented by the general formula (2) forms a cross-hydrogen bond between Z or R ₅₅ and the hydroxy group of the naphthalene ring and the azo group to improve the planarity of the pigment structure, and the intramolecular and intermolecular interactions. As a result, light fastness, heat fastness, solvent resistance and the like are greatly improved.

  Hereinafter, the azo pigment represented by the general formula (2), tautomers thereof, salts or hydrates thereof will be described in detail.

In the general formula (2), R ₂₁ , R ₂₂ , R ₅₅ , R ₅₉ , m, and n are the same as R ₁ , R ₂ , R ₅₅ , R ₅₉ , m, and n defined in the general formula (1). The same. Z represents an electron withdrawing group having a Hammett's σp value of 0.2 or more. In the case of n = 2, it represents a dimer through the general formula (2), R ₂₁ , R ₂₂ , R ₅₅ , R ₅₉ or Z. When n = 3, general formula (2) represents a trimer via R ₂₁ , R ₂₂ , R ₅₅ , R ₅₉ or Z. When n = 4, the general formula (2) represents a tetramer through R ₂₁ , R ₂₂ , R ₅₅ , R ₅₉ or Z. There is no ionic hydrophilic group in the general formula (2).

Examples of the substituent having a Hammett σp value represented by Z of 0.2 or more include the groups described in the description of R _{58 in} the general formula (1).

Preferred substituents and ranges for R ₂₁ , R ₂₂ , R ₅₅ , R ₅₉ , m, and n of the azo pigment represented by the general formula (2) are R ₁ , R ₂ , R ₅₅ , Same as R ₅₉ , m, and n.
From the viewpoint of the effects of the present invention, Z is preferably an acyl group, a carbamoyl group, an alkyloxycarbonyl group, a cyano group, an alkylsulfonyl group, or a sulfamoyl group, more preferably a carbamoyl group, an alkyloxycarbonyl group, or a cyano group. Most preferred is the group.

In terms of the effects of the present invention, the azo pigment represented by the general formula (2) is an amino group in which R ₂₁ may have a substituent, m is 0 or 1, and m is In the case of 1, R ₂₂ is an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, or an aliphatic oxy group, and R ₅₅ contains a nitrogen atom adjacent to the binding site. An aromatic 5- to 6-membered heterocyclic group, wherein R ₅₉ is a hydrogen atom or an aliphatic group, and Z is an acyl group, a carbamoyl group, an alkyloxycarbonyl group, a cyano group, an alkylsulfonyl group, or a sulfamoyl group And n is preferably 1 or 2, R ₂₁ is an amino group which may have a substituent, m is 0, and R ₅₅ is represented by the general formula (Y-1 ) To (Y-13), and R ₅₉ Is more preferably a hydrogen atom or an aliphatic group, Z is a carbamoyl group, an alkyloxycarbonyl group, or a cyano group, and n is 1 or 2, and R ₂₁ has a substituent. An amino group in which m is 0, R ₅₅ is any one of the groups represented by formulas (Y-1) to (Y-6), and R ₅₉ is a hydrogen atom or More preferably, it is an aliphatic group, Z is a carbamoyl group, an alkyloxycarbonyl group, or a cyano group, and n is 1 or 2, and R ₂₁ is an amino group that may have a substituent. M is 0, R ₅₅ is a group represented by the general formula (Y-1), (Y-4), or (Y-6), and R ₅₉ is a hydrogen atom. More preferably, Z is a cyano group and n is 1 or 2.

  In terms of the effects of the present invention, the azo pigment represented by the general formula (1) or the general formula (2) preferably has “total carbon number / number of azo groups” of 40 or less, and 30 or less. The case is more preferable. In terms of the effects of the present invention, the azo pigment represented by the general formula (1) or the general formula (2) preferably has “molecular weight / number of azo groups” of 700 or less. In view of the effect of the present invention, the azo pigment represented by the general formula (1) or the general formula (2) is preferably not substituted with an isoionic substituent of a sulfo group or a carboxy group.

In another embodiment, the azo compound represented by the general formula (1) has a general formula (A-1) to (A-9), (A-11) to (A-13), (A- 17), preferably a group represented by (A-20) to (A-23), (A-27), (A-28), (A-30) to (A-32), Formula (A-11)-(A-13), (A-17), (A-20)-(A-23), (A-27), (A-28), (A-30)-( A-32) is more preferable, and (A-17), (A-20), (A-22) to (A-23), (A-27), (A-28), (A- 31) and a group represented by (A-32) are more preferred, and a group represented by formulas (A-20), (A-28) and (A-32) is more preferred. And a group represented by formula (A-20) There it is most preferable. In general formula (A-20) group _{R 56} represented by is particularly preferably an _{R 59} in the general formula (2).

The present invention includes in its scope tautomers of the azo pigments represented by the general formula (1) or the general formula (2). The general formula (1) or the general formula (2) is shown in the form of an extreme structural formula among several tautomers that can be taken in terms of chemical structure, but is a tautomer other than the described structure. It may be used as a mixture containing a plurality of tautomers.
For example, the azo pigment represented by the general formula (1) includes an azo-hydrazone tautomer represented by the following general formula (1 ′).
The present invention includes within its scope the pigment represented by the following general formula (1 ′), which is a tautomer of the azo pigment represented by the general formula (1).

In general formula (1 ′), G, R ₁ , R ₂ , m, n, and A are the same as those defined in general formula (1).

Of the azo pigments represented by the general formula (1), examples of the particularly preferred azo pigments represented by the general formula (1) are represented by the following general formulas (3-1) to (3-4). Mention may be made of azo pigments. The azo pigment represented by the general formula (1) is preferably an azo pigment represented by the following general formula (3-1) to general formula (3-4).
The azo pigments represented by general formula (3-1) to general formula (3-4) include tautomers, salts or hydrates thereof.
Hereinafter, the azo pigments represented by the general formulas (3-1) to (3-4), tautomers thereof, salts or hydrates thereof will be described in detail.

In general formula (3-1) to general formula (3-4), R ₁ , R ₂ , m, and n are the same as those defined in general formula (1) and general formula (2). X represents a carbon atom or a nitrogen atom, Ax and Bx together with X and the carbon atom represent an aromatic 5- to 6-membered heterocyclic group, and more specifically, a general formula (A- 1) to the group represented by (A-32). Yx represents that fall out of the heterocyclic group as defined in R ₅₅ in the general formula (1) together with the nitrogen atom and carbon atoms. R ₂₃ represents a substituent corresponding to a group obtained by removing a carbonyl group from the corresponding substituent among substituents such as R ₅₁ , R ₅₄ , R ₅₇ , and R ₅₈ defined in the general formula (1). R ′ ₁ represents a corresponding substituent obtained by removing —NH— from the amino group of R ₁ defined by the general formula (1).

In the azo pigments represented by the general formulas (1), (2), and (3-1) to (3-4), many tautomers can be considered.
In the present invention, the azo pigment represented by the general formula (1) preferably has a substituent that forms an intramolecular hydrogen bond or an intramolecular cross-hydrogen bond. It is more preferable to have at least one substituent that forms an intramolecular hydrogen bond, and it is particularly preferable to have at least one substituent that forms an intramolecular cross-hydrogen bond.

Factors in which this structure is preferable include, as shown by the general formulas (3-1) to (3-4), a nitrogen atom constituting a heterocyclic group contained in the azo pigment structure, a hydrogen atom of the hydroxy group of the naphthalene substituent, and Oxygen atom, nitrogen atom of azo group or its tautomer hydrazone group, carbonyl group substituted for azo component contained in azo pigment structure, hydrogen atom and oxygen atom of hydroxy group of naphthalene substituent, and azo It is mentioned that the nitrogen atom of the hydrazone group which is a group or a tautomer thereof easily forms a cross-hydrogen bond in the molecule.
As a result, the planarity of the molecule is improved, the intramolecular / intermolecular interaction is improved, and the crystallinity of the azo pigment represented by the general formula (3-1) or the general formula (3-4) is increased ( It is more preferable because it is easy to form a higher order structure), and the required performance as a pigment is greatly improved in light fastness, heat stability, wet heat stability, water resistance, gas resistance and / or solvent resistance. An example.
Also from this viewpoint, the azo pigment represented by the general formula (1) is preferably a pigment represented by the general formula (2) or (3-1) to (3-4). ), (3-1) or a pigment represented by (3-2) is more preferred, and an azo pigment represented by the general formula (2) is particularly preferred.

  Specific examples of the azo pigment represented by the general formula (1) are shown below, but the azo pigment used in the present invention is not limited to the following examples. The structures of the following specific examples are shown in the form of an ultimate structural formula among several tautomers that can be taken in terms of chemical structure, but may be tautomeric structures other than those described. Needless to say.

  The azo pigment represented by the general formula (1) of the present invention may have any chemical form as long as the chemical structural formula is the general formula (1), the general formula (2), or a tautomer thereof, and is also called polymorph. It may be a pigment.

  Crystal polymorphs refer to the same chemical composition but different arrangement of building blocks (molecules or ions) in the crystal. The crystal structure determines the chemical and physical properties, and each polymorph can be distinguished by its rheology, color, and other color characteristics. Different polymorphs can also be confirmed by X-Ray Diffraction (powder X-ray diffraction measurement result) or X-Ray Analysis (X-ray crystal structure analysis result).

When a crystalline polymorph exists in the azo pigment represented by the general formula (1) or the general formula (2), any polymorph may be used, and a mixture of two or more polymorphs may be used. However, it is preferable that the main component is a crystal type. That is, it is preferable that the crystalline polymorph is not mixed, and the content of the azo pigment having a single crystal type is 70% to 100%, preferably 80% to 100%, more preferably 90% with respect to the entire azo pigment. -100%, more preferably 95% -100, particularly preferably 100%. By using an azo pigment having a single crystal form as a main component, the regularity of the dye molecule arrangement is improved, the intramolecular / intermolecular interaction is strengthened, and a higher-order three-dimensional network is easily formed. . As a result, it is preferable in terms of performance required for pigments such as improvement of hue, light fastness, heat fastness, humidity fastness, oxidizing gas fastness and solvent resistance.
The mixing ratio of crystal polymorphs in azo pigments is based on solid physicochemical measurements such as single crystal X-ray crystal structure analysis, powder X-ray diffraction (XRD), crystal micrograph (TEM), IR (KBr method), etc. I can confirm.

  The tautomerism and / or crystal polymorphism described above can be controlled by the production conditions during the coupling reaction.

  Further, in the present invention, when the azo pigment represented by the general formula (1) has an acid group, a part or all of the acid group may be in a salt form. Acid type pigments may be mixed. Examples of the salt type include salts of alkali metals such as Na, Li and K, ammonium salts optionally substituted with an alkyl group or hydroxyalkyl group, and organic amine salts. Examples of organic amines include lower alkyl amines, hydroxy-substituted lower alkyl amines, carboxy-substituted lower alkyl amines, and polyamines having 2 to 10 alkyleneimine units having 2 to 4 carbon atoms. In the case of these salt types, the type is not limited to one type, and a plurality of types may be mixed.

  Further, in the structure of the pigment used in the present invention, when a plurality of acid groups are contained in one molecule, the plurality of acid groups may be salt type or acid type and may be different from each other.

  In the present invention, the azo pigment represented by the general formula (1) may be a hydrate containing water molecules in the crystal.

The red coloring composition of the present invention may contain two or more kinds of azo pigments represented by the general formula (1).
In the present specification, the term “azo pigment represented by the general formula (1)” is not limited to one kind of azo pigment represented by the general formula (1), but also two or more kinds of the general formula (1). And a combination of the azo pigment represented by the general formula (1) and other pigments described later.

Next, an example of a method for producing the azo pigment represented by the general formula (1) will be described.
The azo pigment represented by the general formula (1) is, for example, a diazonium non-acidic heterocyclic amine represented by the following general formula (4) and an acidic state with the compound represented by the following general formula (5) The azo pigment represented by the general formula (6) of the present invention can be produced by performing a coupling reaction with the above and performing a post-treatment by a conventional method. The azo pigment represented by the general formula (1) is obtained by performing the same operation using the heterocyclic amine corresponding to A in the general formula (1) instead of the heterocyclic amine represented by the general formula (4). Can be manufactured.

In the general formula (4), R ₅₅ , R ₅₈ and R ₅₉ are synonymous with those defined in the general formula (2).

In the general formula (5), R ₁ , R ₂ and m have the same definitions as those defined in the general formula (1).
The reaction scheme is shown below.

In the general formulas (4) to (6), G, R ₁ , R ₂ , R ₅₅ , R ₅₈ , R ₅₉ , m, and n are defined by the general formula (1) or the general formula (2). It is synonymous.

Heterocyclic amines represented by the amino compounds of the general formulas (4) and (A-1) to (A-32) can be obtained as commercial products, but generally known methods are commonly used. For example, it can manufacture by the method of patent 4022271 gazette. The heterocyclic coupler represented by the general formula (5) can be obtained as a commercial product, but can be produced by the method described in JP-A-2008-13472 and a method analogous thereto.
The diazoniumation reaction of the heterocyclic amine represented by the above reaction scheme is carried out at a temperature of 15 ° C. or less with a reagent such as sodium nitrite, nitrosylsulfuric acid, isoamyl nitrite in an acidic solvent such as sulfuric acid, phosphoric acid, and acetic acid. The reaction can be carried out for about 6 minutes to 6 minutes. The coupling reaction is carried out by reacting the diazonium salt obtained by the above-described method with the compound represented by the general formula (5) at 40 ° C. or less, preferably 25 ° C. or less for about 10 minutes to 12 hours. it can.
In the general formula (1) or the general formula (2), the method for synthesizing the azo pigment in the form where n is 2 or more is R _{1 to} R ₂ , R ₅₅ in the general formula (4) or the general formula (5), In R ₅₉ , R _{58 and the} like, raw materials into which a substitutable divalent, trivalent or tetravalent substituent is introduced can be synthesized and synthesized in the same manner as in the above scheme.
In some cases, crystals are precipitated in this way, but in general, water or an alcohol solvent is added to the reaction solution to precipitate the crystals, and the crystals can be collected by filtration. it can. In addition, an alcohol solvent, water or the like can be added to the reaction solution to precipitate crystals, and the precipitated crystals can be collected by filtration. The crystals collected by filtration can be washed and dried as necessary to obtain an azo pigment represented by the general formula (1).

  Although the azo pigment represented by the general formula (1) or the general formula (2) is obtained as a crude azo pigment (crude) by the above production method, it is desirable to perform a post-treatment when used as a pigment in the present invention. . Examples of post-treatment methods include solvent salt milling, salt milling, dry milling, solvent milling, pigment particle control step by grinding treatment such as acid pasting, solvent heating treatment, resin, surfactant and dispersant. The surface treatment process by etc. is mentioned.

  The azo pigment represented by the general formula (1) or the general formula (2) of the present invention is preferably subjected to solvent heat treatment and / or solvent salt milling as a post-treatment.

The average primary particle diameter of the azo pigment represented by the general formula (1) is preferably 100 nm or less, more preferably 80 nm or less.
The average primary particle diameter of the azo pigment represented by the general formula (1) can be easily adjusted within the above range by, for example, performing solvent salt milling. The average primary particle diameter of the azo pigment can also be adjusted by dry milling or the like.

  As the azo pigment represented by the general formula (1), those having an average primary particle diameter of 100 nm or less by solvent salt milling are preferable, and those having an average primary particle diameter of 80 nm or less are more preferable.

  Examples of the solvent used in the solvent heat treatment include water, aromatic hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as chlorobenzene and o-dichlorobenzene, and alcohols such as isopropanol and isobutanol. Examples thereof include solvents, polar aprotic organic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, glacial acetic acid, pyridine, and mixtures thereof. An inorganic or organic acid or base may be further added to the solvents mentioned above. The temperature of the solvent heat treatment varies depending on the desired average primary particle diameter of the pigment, but is preferably 40 to 150 ° C, more preferably 60 to 100 ° C. The treatment time is preferably 30 minutes to 24 hours.

As solvent salt milling, for example, a crude azo pigment, an inorganic salt, and an organic solvent that does not dissolve the crude azo pigment are charged into a kneader and kneaded and ground therein.
As the inorganic salt, a water-soluble inorganic salt can be preferably used. For example, an inorganic salt such as sodium chloride, potassium chloride, sodium sulfate is preferably used.
It is more preferable to use an inorganic salt having an average primary particle size of 0.5 to 50 μm. The amount of the inorganic salt used is preferably 3 to 20 times by mass, more preferably 5 to 15 times by mass with respect to the crude azo pigment.
As the organic solvent, a water-soluble organic solvent can be suitably used, and the solvent easily evaporates due to a temperature rise during kneading, so that a high boiling point solvent is preferable from the viewpoint of safety. Examples of such organic solvents include diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, diethylene glycol Propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene Glycol or mixtures thereof. The amount of the water-soluble organic solvent used is preferably 0.1 to 5 times by mass with respect to the crude azo pigment. The kneading temperature is preferably 20 to 130 ° C, particularly preferably 40 to 110 ° C. As a kneader, for example, a kneader or a mix muller can be used.

As the solvent salt milling, it is also preferable to use the method described in paragraphs 0007 to 0071 of JP2009-263501A.
That is, this preferred solvent salt milling uses, as an attrition agent, anhydrous sodium sulfate for pigment attrition having an average particle size of 5.5 μm or less and a content of particle size of 10.0 μm or more of 5 vol% or less. Solvent salt milling used.
Here, it is preferable that the anhydrous sodium sulfate for pigment grinding has an average particle size of 2.0 μm or more and 4.0 μm or less, and a content of particle size of 10.0 μm or more is 1% by volume or less. The anhydrous sodium sulfate for pigment grinding preferably has a water content of 1.0% by mass or less. Moreover, it is preferable that the anhydrous sodium sulfate for pigment grinding contains an anti-caking agent.

<(B) Yellow pigment>
Examples of yellow pigments include C.I. among the compounds classified as Pigment in the color index (CI; issued by The Society of Dyers and Colorists). I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc. Etc. can be applied.

  Among these yellow pigments, C.I. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185 are preferable, and C.I. I pigment yellow 139 is more preferable.

<Other pigments>
The pigment dispersion composition of the present invention may contain other pigments in addition to (A) the red pigment and (B) the yellow pigment as long as the object of the present invention is not hindered.

  Other pigments are not particularly limited, for example, azo pigments, disazo pigments, benzimidazolone pigments, condensed azo pigments, azo lake pigments, anthraquinone pigments, diketopyrrolopyrrole pigments, quinacridone pigments, One or more pigments selected from isoindoline pigments, isoindolinone pigments, perinone pigments, perylene pigments and the like and / or derivatives thereof may be used.

Other pigments include compounds classified as Pigments in the Color Index (CI; issued by The Society of Dyers and Colorists), that is, the following Color Index (CI) numbers: Can be mentioned.
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73,
C. I. Pigment Green 7, 10, 36, 37, 58
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 were changed to OH. Things, 80,
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42,
C. I. Pigment Brown 25, 28,
C. I. Pigment Black 1, 7 and the like.
However, the present invention is not limited to these.

Among these, other pigments that can be preferably used include the following.
C. I. Pigment Orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,
C. I. Pigment Violet 19, 23, 29, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Green 7, 36, 37, 58
C. I. Pigment Black 1, 7

  In addition, as other pigments, inorganic pigments may be used. Specific examples thereof include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red rose (red iron oxide (III )), Cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black and the like.

  In particular, in the pigment dispersion composition of the present invention, from the viewpoint of further improving spectral characteristics (hue) as a red pattern (red color filter), in addition to the azo pigment represented by the general formula (1), red It is preferable to contain at least one pigment having a hue selected from (Red), yellow (Yellow), orange (Orange), and violet. These pigments include C.I. exemplified above. I. At least one pigment can be selected from the numbered pigments. Thereby, the transmittance on the short wavelength side (for example, a wavelength of 500 nm or less (more preferably, a wavelength of 400 nm or less)) can be further suppressed, and a better red hue can be obtained.

In the red coloring composition of the present invention, the azo pigment represented by the general formula (1), which is a preferred red pigment, and other pigments (particularly, red, yellow, orange, and violet) are selected. When the pigment having a hue) is used in combination, the content of the other pigment is in the total mass of the pigment in the red coloring composition of the present invention (or the colored curable composition of the present invention including the same), It is preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% by mass or less.
There is no particular limitation on the lower limit of the content of other pigments (in particular, pigments having a hue selected from red, yellow, orange, and violet) contained in addition to the azo pigment represented by the general formula (1). However, from the viewpoint of adjusting the spectral characteristics, 5% by mass is preferable, and 10% by mass is more preferable.

  The total mass of the pigment contained in the red coloring composition of the present invention is preferably 30% by mass to 65% by mass, more preferably 45% by mass to 65% by mass, and 55% by mass to 65% by mass with respect to the solid content. More preferred is mass%.

(Dispersant)
The red coloring composition of the present invention contains at least one dispersant.
There is no limitation in particular as a dispersing agent, A well-known pigment dispersing agent can be used.

  Examples of suitable dispersants include, for example, a graft copolymer containing a nitrogen atom, and at least one repeating unit selected from repeating units represented by any one of the general formulas (I) and (II). Examples thereof include polymer compounds.

<Graft copolymer containing nitrogen atoms>
As the graft copolymer containing a nitrogen atom, those having a repeating unit containing a nitrogen atom in the main chain are preferred. Among these, a graft copolymer having a repeating unit represented by the following general formula (A) and / or a repeating unit represented by the following general formula (B) is preferable.

In the general formula (A), R ₁ represents an alkylene group having 1 to 5 carbon atoms, and A represents a hydrogen atom or a group represented by the following general formulas (C) to (E).
In the general formula (A), R ₁ represents a linear or branched alkylene group having 1 to 5 carbon atoms such as methylene, ethylene or propylene, preferably 2 to 3 carbon atoms, more preferably ethylene. It is a group. A represents either a hydrogen atom or a group represented by the following general formulas (C) to (E), preferably a group represented by the general formula (C).

In general formula (B), R < ₁ > and A are synonymous with R < ₁ > and A in general (A).

In General Formula (C), W ₁ represents a linear or branched alkylene group having 2 to 10 carbon atoms, and among them, an alkylene group having 4 to 7 carbon atoms such as butylene, pentylene, and hexylene is preferable. p represents an integer of 1 to 20, preferably an integer of 5 to 10.

In general formula (D), Y ₁ represents a divalent linking group. Among them, an alkylene group having 1 to 4 carbon atoms such as ethylene and propylene, and an alkyleneoxy having 1 to 4 carbon atoms such as ethyleneoxy and propyleneoxy. Groups are preferred. W ₂ represents a linear or branched alkylene group having 2 to 10 carbon atoms such as ethylene, propylene, or butylene, and among them, an alkylene group having 2 to 3 carbon atoms such as ethylene or propylene is preferable. Y ₂ represents a hydrogen atom or CO—R ₂ (R ₂ represents an alkyl group having 1 to 10 carbon atoms such as ethyl, propyl, butyl, pentyl, hexyl, etc .; 5 is preferred). q represents an integer of 1 to 20, preferably an integer of 5 to 10.

In the general formula (E), W ₃ represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 5 carbon atoms having 1 to 5 hydroxyl groups, and in particular, an alkyl group having 10 to 20 carbon atoms such as stearyl, A C10-20 hydroxyalkyl group having 1-2 hydroxyl groups such as monohydroxystearyl is preferred.

The content of the repeating unit represented by the formula (A) or (B) in the “graft copolymer containing nitrogen atom” is preferably higher, and is usually 50 mol% or more, preferably 70 mol%. That's it. The repeating unit represented by the formula (A) and the repeating unit represented by the formula (B) may both be present, and the content ratio is not particularly limited, but preferably the formula (A) It is preferable to contain a larger number of repeating units. The total number of repeating units represented by formula (A) or formula (B) is usually 1 to 100, preferably 10 to 70, and more preferably 20 to 50. Moreover, repeating units other than Formula (A) and Formula (B) may be included, and examples of other repeating units include an alkylene group and an alkyleneoxy group. The above-mentioned “graft copolymer containing a nitrogen atom” preferably has a terminal of —NH ₂ and —R ₁ —NH ₂ (R ₁ is the same as R ₁ ).

The “graft copolymer containing nitrogen atom” may have a main chain which is linear or branched. The amine value of the graft copolymer is usually 5 to 100 mgKOH / g, preferably 10 to 70 mgKOH / g, more preferably 15 to 40 mgKOH / g or less.
When the amine value is 5 mgKOH / g or more, the dispersion stability can be further improved, and the viscosity can be further stabilized. When the amine value is 100 mgKOH / g or less, the residue can be further suppressed, and the deterioration of the electrical characteristics after the liquid crystal panel is formed can be further suppressed.

  As a weight average molecular weight measured by GPC of the said "graft copolymer containing a nitrogen atom", 3000-100000 are preferable and 5000-50000 are especially preferable. When the weight average molecular weight is 3000 or more, aggregation of the coloring material can be further suppressed, and higher viscosity and gelation can be further suppressed. When it is 100,000 or less, the viscosity increase of the copolymer itself can be further suppressed, and the lack of solubility in the organic solvent can be further suppressed.

  As a method for synthesizing the dispersing agent, a known method can be employed. For example, a method described in JP-B-63-30057 can be used.

<High molecular compound containing at least one repeating unit selected from repeating units represented by any one of general formulas (I) and (II)>
The dispersant in the present invention includes at least one repeating unit selected from repeating units represented by any one of the following general formulas (I) and (II) from the viewpoint of further improving dispersion stability. A polymer compound (hereinafter sometimes referred to as “specific polymer”) is preferred.

In general formulas (I) and (II), R ^{1 to} R ⁶ each independently represents a hydrogen atom or a monovalent organic group, and X ¹ and X ² each independently represent —CO—, — C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group, L ¹ and L ² each independently represent a single bond or a divalent organic linking group, A ¹ and A ² each independently represent a monovalent organic group, m and n each independently represents an integer of 2 to 8, and p and q are each independently an integer of 1 to 100. Represents.

The general formulas (I) and (II) will be described in detail.
In general formulas (I) and (II), R ^{1 to} R ⁶ each independently represent a hydrogen atom or a monovalent organic group. As the monovalent organic group, a substituted or unsubstituted alkyl group is preferable. As an alkyl group, a C1-C12 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.
When the alkyl group has a substituent, examples of the substituent include a hydroxy group, an alkoxy group (preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms), a methoxy group, an ethoxy group, Examples include a cyclohexyloxy group.
Specific examples of preferred alkyl groups include methyl, ethyl, propyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl, 2-hydroxyethyl, A 3-hydroxypropyl group, a 2-hydroxypropyl group, and a 2-methoxyethyl group are exemplified.

In general formulas (I) and (II), R ¹ , R ² , R ⁴ , and R ⁵ are preferably hydrogen atoms, and R ³ and R ⁶ are each a hydrogen atom or a methyl group on the pigment surface. It is most preferable from the viewpoint of adsorption efficiency.

In the general formulas (I) and (II), X ¹ and X ² are each independently —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group. Represents. Among these, —C (═O) O—, —CONH—, or a phenylene group is preferable from the viewpoint of adsorptivity to the pigment, and —C (═O) O— is most preferable.

In general formulas (I) and (II), L ¹ and L ² each independently represent a single bond or a divalent organic linking group. The divalent organic linking group is preferably a substituted or unsubstituted alkylene group or a divalent organic linking group comprising the alkylene group and a hetero atom or a partial structure containing a hetero atom. Here, the alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and particularly preferably an alkylene group having 1 to 4 carbon atoms. Moreover, as a hetero atom in the partial structure containing a hetero atom, an oxygen atom, a nitrogen atom, and a sulfur atom are mentioned, for example, Among these, an oxygen atom or a nitrogen atom is preferable.
Specific examples of preferable alkylene groups include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.
When the alkylene group has a substituent, examples of the substituent include a hydroxy group.
The divalent organic linking group includes a heteroatom or a heteroatom selected from —C (═O) —, —OC (═O) —, and —NHC (═O) — at the end of the above alkylene group. A compound having a partial structure and linked to an adjacent oxygen atom via the heteroatom or a partial structure containing a heteroatom is preferable from the viewpoint of adsorptivity to the pigment. Here, the adjacent oxygen atom means an oxygen atom that is bonded to L ¹ in the general formula (I) and L ² in the general formula (II) on the side chain end side.

In general formulas (I) and (II), A ¹ and A ² each independently represents a monovalent organic group. As the monovalent organic group, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group is preferable.
Examples of preferable alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group.

As the substituent of the substituted alkyl group, a monovalent non-metallic atomic group other than hydrogen is used. Preferred examples include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups. Group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diaryl Amino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy Group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy , Arylsulfoxy group, acyloxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N '-Arylureido group, N', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido group N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido group N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-aryluree Id group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl- N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group , Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group An alkylsulfinyl group, Arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkyls Rufinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkyl Sulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonato group), Alkyl phosphono group _{(-PO 3 (alkyl) 2)} , diaryl phosphono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonate) Group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonatoxy group), dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), diarylphosphonooxy group (— OPO _{3 (aryl) 2),} alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )) Monoalkyl phosphono group _(-OPO 3 H (alkyl)) and its conjugated base group (hereinafter referred to as alkylphosphonato group), monoarylphosphono group _(-OPO 3 H (aryl)) and its conjugate Examples thereof include a base group (hereinafter referred to as an arylphosphonatoxy group), a cyano group, a nitro group, an aryl group, a heteroaryl group, an alkenyl group, an alkynyl group, and a silyl group.
Specific examples of the alkyl group in these substituents include the alkyl groups described above, and these may further have a substituent.
Examples of the substituent include an alkoxy group, aryloxy group, alkylthio group, arylthio group, N, N-dialkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, aryl group, hetero An aryl group, an alkenyl group, an alkynyl group, and a silyl group are preferable from the viewpoint of dispersion stability.

  Specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxy Phenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, Ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group It can be exemplified phosphonophenyl phenyl group.

As A ¹ and A ² , from the viewpoint of dispersion stability and developability, a straight chain having 1 to 20 carbon atoms, a branched structure having 3 to 20 carbon atoms, and a number having 5 to 20 carbon atoms Cyclic alkyl groups are preferable, linear alkyl groups having 4 to 15 carbon atoms, branched alkyl groups having 4 to 15 carbon atoms, and cyclic alkyl groups having 6 to 10 carbon atoms are more preferable. Even more preferred are linear alkyl groups of 6 to 10 and branched alkyl groups of 6 to 12 carbon atoms.

  In general formulas (I) and (II), m and n each independently represents an integer of 2 to 8. In view of dispersion stability and developability, 4 to 6 is preferable, and 5 is most preferable.

  In general formulas (I) and (II), p and q each independently represents an integer of 1 to 100. Two or more different p and different q may be mixed. p and q are preferably 5 to 60, more preferably 5 to 40, and still more preferably 5 to 20 from the viewpoints of dispersion stability and developability.

  As the specific polymer, those containing a repeating unit represented by formula (I) are preferable from the viewpoint of dispersion stability.

  Moreover, as a repeating unit represented by general formula (I), it is more preferable that it is a repeating unit represented by the following general formula (I) -2.

In General Formula (I) -2, R ^{1 to} R ³ each independently represents a hydrogen atom or a monovalent organic group, La represents an alkylene group having 2 to 10 carbon atoms, and Lb represents − C (═O) — or —NHC (═O) —, A ¹ represents a monovalent organic group, m represents an integer of 2 to 8, and p represents an integer of 1 to 100. Represent.

  The repeating unit represented by the general formula (I), (II), or (I) -2 is a simple unit represented by the following general formula (i), (ii), or (i) -2, respectively. The polymer is introduced as a repeating unit of the polymer compound by polymerization or copolymerization.

In general formulas (i), (ii), and (i) -2, R ^{1 to} R ⁶ each independently represent a hydrogen atom or a monovalent organic group, and X ¹ and X ² are each independently Represents —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group, and L ¹ and L ² each independently represent a single bond or a divalent group. La represents an alkylene group having 2 to 10 carbon atoms, Lb represents —C (═O) —, or —NHC (═O) —, and A ¹ and A ² represent Each independently represents a monovalent organic group, m and n each independently represent an integer of 2 to 8, and p and q each independently represents an integer of 1 to 100.

  Preferred specific examples of the monomer represented by the general formula (i), (ii), or (i) -2 [monomer (XA-1) to (XA-23)] are listed below. However, the present invention is not limited to these.

  The specific polymer may contain at least one type of repeating unit selected from the repeating units represented by any one of the general formulas (I) and (II), and may contain only one type. And two or more types may be included.

  In the specific polymer, the content of the repeating unit represented by any one of the general formulas (I) and (II) is not particularly limited, but the total repeating unit contained in the polymer is 100% by mass. In this case, the repeating unit represented by any one of the general formulas (I) and (II) is preferably contained in an amount of 5% by mass or more, more preferably 50% by mass, and 50% by mass to 80% by mass. It is more preferable to contain.

The specific polymer is represented by the above-described general formulas (i), (ii), and (i) -2 and a monomer having a functional group that can be adsorbed to the pigment for the purpose of enhancing adsorption to the pigment. A polymer compound obtained by copolymerizing with a monomer is preferable.
Specific examples of the monomer having a functional group capable of adsorbing to the pigment include a monomer having an acidic group, a monomer having an organic dye structure or a heterocyclic structure, a monomer having a basic nitrogen atom, and an ionic group. A monomer etc. can be mentioned. Of these, monomers having an acidic group, and monomers having an organic dye structure or a heterocyclic structure are preferable from the viewpoint of adsorption to the pigment.

Examples of the monomer having an acidic group include a vinyl monomer having a carboxyl group and a vinyl monomer having a sulfonic acid group.
Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, succinic anhydride, cyclohexanedicarboxylic anhydride, ω- Carboxy-polycaprolactone mono (meth) acrylate can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group. Of these, monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, maleic anhydride, phthalic anhydride, succinic anhydride, and cyclohexanedicarboxylic anhydride from the viewpoint of developing removability of unexposed areas. An addition reaction product with a cyclic anhydride such as

  Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester) and phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester) and the like.

  The specific polymer preferably includes a repeating unit derived from a monomer having an acidic group as described above. By including such a repeating unit, when the pigment dispersion composition of the present invention is applied to a colored curable composition, the development removability of the unexposed area is excellent.

  The specific polymer may contain only one type of repeating unit derived from a monomer having an acidic group, or may contain two or more types.

  In the specific polymer, the content of the acidic group introduced into the side chain by the monomer having an acidic group is preferably 50 mgKOH / g or more, and particularly preferably 50 mgKOH / g to 200 mgKOH / g. That is, in terms of suppressing the formation of precipitates in the developer, the content of the repeating unit derived from the monomer having an acidic group is preferably 50 mgKOH / g or more. In order to effectively suppress the formation of secondary aggregates, which are aggregates of primary particles of pigment, or to effectively weaken the cohesive force of secondary aggregates, the content of acidic groups is 50 mgKOH / g to It is preferable that it is 200 mgKOH / g.

  Examples of the monomer having an organic dye structure or a heterocyclic structure include, for example, specific monomers, maleimides, and maleimide derivatives described in paragraph numbers 0048 to 0070 of JP-A-2009-256572. 1 type selected from a group is mentioned.

  Examples of the monomer having a basic nitrogen atom include (meth) acrylic acid ester, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and (meth) acrylic acid. 1- (N, N-dimethylamino) -1,1-dimethylmethyl, N, N-dimethylaminohexyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N (meth) acrylic acid, N-diisopropylaminoethyl, N, N-di-n-butylaminoethyl (meth) acrylate, N, N-di-i-butylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate, (meth ) Piperidinoethyl acrylate, 1-pyrrolidinoethyl (meth) acrylate, N, N-methyl-2-pyrrole (meth) acrylate And (meth) acrylamides include N- (N ′, N′-dimethylaminoethyl) acrylamide, N- (N ′, N ′), and the like. -Dimethylaminoethyl) methacrylamide, N- (N ', N'-diethylaminoethyl) acrylamide, N- (N', N'-diethylaminoethyl) methacrylamide, N- (N ', N'-dimethylaminopropyl) Acrylamide, N- (N ′, N′-dimethylaminopropyl) methacrylamide, N- (N ′, N′-diethylaminopropyl) acrylamide, N- (N ′, N′-diethylaminopropyl) methacrylamide, 2- ( N, N-dimethylamino) ethyl (meth) acrylamide, 2- (N, N-diethyl) Mino) ethyl (meth) acrylamide, 3- (N, N-diethylamino) propyl (meth) acrylamide, 3- (N, N-dimethylamino) propyl (meth) acrylamide, 1- (N, N-dimethylamino)- 1,1-dimethylmethyl (meth) acrylamide and 6- (N, N-diethylamino) hexyl (meth) acrylamide, morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide, etc. Examples of styrenes include N, N-dimethylaminostyrene, N, N-dimethylaminomethylstyrene, and the like.

  Moreover, it is also possible to use a monomer having a urea group, a urethane group, a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, or a hydroxyl group. Specific examples include monomers having the following structure.

  Examples of the monomer having an ionic group include vinyl monomers having an ionic group (anionic vinyl monomers and cationic vinyl monomers). Examples of the anionic vinyl monomer include alkali metal salts of vinyl monomers having an acidic group, salts with organic amines (eg, tertiary amines such as triethylamine and dimethylaminoethanol), and the like. As the vinyl monomer, the nitrogen-containing vinyl monomer is an alkyl halide (alkyl group: C1-18, halogen atom: chlorine atom, bromine atom or iodine atom); benzyl halide such as benzyl chloride or benzyl bromide; Alkylsulfonic acid esters such as acids (alkyl groups: C1-18); arylsulfonic acid alkyl esters such as benzenesulfonic acid and toluenesulfonic acid (alkyl groups: C1-18); dialkyl sulfates (alkyl groups: C1-4), etc. Quaternized with dialkyldiallylane Such as salt, and the like.

  The monomer having a functional group capable of adsorbing to the pigment can be appropriately selected according to the type of pigment to be dispersed, and these may be used alone or in combination of two or more.

  The specific polymer may further contain a repeating unit derived from a copolymerizable vinyl monomer as long as the effect is not impaired.

  Although it does not restrict | limit especially as a vinyl monomer which can be used here, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, ( Preference is given to meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like. Specific examples of such vinyl monomers include the following compounds. In addition, in this specification, when showing either or both of "acryl and methacryl", it may describe as "(meth) acryl".

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) acrylic acid Diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, ( Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo (meth) acrylate Pentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate And (meth) acrylic acid tribromophenyloxyethyl.

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, etc. are mentioned.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.
Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

A preferred embodiment of the specific polymer has at least a monomer represented by the general formula (i), (ii), or (i) -2, a monomer having an acidic group, or an organic dye structure or a heterocyclic structure. A monomer is copolymerized, and more preferably, at least a monomer represented by the general formula (i) -2 and a monomer having an acidic group are copolymerized.
According to this embodiment, it is possible to provide a pigment dispersion composition that is excellent in pigment adsorption and excellent in developability.

The preferred molecular weight of the specific polymer is preferably a weight average molecular weight (Mw) in the range of 5000 to 100,000 and a number average molecular weight (Mn) in the range of 2500 to 50000. More preferably, the weight average molecular weight (Mw) is in the range of 10,000 to 50,000, and the number average molecular weight (Mn) is in the range of 5,000 to 30,000.
In particular, the weight average molecular weight (Mw) is most preferably in the range of 10,000 to 30000, and the number average molecular weight (Mn) is in the range of 5000 to 15000.
That is, the weight average molecular weight (Mw) of the specific polymer is 1000 or more from the viewpoint of effectively loosening the secondary aggregate, which is an aggregate of primary particles of the pigment, or effectively weakening the reaggregation. It is preferable that Further, from the viewpoint of developability when producing a color filter with the colored curable composition containing the red coloring composition of the present invention, the weight average molecular weight (Mw) of the specific polymer may be 30000 or less. preferable.

The specific polymer includes, for example, a monomer represented by the general formula (i), (ii), or (i) -2, and another radical polymerizable compound (as described above, various monomers). And can be produced by a normal radical polymerization method.
In general, a suspension polymerization method or a solution polymerization method is used. Examples of the solvent used for synthesizing such a specific polymer include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxy. Examples include ethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate. It is done. These solvents may be used alone or in combination of two or more.
In the radical polymerization, a radical polymerization initiator can be used, and a chain transfer agent (eg, 2-mercaptoethanol and dodecyl mercaptan) can be further used.

(Alkali-soluble resin)
The red coloring composition of the present invention may contain an alkali-soluble resin.
The alkali-soluble resin contains a polymer (a) obtained by polymerizing a monomer component essentially comprising a compound represented by the following general formula (ED) (hereinafter sometimes referred to as “ether dimer”). It is also preferable to do. By using the polymer (a), when the red coloring composition of the present invention is applied to a colored curable composition, a cured coating film having excellent heat resistance and transparency can be formed.

  As the alkali-soluble resin, for example, a benzyl (meth) acrylate / (meth) acrylic acid copolymer and a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are also suitable. In addition, a copolymer of 2-hydroxyethyl methacrylate, a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 2-hydroxy -3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / Benzyl methacrylate / methacrylic acid copolymer.

Moreover, in order to improve the crosslinking efficiency of the colored curable composition containing the red coloring composition of the present invention, an alkali-soluble resin having a polymerizable group may be used.
As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful. As an alkali-soluble resin containing these polymerizable groups, an isocyanate group and an OH group are reacted in advance to leave one unreacted isocyanate group and a compound containing a (meth) acryloyl group and an acrylic resin containing a carboxyl group; Urethane-modified polymerizable double bond-containing acrylic resin obtained by the above reaction, unsaturated group-containing acrylic obtained by reaction of an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule Resin, acid pendant type epoxy acrylate resin, OH group-containing acrylic resin and polymerizable double bond-containing acrylic resin obtained by reacting a polymerizable double bond, OH group-containing acrylic resin and isocyanate Resin obtained by reacting a compound having a polymerizable group, Japanese Patent Application Laid-Open No. 2002-229207 And a resin obtained by performing a basic treatment on a resin having an ester group having a leaving group such as a halogen atom or a sulfonate group at the α-position or β-position described in JP-A-2003-335814 Etc. are preferable.

The acid value of the alkali-soluble resin is preferably 30 mgKOH / g to 200 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, and most preferably 70 to 120 mgKOH / g.
Further, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and most preferably 7,000 to 20,000.

  When the alkali-soluble resin is contained in the red coloring composition, the content thereof is preferably 1 to 15% by mass, more preferably 2 to 12% by mass, based on the total solid content of the composition. Yes, particularly preferably 3 to 10% by mass.

  The content of the dispersant (for example, the specific polymer) in the red coloring composition of the present invention is a mass ratio of pigment (all pigments including at least a red pigment and a yellow pigment): dispersant = 1: 0.1. ˜1: 2 is preferable, more preferably 1: 0.2 to 1: 1, and still more preferably 1: 0.4 to 1: 0.7.

<Pigment derivative>
The red coloring composition of the present invention may contain pigment derivatives such as anthraquinone derivatives, triazine derivatives, diketopyrrolopyrrole derivatives, phthalocyanine pigment derivatives, and azo pigment derivatives.
In the red coloring composition of the present invention, when the azo pigment represented by the general formula (1) is used, the dispersion stability is further improved by using a pigment derivative and a dispersant in combination.

A pigment derivative may be used individually by 1 type, and may use 2 or more types together.
In the present invention, a part having affinity with the dispersant or a pigment derivative having a polar group introduced is adsorbed on the surface of the treated pigment, and this is used as an adsorption point of the dispersant, whereby the pigment is made into fine particles. It can be dispersed in the dispersion composition and re-aggregation can be prevented. That is, the pigment derivative has an effect of promoting adsorption of a polymer dispersant such as a specific polymer by modifying the pigment surface.

A suitable example of the pigment derivative is an azo pigment derivative.
Specifically, the azo pigment derivative is a compound in which an azo pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced into a side chain as a substituent.

  Examples of the azo pigment derivative in the present invention include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, and JP-A-8-295810. Those described in Kaihei 11-199796, JP-A 2005-234478, JP-A 2003-240938, JP-A 2001-356210, JP-A 2000-239554, and the like can be used.

  As the azo pigment derivative in the present invention, a compound represented by the following general formula (P1) is particularly preferable among the azo pigment derivatives from the viewpoint of further improving the dispersion stability.

  In general formula (P1), A represents a component capable of forming an azo pigment together with XY. A can be arbitrarily selected as long as it is a compound capable of forming an azo pigment by coupling with a diazonium compound. Specific examples of A will be shown below, but the present invention is not limited to these specific examples.

  In general formula (P1), X is a single bond (meaning that Y is directly connected to —N═N—) or a group selected from a divalent linking group represented by the following structural formula. Represents.

  In general formula (P1), Y represents a group represented by the following general formula (P2).

In general formula (P2), Z represents a lower alkylene group. Z is represented as — (CH ₂ ) _b —, wherein b represents an integer of 1 to 5, preferably 2 or 3. In general formula (P2), —NR ₂ represents a lower alkylamino group or a 5- to 6-membered saturated heterocyclic ring containing a nitrogen atom. The -NR _2, when a lower alkyl amino group _is represented as _{-N (C n H 2n + 1} ) 2, n represents an integer of 1 to 4, preferably represents 1 or 2. On the other hand, when the —NR ₂ represents a 5- to 6-membered saturated heterocycle containing a nitrogen atom, a heterocycle represented by the following structural formula is preferable.

Z and —NR ₂ in formula (P2) each may have a lower alkyl group or an alkoxy group as a substituent. In the general formula (P2), a represents 1 or 2, preferably 2.

  Specific examples (specific examples 1 to 22) of the compound represented by the general formula (P1) are shown below, but the present invention is not limited to these specific examples.

As content of the pigment derivative in the red coloring composition of this invention, 0.1 mass%-80 with respect to all the pigments containing at least red pigments and yellow pigments, such as an azo pigment represented by General formula (1). It is preferably in the range of mass%, more preferably in the range of 1 mass% to 65 mass%, and particularly preferably in the range of 3 mass% to 50 mass%. When the content of the pigment derivative is within this range, the pigment can be dispersed well while keeping the viscosity low, and the dispersion stability after dispersion can be improved.
By applying this red coloring composition to the production of a color filter, the heat resistance of the color filter can be improved. Further, a color filter having high transmittance, excellent color characteristics, and high contrast can be obtained.

<Solvent etc.>
The red coloring composition of the present invention can be suitably prepared using a solvent.
Solvents include fatty acid esters such as ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol; benzene, toluene, xylene Aromatics such as methanol, ethanol, n-propanol, isopropanol, n-butanol; ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol , Polypropylene glycol, trimethylene glycol, hexanetriol, etc. Recalls; Glycerin; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and other alkylene glycol monoalkyl ethers; triethylene glycol dimethyl ether, tri Alkylene glycol dialkyl ethers such as ethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether; ethers such as tetrahydrofuran, dioxane, diethylene glycol diethyl ether; monoethanolamine, diethanolamine, triethanolamine Nitrogen-containing polar organic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone ; Water etc. are mentioned.

Among these solvents, those which are water-soluble may be mixed with water and used as an aqueous medium.
Moreover, you may mix and use 2 or more types chosen from said solvent except water, and may use it as an oil-based medium. In this case, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl It is a mixed solution composed of two or more selected from carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.
The content of the organic solvent in the red coloring composition is preferably such that the total solid content of the composition is 5 to 80% by mass, more preferably 5 to 60% by mass, from the viewpoint of applicability. 10-50 mass% is especially preferable.

  The red coloring composition of this invention may contain other components other than the above as needed.

<Preparation of red coloring composition>
The red coloring composition of the present invention can be prepared through a mixing and dispersing step of mixing and dispersing using various mixers and dispersers.
The mixing and dispersing step preferably comprises kneading and dispersing followed by fine dispersion treatment, but kneading and dispersing can be omitted.

  Specifically, the red coloring composition of the present invention uses, for example, a azo pigment represented by the general formula (1), which is a red pigment, a yellow pigment, a dispersant, an azo pigment derivative, and a solvent, using a dispersion device. It is preferable to obtain by dispersing.

  Dispersing devices include simple stirrer, impeller stirring method, in-line stirring method, mill method (for example, colloid mill, ball mill, sand mill, bead mill, attritor, roll mill, jet mill, paint shaker, agitator mill, etc.), ultrasonic method Further, a high-pressure emulsification dispersion system (high-pressure homogenizer; specific commercially available devices such as gorin homogenizer, microfluidizer, DeBEE2000, etc.) can be used.

More specifically, the red coloring composition of the present invention includes, for example, an azo pigment represented by the general formula (1), a yellow pigment, a dispersant, an azo pigment derivative, and a solvent, a vertical or horizontal sand grinder. Using a pin mill, a slit mill, an ultrasonic disperser, or the like, fine dispersion can be performed with beads made of glass having a particle diameter of 0.01 mm to 1 mm, zirconia, or the like.
In addition, before carrying out fine dispersion with beads, use a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single-screw or twin-screw extruder, etc. It is also possible to carry out the kneading and dispersing process while giving.

For details on kneading and dispersing, see T.W. C. “Paint Flow” by Patton
and Pigment Dispersion "(published by John Wiley and Sons, 1964), etc., and the method described herein can also be applied to the present invention.

[Colored curable composition]
The colored curable composition of the present invention contains the above-described red colored composition of the present invention, a photopolymerization initiator, and a polymerizable compound.
The colored curable composition of the present invention has the above-described constitution, whereby the dispersion stability of the pigment such as the azo pigment represented by the general formula (1) is improved and the fine colored pattern is obtained. The pattern performance of the colored pattern can be improved.

<Photopolymerization initiator>
The colored curable composition of the present invention contains a photopolymerization initiator.
Examples of the photopolymerization initiator include a benzophenone photopolymerization initiator, an acetophenone photopolymerization initiator, a benzoin photopolymerization initiator, a benzoin ether photopolymerization initiator, a thioxanthone photopolymerization initiator, and an anthraquinone photopolymerization initiator. 1 or more types selected from an agent, a naphthoquinone photopolymerization initiator, a triazine photopolymerization initiator, and an oxime photopolymerization initiator. A known photosensitizer may be used together with these photopolymerization initiators.
Among these, an oxime photopolymerization initiator is preferable from the viewpoint of improving pattern formability (pattern curability) and suppressing development residue.
The oxime photopolymerization initiator is preferably a compound that decomposes by light and initiates and accelerates a polymerization reaction of a radical polymerizable monomer, and more preferably has an absorption in a wavelength region of 300 to 500 nm. The reason why the oxime photopolymerization initiator is good is presumed that a rectangular pattern can be formed after development because the decomposition efficiency by light is extremely high and higher curability is obtained.

  Examples of the oxime photopolymerization initiator in the present invention include J.I. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP 2000-66385 A, JP 2000-80068 A (paragraph numbers 0004-0296), Special Table 1004-534797 And the compounds described in JP-A-2001-233842, WO-02 / 100903A1, JP-A-2006-342166 (paragraph numbers 0004-0264), and the like.

  Moreover, as an oxime system initiator, the compound represented by the following general formula (O-I) is preferable from a viewpoint of obtaining the effect of pattern formation improvement and development residue suppression more effectively.

In General Formula (O-I), R ¹ represents an alkyl group or an aryl group which may have a substituent. R ² represents an acyl group which may have a substituent, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. The alkynyl group which may have or the acetyl group which may have a substituent is represented. R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a monovalent organic group. R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ may combine with each other to form a 5-membered ring or a 6-membered ring.
Here, examples of the substituent that can be introduced into the alkyl group, aryl group, and acyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-propyl group, a t-butyl group, A chloro group, a bromo group, etc. are mentioned.

Preferred R ¹ is an alkyl group having 1 to 12 carbon atoms or a 4- (alkylthio having 1 to 4 carbon atoms) phenyl group. Preferred R ² is an acetyl group or an acyl group.
Preferred organic groups when R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ represent a monovalent organic group include a methyl group, an ethyl group, a methoxy group, an ethoxy group, a phenoxy group, and a thiophenoxy group. Among them, a phenoxy group and a thiophenoxy group are preferable.
R ³ , R ⁴ , R ⁶ and R ⁷ are preferably hydrogen atoms. R ⁵ is preferably a group represented by —SR ⁸ , where R ⁸ represents a phenyl group which may have a substituent. More preferred R ⁵ is a group represented by the following formula.

  Among the oxime initiators represented by the general formula (O-I), examples of suitable oxime initiators include compounds represented by the following general formula (O-II).

In general formula (O-II), R ⁹ has the same meaning as R ² in general formula (O-I). X ³ represents a monovalent substituent, and when n 2 represents an integer of 2 to 5, a plurality of X ³ may be the same or different from each other. A ⁰ represents a divalent organic group, and Ar represents an aryl group. n2 is an integer of 1-5.

In the general formula (O-II), examples of the monovalent organic group represented by X ³ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-propyl group, and a t-butyl group. , A methoxy group, an ethoxy group, and the like.
In the general formula (O-II), examples of the divalent organic group represented by A ⁰ include alkylene having 1 to 12 carbon atoms, cyclohexylene, and alkynylene.

In general formula (O-II), the aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and the aryl group may have a substituent. Examples of the substituent that can be introduced into the aryl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-propyl group, a t-butyl group, a methoxy group, and an ethoxy group.
Among these, Ar is preferably a substituted or unsubstituted phenyl group from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  In the present invention, specific examples of the oxime photoinitiator include the following compounds (I-1) to (I-6), and particularly preferred compounds are included in the general formula (O-I). (I-2) to (I-6). Among them, (I-2) is most preferable because the development residue at the time of pattern formation is particularly small.

  Specific names of oxime photopolymerization initiators that can be used in the present invention include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2 -(O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2- Hexanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl]- 1,2-octanedione, 2- (O-benzoyloxime) -1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-ben Iloxime) -1- [4- (ethylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl -6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazole-3 -Yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O- Cetyl) -1- [9-ethyl-6- (2-butyl benzoyl) -9H- carbazol-3-yl] ethanone and the like. However, it is not limited to these.

  Particularly preferred specific examples of the oxime photopolymerization initiator include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime)- 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone. Examples of such oxime photopolymerization initiators include CGI-124 and CGI-242 (manufactured by Ciba Specialty Chemicals).

As content of the photoinitiator (for example, oxime type photoinitiator) in the colored curable composition of this invention, it is preferable that it is 1.0 mass%-15.0 mass% in a total solid. 1.0 mass% to 12.5 mass% is more preferable, 1.0 mass% to 10.0 mass% is still more preferable, and 1.0 mass% to 5.0 mass% is more preferable. It is particularly preferred.
Within this range, good sensitivity, pattern formability, and coating film uniformity can be obtained.

<Polymerizable compound>
The colored curable composition of the present invention contains at least one polymerizable compound.
As the polymerizable compound, a known polymerizable compound can be used, and it may be a monofunctional polymerizable compound, but from the viewpoint of further improving pattern formation, a polyfunctional polymerizable compound is preferable, A trifunctional or higher functional polymerizable compound is more preferable.
The polymerizable compound is preferably an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. More preferably. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. The polymerizable compound has a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof.

Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.
Moreover, as a polymeric compound, you may use the polymeric compound described in Unexamined-Japanese-Patent No. 2009-256572 paragraph number 0118-0128.

  In addition, the polymerizable compound in the present invention is described in paragraph numbers 0029 to 0056 of JP2009-244807A and paragraphs 0038 to 0051 of JP2009-229761 from the viewpoint of pattern formation and the like. A photocurable compound (polymerizable compound), for example, at least one polymerizable compound selected from the group of compounds represented by the following general formula (Mi) or (M-ii) preferable.

In general formulas (M-i) and (M-ii), each E independently represents — ((CH ₂ ) _y CH ₂ O) — or — ((CH ₂ ) _y CH (CH ₃ ) O). -Represents each independently an integer of 0 to 10, and each X independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.
In general formula (Mi), the sum total of the acryloyl group and the methacryloyl group is 3 or 4, m represents the integer of 0-10 each independently, and the sum of each m is an integer of 0-40. is there. However, when the total of each m is 0, any one of X is a carboxyl group.
In general formula (M-ii), the sum total of acryloyl group and methacryloyl group is 5 or 6, each n independently represents an integer of 0 to 10, and the sum of each n is an integer of 0 to 60. is there. However, when the total of each n is 0, any one of X is a carboxyl group.

In general formula (Mi), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Moreover, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable as the sum total of each m.
In general formula (M-ii), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Further, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
In general formula (M-i) or the general formula (M-ii) in the _{- ((CH 2) y CH} 2 O) - or _{- ((CH 2) y CH} (CH 3) O) - , the oxygen A form in which the end on the atom side is bonded to X is preferred.

The compounds represented by the general formula (M-i) or (M-ii) may be used alone or in combination of two or more. In particular, in the general formula (M-ii), a form in which all six Xs are acryloyl groups is preferable.
Yes.

  The compound represented by the general formula (M-i) or (M-ii) is obtained by a ring-opening addition reaction of ethylene oxide or propylene oxide with pentaerythritol or dipentaerythritol, which is a conventionally known process. It can be synthesized from a step of bonding a ring-opening skeleton and a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with a terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (Mi) or (M-ii).

  Among the compounds represented by the formulas (Mi) and (M-ii), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable. Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”), and among them, exemplary compounds (a) and (b) ), (C), (f) are preferred.

  Examples of commercially available products of the specific photocurable compounds represented by the formulas (M-i) and (M-ii) include SR-494 which is a tetrafunctional acrylate having four ethyleneoxy groups manufactured by Sartomer, Nippon Kayaku. Examples thereof include DPCA-60, which is a hexafunctional acrylate having 6 pentyleneoxy groups, and TPA-330, which is a trifunctional acrylate having 3 isobutyleneoxy groups.

  As content of the polymeric compound in the colored curable composition of this invention, it is preferable that it is 5 mass%-70 mass% with respect to the total solid, and it is more preferable that it is 10 mass%-60 mass%. preferable.

<Alkali-soluble resin>
The colored curable composition of the present invention preferably further contains an alkali-soluble resin. By containing an alkali-soluble resin, developability and pattern formation are improved.

  The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group (for example, carboxyl group, phosphoric acid group, sulfonic acid group, etc.). Of these, more preferred are those which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.

  For production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

As the linear organic polymer used as the alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferable, such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, and a crotonic acid copolymer. , Maleic acid copolymers, partially esterified maleic acid copolymers, etc., acidic cellulose derivatives having a carboxylic acid in the side chain, and polymers having a hydroxyl group added with an acid anhydride. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Examples of vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile,
Examples thereof include vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, and polymethyl methacrylate macromonomer.

  The alkali-soluble resin may contain a polymer (a) obtained by polymerizing a monomer component essentially containing a compound represented by the following general formula (ED) (hereinafter also referred to as “ether dimer” as appropriate). preferable.

  By using the polymer (a), the colored curable resin composition of the present invention can form a cured coating film that is extremely excellent in heat resistance and transparency.

In General Formula (ED), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

In the general formula (ED), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited, and examples thereof include methyl, ethyl, n Linear or branched alkyl groups such as -propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, t-butylcyclohexyl , Alicyclic groups such as dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; benzyl An alkyl group substituted with an aryl group such as; Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance.

  Specific examples of the ether dimer include dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di ( n-propyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2,2 '-[Oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2'-[oxybis (methylene)] bis-2-propenoate Di (stearyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2-ethylhexyl) ) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-ethoxyethyl) ) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 ′-[oxybis (methylene) Bis-2-propenoate, dicyclohexyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) Cyclohexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tricyclo Decanyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 ′ -[Oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate and the like. Among these, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2′- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be only one kind or two or more kinds.

  The proportion of the ether dimer in the monomer for obtaining the polymer (a) is not particularly limited, but from the viewpoint of the transparency and heat resistance of the coating film formed from the colored curable resin composition, In a body component, 2-60 mass% is preferable, More preferably, it is 5-55 mass%, More preferably, it is 5-50 mass%.

  The polymer (a) may be a copolymer obtained by copolymerizing other monomers together with an ether dimer.

  Other monomers that can be copolymerized with the ether dimer include, for example, a monomer for introducing an acid group, a monomer for introducing a radical polymerizable double bond, and an epoxy group. Monomers and other copolymerizable monomers other than these may be mentioned. Only 1 type may be used for such a monomer and it may use 2 or more types.

Examples of the monomer for introducing an acid group include monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid, monomers having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide, maleic anhydride, and anhydride. And monomers having a carboxylic anhydride group such as itaconic acid. Among these, (meth) acrylic acid is particularly preferable.
The monomer for introducing an acid group may be a monomer that can give an acid group after polymerization, for example, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, Examples thereof include a monomer having an epoxy group such as glycidyl (meth) acrylate, and a monomer having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate. When using a monomer for introducing a radical polymerizable double bond, when using a monomer capable of imparting an acid group after polymerization, it is necessary to perform a treatment for imparting an acid group after polymerization. The treatment for adding an acid group after polymerization varies depending on the type of monomer, and examples thereof include the following treatment. In the case of using a monomer having a hydroxyl group, for example, a treatment of adding an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride or the like can be mentioned. In the case of using a monomer having an epoxy group, for example, a compound having an amino group and an acid group such as N-methylaminobenzoic acid or N-methylaminophenol is added, or, for example, (meth) acrylic For example, a treatment of adding an acid anhydride such as succinic acid anhydride, tetrahydrophthalic acid anhydride, maleic acid anhydride to the hydroxyl group generated after adding an acid such as an acid can be mentioned. In the case of using a monomer having an isocyanate group, for example, a treatment of adding a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid can be mentioned.

  When the monomer for obtaining the polymer (a) includes a monomer for introducing an acid group, the content ratio is not particularly limited, but is 5 to 70% by mass in all monomer components. Preferably, it is 10-60 mass%.

  Examples of the monomer for introducing a radical polymerizable double bond include, for example, monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid; carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride Monomers having a group; monomers having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether; . When using a monomer for introducing a radical polymerizable double bond, it is necessary to perform a treatment for imparting a radical polymerizable double bond after polymerization. The treatment for imparting a radical polymerizable double bond after polymerization differs depending on the type of monomer that can impart a radical polymerizable double bond to be used, and examples thereof include the following treatment. If a monomer having a carboxyl group such as (meth) acrylic acid or itaconic acid is used, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p- ) Treatment of adding a compound having an epoxy group such as vinylbenzyl glycidyl ether and a radically polymerizable double bond. In the case of using a monomer having a carboxylic anhydride group such as maleic anhydride or itaconic anhydride, a treatment for adding a compound having a hydroxyl group and a radical polymerizable double bond such as 2-hydroxyethyl (meth) acrylate Is mentioned. If a monomer having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzylglycidyl ether is used, (meth) The process which adds the compound which has acid groups, such as acrylic acid, and a radically polymerizable double bond is mentioned.

  When the monomer for obtaining the polymer (a) includes a monomer for introducing a radical polymerizable double bond, the content ratio is not particularly limited, but among all monomer components, 70 mass% is preferable, More preferably, it is 10-60 mass%.

Examples of the monomer for introducing an epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. Can be mentioned.
When the monomer for obtaining the polymer (a) includes a monomer for introducing an epoxy group, the content ratio is not particularly limited, but is 5 to 70% by mass in all monomer components. Preferably, it is 10-60 mass%.

  Examples of other copolymerizable monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylate n. -Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2- (meth) acrylic acid 2- (Meth) acrylic acid esters such as hydroxyethyl; aromatic vinyl compounds such as styrene, vinyltoluene and α-methylstyrene; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; butadiene, isoprene and the like Butadiene or substituted butadiene compounds; ethylene, propylene, vinyl chloride Ethylene or substituted ethylene compound such as acrylonitrile, vinyl esters such as vinyl acetate; and the like. Among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable in terms of good transparency and resistance to heat resistance.

  When the monomer for obtaining the polymer (a) contains other copolymerizable monomers, the content is not particularly limited, but is preferably 95% by mass or less, and 85% by mass or less. More preferred.

The weight average molecular weight of the polymer (a) is not particularly limited, but is preferably 2000 to 200000, more preferably from the viewpoint of the viscosity of the colored curable resin composition and the heat resistance of the coating film formed from the composition. It is 5000-100000, More preferably, it is 5000-20000.
When the polymer (a) has an acid group, the acid value is preferably 30 to 500 mgKOH / g, more preferably 50 to 400 mgKOH / g.

The polymer (a) can be easily obtained by polymerizing at least the above monomer having an ether dimer as an essential component. At this time, the cyclization reaction of the ether dimer proceeds simultaneously with the polymerization to form a tetrahydropyran ring structure.
There is no restriction | limiting in particular as a polymerization method applied to the synthesis | combination of a polymer (a), Although conventionally well-known various polymerization methods can be employ | adopted, It is preferable especially by a solution polymerization method. Specifically, for example, the polymer (a) can be synthesized according to the method for synthesizing the polymer (a) described in JP-A-204-300204.

  Hereinafter, although the exemplary compound of a polymer (a) is shown, this invention is not limited to these. The composition ratio of the exemplary compounds shown below is mol%.

  Among these alkali-soluble resins, particularly preferred are benzyl (meth) acrylate / (meth) acrylic acid copolymers and benzyl (meth) acrylate / (meth) acrylic acid / other monomeric multi-component monomers. A polymer is included. In addition, a copolymer of 2-hydroxyethyl methacrylate, a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 2-hydroxy -3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / Benzyl methacrylate / methacrylic acid copolymer.

Moreover, in order to improve the crosslinking efficiency of the colored curable composition in the present invention, an alkali-soluble resin having a polymerizable group may be used.
As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful. As an alkali-soluble resin containing these polymerizable groups, an isocyanate group and an OH group are reacted in advance to leave one unreacted isocyanate group and a compound containing a (meth) acryloyl group and an acrylic resin containing a carboxyl group; Urethane-modified polymerizable double bond-containing acrylic resin obtained by the above reaction, unsaturated group-containing acrylic obtained by reaction of an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule Resin, acid pendant type epoxy acrylate resin, OH group-containing acrylic resin and polymerizable double bond-containing acrylic resin obtained by reacting a polymerizable double bond, OH group-containing acrylic resin and isocyanate Resin obtained by reacting a compound having a polymerizable group, Japanese Patent Application Laid-Open No. 2002-229207 And a resin obtained by performing a basic treatment on a resin having an ester group having a leaving group such as a halogen atom or a sulfonate group at the α-position or β-position described in JP-A-2003-335814 Etc. are preferable.

The acid value of the alkali-soluble resin is preferably 30 mgKOH / g to 200 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, and most preferably 70 to 120 mgKOH / g.
Further, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and most preferably 7,000 to 20,000.

  As content in the colored curable composition of alkali-soluble resin, 0.5 mass%-15 mass% are preferable with respect to the total solid of this composition, More preferably, 1 mass%-12 mass% Especially preferably, it is 1 mass%-10 mass%.

<Solvent>
In general, the colored curable composition of the present invention can be suitably prepared by using a solvent together with the aforementioned components.
Examples of the solvent used 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 lactic acid. Methyl, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate; methyl 3-oxypropionate, ethyl 3-oxypropionate Alkyl 3-esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxy Ethyl propionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy- Methyl 2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, pyruvate Propyl, 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 No ethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones such as methyl ethyl ketone , Cyclohexanone, 2-heptanone, 3-heptanone and the like; aromatic hydrocarbons such as toluene and xylene.

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, propylene glycol methyl ether acetate, etc. Is preferred.
You may use a solvent in combination of 2 or more types besides using independently.

<Surfactant>
Various surfactants may be added to the colored curable composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, and an anionic surfactant can be used.
In particular, by containing a fluorosurfactant, the liquid properties (particularly fluidity) when used as a coating liquid can be further improved, and the uniformity of coating thickness and liquid saving can be further improved.
That is, in a colored photosensitive composition containing a fluorosurfactant, the wettability to the coated surface is improved by lowering the interfacial tension between the coated surface and the coating liquid, and coating onto the coated surface is performed. Improves. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

  The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. When the fluorine content is within this range, it is effective in terms of coating thickness uniformity and liquid-saving properties, and the solubility in the composition is also good.

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F780, F781 (above, manufactured by DIC Corporation), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC- 103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, K393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), "Solsperse 20000 (Nippon Lubrizol ( Etc.).

  In particular, the fluorosurfactant is effective in preventing coating unevenness and thickness unevenness when forming a thin coating film using the colored photosensitive composition of the present invention. Furthermore, it is also effective when the colored photosensitive composition of the present invention is applied to slit coating that easily causes liquid breakage.

  Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, etc. It is.

  Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

  Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.

Examples of silicone surfactants include Toray Dow Corning Co., Ltd. “Torre Silicone DC3PA”, “Torre Silicone SH7PA”, “Torre Silicone DC11PA”, “Torre Silicone SH21PA”, “Torre Silicone SH28PA”, “Torre Silicone” “SH29PA”, “Tore Silicone SH30PA”, “Tore Silicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF-” manufactured by Momentive Performance Materials, Inc. 4452 ”,“ KP341 ”,“ KF6001 ”,“ KF6002 ”manufactured by Shin-Etsu Silicone Co., Ltd.,“ BYK307 ”,“ BYK323 ”,“ BYK330 ”manufactured by BYK Chemie, and the like.
Only one type of surfactant may be used, or two or more types may be combined.

  The addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass and more preferably 0.005% by mass to 1.0% by mass with respect to the total mass of the colored photosensitive composition. .

<Thermal polymerization inhibitor>
Furthermore, you may add a thermal-polymerization inhibitor (polymerization inhibitor) to the coloring photosensitive composition of this invention.
Examples of the thermal polymerization inhibitor include 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, and the like are useful.

<Other ingredients>
In the colored curable composition of the present invention, if necessary, a sensitizing dye, an epoxy resin, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, a filler, a polymer compound other than the alkali-soluble resin, Various additives such as an adhesion promoter represented by a silane coupling agent, an antioxidant, an ultraviolet absorber, and an anti-aggregation agent can be contained.
As other components, for example, each component described in paragraphs 0155 to 0217 of JP-A-2009-256572 can be used.

  The colored curable composition of the present invention comprises a polymerizable compound, a photopolymerization initiator, and, if necessary, an alkali-soluble resin, a solvent, and a surfactant with respect to the pigment dispersion composition of the present invention described above. It can prepare by adding additives, such as.

  When the colored curable composition of the present invention contains an azo pigment represented by the general formula (1) as a red pigment, the pigment dispersibility is further improved and the color characteristics are also excellent.

  The colored curable composition of the present invention is preferably used for forming a colored region of a color filter that requires fine and good color characteristics. Examples of the color filter include color filters for solid-state image sensors, liquid crystal display devices, and organic EL display devices, and solid-state image sensor color filters are particularly preferable.

≪Color filter for solid-state imaging device and manufacturing method thereof≫
The method for producing a color filter for a solid-state imaging device of the present invention comprises a step of forming a colored curable composition layer by applying the above-described colored curable composition of the present invention on a support (hereinafter referred to as “colored curing”). Development of the colored curable composition layer after exposure), a step of exposing the colored curable composition layer through a mask (hereinafter also referred to as “exposure process”), and developing the colored curable composition layer after exposure. Forming a colored pattern (hereinafter also referred to as “colored pixel”) (hereinafter also referred to as “developing step”).
Moreover, the color filter for solid-state image sensors of this invention is manufactured by the manufacturing method of the color filter for solid-state image sensors of this invention.

The color filter for solid-state image sensor of the present invention only needs to have at least a red pattern (red pixel) manufactured by the method for manufacturing a color filter for solid-state image sensor of the present invention.
As a specific form of the color filter for a solid-state imaging device of the present invention, for example, at least a form of a multicolored color filter that combines a red pattern and another colored pattern (for example, at least a red pattern, a blue pattern, and a green pattern) A color filter having three or more colors is preferable.
Hereinafter, the color filter for the solid-state imaging device may be simply referred to as “color filter”.

<Colored curable composition layer forming step>
In the colored curable composition layer forming step, the colored curable composition layer of the present invention is applied to the support to form the colored curable composition layer.
As a support that can be used in this step, for example, a solid-state imaging device in which an imaging device (light receiving device) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) is provided on a substrate (for example, a silicon substrate). A substrate can be used.
The colored pattern in the present invention may be formed on the imaging element forming surface side (front surface) of the solid-state imaging element substrate, or may be formed on the imaging element non-forming surface side (back surface).
A light-shielding film may be provided between the image sensors on the solid-state image sensor substrate or on the back surface of the solid-state image sensor substrate.
Further, if necessary, an undercoat layer may be provided on the support for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface.

  As a method for applying the colored curable composition of the present invention to the support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like can be applied. .

  The coating thickness of the colored curable composition layer is preferably 0.1 μm to 5 μm, more preferably 0.2 μm to 2 μm, and even more preferably 0.2 μm to 1 μm.

  The colored curable composition layer applied on the substrate can be dried (pre-baked) at a temperature of 50 ° C. to 140 ° C. for 10 seconds to 300 seconds using a hot plate, oven, or the like.

<Exposure process>
In the exposure step, the colored curable composition layer formed in the colored curable composition layer forming step is subjected to pattern exposure using an exposure device such as a stepper through a mask having a predetermined mask pattern.
As radiation (light) that can be used for exposure, ultraviolet rays such as g-line and i-line are particularly preferable (particularly preferably i-line). Irradiation dose (exposure amount) is more preferably preferably ^{50~1000mJ / cm 2 30~1500mJ / cm 2} , 80~500mJ / cm 2 being most preferred.

<Development process>
Next, by performing an alkali development treatment, the colored curable composition layer of the non-light-irradiated portion in the exposure step is eluted in the alkaline aqueous solution, and only the photocured portion remains.
The developer is preferably an organic alkali developer that does not cause damage to the underlying image sensor or circuit. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.

Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5, 4, 0] -7-undecene and the like, and an alkaline aqueous solution obtained by diluting these alkaline agents with pure water so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. Is preferably used as a developer.
In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

Next, it is preferable to carry out heat treatment (post-bake) after washing away excess developer and drying.
If a multicolor coloring pattern is to be formed, a cured film can be produced by sequentially repeating the above steps for each color. Thereby, a color filter is obtained.
The post-baking is a heat treatment after development to complete the curing, and a heat curing treatment is usually performed at 150 to 240 ° C., preferably 180 to 240 ° C.
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater or the like so that the coating film after development is in the above condition. be able to.

  In addition, the manufacturing method of this invention may have a well-known process as a manufacturing method of the color filter for solid-state image sensors as processes other than the above as needed. For example, after performing the above-described colored curable composition layer forming step, exposure step, and development step, a curing step of curing the formed colored pattern by heating and / or exposure may be included as necessary. .

In addition, when using the colored curable composition of the present invention, for example, clogging of the nozzle of the coating device discharge section and piping, clogging of the colored curable composition and pigment in the coating machine due to adhesion, sedimentation, drying, etc. May occur. Therefore, in order to efficiently clean the contamination caused by the colored curable composition of the present invention, it is preferable to use the solvent related to the present composition as the cleaning liquid. JP-A-7-128867, JP-A-7-146562, JP-A-8-278737, JP-A-2000-273370, JP-A-2006-85140, JP-A-2006-291191, The cleaning liquids described in JP2007-2101A, JP2007-2102A, JP2007-281523A, and the like can also be suitably used for cleaning and removing the colored curable composition according to the present invention.
Of the above, alkylene glycol monoalkyl ether carboxylate and alkylene glycol monoalkyl ether are preferred.
These solvents may be used alone or in combination of two or more. When mixing 2 or more types, it is preferable to mix the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group. The mass ratio of the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 80/20. In a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), the ratio is particularly preferably 60/40. In addition, in order to improve the permeability of the cleaning liquid with respect to contaminants, a surfactant related to the present composition described above may be added to the cleaning liquid.

  Since the color filter for solid-state imaging device of the present invention uses the colored curable composition of the present invention, it has excellent spectral characteristics, suppressed development residue, and excellent heat resistance of the colored pattern. . Moreover, when formed using the azo pigment represented by the general formula (1), the spectral characteristics as red are particularly excellent.

  The color filter for a solid-state imaging device of the present invention can be suitably used for a solid-state imaging device such as a CCD or CMOS, and is particularly suitable for a CCD or CMOS having a high resolution exceeding 1 million pixels. The color filter for a solid-state image sensor of the present invention can be used as a color filter disposed between, for example, a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for condensing light.

The film thickness of the colored pattern (colored pixel) in the color filter for the solid-state imaging device is preferably 2.0 μm or less, and more preferably 1.0 μm or less.
Further, the size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.7 μm or less.

≪Solid-state imaging device≫
The solid-state image sensor of the present invention includes the above-described color filter for a solid-state image sensor of the present invention.
The configuration of the solid-state imaging device of the present invention is a configuration provided with the color filter for the solid-state imaging device of the present invention, and is not particularly limited as long as the configuration functions as a solid-state imaging device. A configuration is mentioned.
A transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) is provided on the support, and the transfer electrodes are formed on the photodiodes and the transfer electrodes. Having a light-shielding film made of tungsten or the like that is opened only in the light-receiving part of the photodiode, and having a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part, It is the structure which has the color filter for solid-state image sensors of this invention on a device protective film.
Further, a configuration having light collecting means (for example, a microlens, etc., the same shall apply hereinafter) on the device protective layer and under the color filter (on the side close to the support), or a structure having the light collecting means on the color filter. Etc.

  The present invention will be described more specifically with reference to the following examples. The materials, reagents, ratios, equipment, operations, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In the following examples, “%” and “parts” represent “% by mass” and “parts by mass” unless otherwise specified, and the molecular weight indicates the weight average molecular weight.

[Example 1]
<Preparation of pigment dispersion composition P>
(Preparation of pulverized sodium sulfate (crushed sodium sulfate))
Dry air was fed into a 0.65 MPa jet mill (Nisshin Engineering Co., Ltd., air-flow pulverizer, Super Jet Mill), and raw material mirabilite (Mitajiri Chemical Industry Co., Ltd., neutral anhydrous mirabilite, average particle size) Was supplied at a rate of 20 kg / hr and pulverized continuously. The pulverized salt cake discharged from the pulverizer was collected in a lump with a bag filter.
Add powder frame mirabilite to isobutyl alcohol, disperse with ultrasonic waves (for 1 minute), measure the particle size distribution with a particle size measuring device (manufactured by Nikkiso Co., Ltd., Microtrac particle size distribution measuring device, MT-3300II), and average The particle diameter D50 was determined to be 3.19 μm. Furthermore, the volume% of large particles having a size of 10 μm or more was read from the particle size distribution data and found to be 0.00 volume%.

(Polent solvent salt milling)
The following pigment 1 (red pigment), which is an azo pigment represented by the general formula (1), was refined by solvent salt milling. Details will be described below.

Solvent salt milling of Pigment 1 was performed according to the following procedure.
First, 3000 g of the pulverized mirabilite was added to a double-arm kneader (manufactured by Moriyama, 5 L kneader Σ type, hereinafter referred to as “kneader”), and 300 g of pigment 1 was further added and mixed for 5 minutes. 900 g of diethylene glycol (DEG) (manufactured by Nippon Shokubai Co., Ltd.) was added to the mixture and kneaded. The temperature is controlled so that the temperature of the kneaded material in the kneader is 50 ° C., and the kneaded material is kneaded for 10 hours (hereinafter, the kneaded material is referred to as magma). The above operation was defined as a miniaturization process.

Next, the magma which completed the refinement | miniaturization process was taken out, and it moved to the tank which can be temperature-controlled. 20 L of deionized water was previously stored in the tank. The magma was dispersed by stirring with a stirrer at 150 rpm for 2 hours. The resulting dispersion was transferred to Nutsche and filtered. After filtration, it was washed with deionized water until the electrical conductivity of the washing wastewater was 3 μS / cm or less (a fine pigment containing a large amount of water that has been washed is referred to as a pigment paste).
The pigment paste after washing with water was taken out, placed on a drying shelf (material SUS304), further transferred to a dryer and dried at 80 to 105 ° C. for 15 hours (the dried finer pigment is referred to as a drying block).
The dried block was pulverized with a pulverizer (manufactured by Kyoritsu Riko Co., Ltd., small pulverizer, sample mill SK-M2).
As described above, solvent salt milling of the pigment 1 was performed. For the preparation of the following pigment dispersion composition P, the pigment 1 after the above solvent salt milling was used.

  Further, Pigment Yellow 139 (PY139) was prepared as Pigment 4 and refined by solvent salt milling in the same manner as Pigment 1 to obtain Pigment 4 after solvent salt milling.

  It was 60 nm when the average primary particle diameter of the pigment 1 after salt milling was confirmed with the transmission electron microscope. The particle diameter of the pigment 4 confirmed in the same manner as the pigment 1 was 30 nm.

(Preparation of pigment dispersion composition P)
A mixed liquid having the following composition was mixed and dispersed by a bead mill for 2 hours to prepare a red pigment dispersion composition P which is a red coloring composition of the present invention.
-Composition-
A mixture of pigment 1 after solvent salt milling and Pigment Yellow 139 (PY139) (mass ratio [pigment 1 / PY139] = 100/30) 11.8 parts. Pigment derivative 1 (azo pigment derivative) shown below. 1.2 parts ・ Dispersant 1 below (weight average molecular weight 35000, side chain acid group 100 mgKOH / g)
4.8 parts propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA)
... 82.2 parts

  In the pigment dispersion composition P, the pigment 1 is the main pigment and the pigment yellow 139 is the pigment 4 which is the sub-pigment.

  The obtained red pigment dispersion composition P was measured for volume average particle size using a Nanotrac UPA particle size analyzer (UPA-EX150; manufactured by Nikkiso Co., Ltd.), and found to be 5 nm.

<Dispersion stability evaluation>
For the red pigment dispersion composition P, using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., RE-85L), the viscosity η1 (unit: mPa · s) immediately after dispersion, and after dispersion, room temperature (25 ° C. The same applies hereinafter.) The viscosity η2 (unit mPa · s) after standing for 1 week was measured at room temperature, and the amount of thickening [η2−η1] was calculated. Furthermore, based on the calculated thickening amount, the dispersion stability was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1. The smaller the amount of thickening, the better the dispersion stability.
-Evaluation criteria-
A: Thickening amount is 2 mPa · s or less ○: Thickening amount is greater than 2 mPa · s and 3 mPa · s or less Δ: Thickening amount is greater than 3 mPa · s and 4 mPa · s or less X: Thickening amount is from 4 mPa · s large

<Preparation of red colored curable composition R>
Using the above-mentioned pigment dispersion composition P, a red colored curable composition R was prepared by mixing and stirring so as to have the following composition.
(composition)
Red pigment dispersion composition P 58.3 parts Polymerizable compound (Exemplary compound (b)) 0.7 parts Oxime photopolymerization initiator (CGI-124 manufactured by Ciba Specialty Chemicals)
0.6 parts polymerization inhibitor (p-methoxyphenol) 0.0003 parts alkali-soluble resin 1 (polymer (a) obtained by polymerizing monomer components essentially containing ether dimer, weight average molecular weight 12000 1.1 parts Fluorosurfactant (1.0% PGMEA solution of MegaFick F781 manufactured by DIC)
... 4.2 parts, solvent (propylene glycol monomethyl ether acetate) ... 15.1 parts

  The composition ratio of the alkali-soluble resin 1 is mol%. The alkali-soluble resin 1 was synthesized according to the method described in JP-A-2004-300204.

<Production of red color filter>
The red colored curable composition R prepared above is applied to the device forming surface side of an 8-inch device-formed silicon wafer (solid-state imaging device substrate) sprayed with hexamethyldisilazane in advance, and is photocurable. A film was formed. Then, heat treatment (pre-baking) was performed for 180 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.6 μm.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), a pattern is formed at a dose of 150 mJ / cm ² through a photomask for forming a 1.0 μm square red pixel at a wavelength of 365 nm. Exposure was performed.
Then, the silicon wafer on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type; manufactured by Chemitronics), and CD-2000 (Fuji Film Electronics). Paddle development was performed at 23 ° C. for 180 seconds using a 40% diluted solution (manufactured by Materials Co., Ltd.) to form a red pattern on the silicon wafer.

A silicon wafer on which a red pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer is rotated at a rotation speed of 50 rpm by a rotating device, and pure water is sprayed from the upper part of the rotation center from a jet nozzle. And then rinsed and then spray dried.
Next, it heated for 5 minutes with a 200 degreeC hotplate, and obtained the red pattern (red color filter) on the silicon wafer.

  When the pattern shape of the obtained red color filter was observed with an optical microscope (magnification 1000 times) and a scanning electron microscope (SEM) (magnification 20000 times), the pattern shape was good and the pattern formability was also good. It was.

<Evaluation of development residue>
The obtained silicon wafer with a red color filter was observed with a scanning electron microscope (SEM) (magnification 20000 times), and the development residue was evaluated according to the following evaluation criteria.
-Evaluation criteria-
A: Less than 10 / area (field of view)
○: 10 or more and less than 30 / area (field of view)
Δ: 30 or more and less than 50 / area (field of view)
×: 50 or more / area (field of view)
The evaluation result of the non-formation area of the colored pattern formed in Example 1 was “◎”, and it was confirmed that the development residue was suppressed.

<Measurement of spectral characteristics>
Next, in the production of the red color filter, the 8 inch device-formed silicon wafer is replaced with a glass substrate, the pattern exposure is changed to the entire surface exposure, and a red film having a dry film thickness of 0.6 μm is formed on the glass substrate. A membrane (colored permeable membrane) was formed.
The spectral characteristics (transmittance at each wavelength) of the obtained red film were measured by MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.).
As spectral characteristics of the red film formed in Example 1, the transmittance at 400 nm was 9%, the transmittance at 525 nm was 3%, the transmittance at 600 nm was 81%, and the transmittance at 700 nm was 99%. From this, it was confirmed that the red film exhibits good spectral characteristics as red.

[Examples 2 to 15 and Comparative Examples 1 to 10]
In Example 1, the pigment dispersion composition and the colored curable composition were the same as in Example 1 except that the types of the main pigment, sub-pigment, pigment derivative, and dispersant were changed as shown in Table 1 below. And a red color filter were produced and evaluated in the same manner as in Example 1.
In addition, about the pigment 1 used for the comparative example 1, the pigment 3 used for the comparative example 3, and the pigment 4 used for the comparative example 5, what was not refined | miniaturized by solvent milling was used.

Table 1 below summarizes the evaluations obtained for Examples 1 to 18 and Comparative Examples 1 to 3.
In Table 1, measured values are shown for the wavelength (nm) (characteristic (1) in the present invention) at which a transmittance of 50% was obtained. In addition, the transmittance (characteristics (2) to (5)) at 400 nm, 525 nm, 600 nm, and 700 nm is indicated by “」 ”for those satisfying the respective characteristics according to the present invention, and those not satisfied “×” is shown.
Moreover, when the pattern shape of the obtained red color filter was observed with an optical microscope (magnification 1000 times) and a scanning electron microscope (SEM) (magnification 20000 times), the red color filter obtained in each example was In all cases, the pattern shape was good, and the pattern formability was also good.

  Each component described in Table 1 is as follows.

Pigment 4: Pigment Yellow 139
Pigment 5: Pigment Red 254
Pigment 6: Pigment Red 177

The weight average molecular weight of the dispersant 2 is 28500, and the amount of acidic groups in the side chain is 73 mgKOH / g.
The weight average molecular weight of the dispersant 3 is 30000, and the amount of acidic groups in the side chain is 60 mgKOH / g.
The weight average molecular weight of the dispersant 4 is 21,000, and the amount of acidic groups in the side chain is 55 mgKOH / g.

As shown in Table 1, the nuclear pigment dispersion composition of the example (the red coloring composition of the present invention) had a small amount of thickening and good dispersion stability. Moreover, the Example using the dispersing agents 1-4 showed the especially favorable dispersion stability. Moreover, the spectral spectrum of the color filter produced using these pigment dispersion compositions was excellent in spectral characteristics, and the colored pattern also suppressed the development residue.
On the other hand, in the pigment dispersion compositions of Comparative Examples 1, 2, 4, 5, 7, 8, and 10-13, good spectral characteristics were not obtained.

Claims (10)

(A) A red coloring composition containing a red pigment, (B) a yellow pigment, and (C) a dispersant, wherein the (A) red pigment is an azo pigment represented by the following general formula (1), (B) The yellow pigment is C.I. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, and 185, and (C) the dispersing agent is A polymer compound containing at least one repeating unit selected from repeating units represented by formula (I) and general formula (II), and having a film thickness of 0. A red colored composition that satisfies all of the following characteristics (1) to (5) when a colored permeable membrane of 6 μm is formed.
(1) The range of the wavelength of light from which 5% transmittance is obtained is 583 nm or more and less than 587 nm (2) The transmittance of light having a wavelength of 400 nm is 15% or less (3) The transmittance of light having a wavelength of 525 nm is 5% or less (4 ) The transmittance of light with a wavelength of 600 nm is 75% or more (5) The transmittance of light with a wavelength of 700 nm is 95% or more


[In General Formula (1), G represents a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group, and R ₁ represents an amino group, an aliphatic oxy group, or an aliphatic group that may have a substituent. Represents a group, an aryl group, or a heterocyclic group, and R ₂ represents a substituent.
A represents any of the groups represented by the following general formulas (A-1) to (A-32).
m represents an integer of 0 to 5, and n represents 1.
There is no ionic hydrophilic group in the general formula (1). ]


[In General Formulas (A-1) to (A-32), R _{51 to} R ₅₉ each independently represent a hydrogen atom or a substituent, and adjacent substituents are bonded to each other to form a 5- to 6-membered ring. May be formed. * Represents the bonding position with the azo group in the general formula (1). ]


[In General Formulas (I) and (II), R ^{1 to} R ⁶ each independently represent a hydrogen atom or a monovalent organic group, and X ¹ and X ² each independently represent —CO—, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group, L ¹ and L ² each independently represent a single bond or a divalent organic linking group. , A ¹ and A ² each independently represent a monovalent organic group, m and n each independently represents an integer of 2 to 8, and p and q each independently represents 1 to 100. Represents an integer. ] The red coloring composition according to claim 1 , wherein the azo pigment represented by the general formula (1) is an azo pigment represented by the following general formula (2).


In [general formula (2), R ₂₁ is an optionally substituted amino group, an aliphatic oxy group, an aliphatic group, an aryl group, or a heterocyclic group, R ₂₂ represents a substituent. R ₅₅ and R ₅₉ each independently represent a hydrogen atom or a substituent.
m represents an integer of 0 to 5, and n represents 1 .
Z represents an electron withdrawing group having a Hammett's σp value of 0.2 or more .
One general formula (2) it does not have an ionic hydrophilic group in. ] The red color according to claim 1 or 2, wherein the azo pigment represented by the general formula (1) is a solvent salt milled azo pigment, and the particle size of the pigment after the solvent salt milling is 100 nm or less. Coloring composition. The (B) yellow pigment is C.I. I. It is a pigment yellow 139, The red coloring composition of any one of Claims 1-3 . The red coloring composition according to any one of claims 1 to 4, wherein the polymer compound has an acidic group in a side chain in a range of 50 mgKOH / g to 200 mgKOH / g. The colored curable composition containing the red coloring composition of any one of Claims 1-5, a photoinitiator, and a polymeric compound. The colored curable composition according to claim 6 , wherein the photopolymerization initiator is an oxime photopolymerization initiator. A step of forming a colored curable composition layer by applying the colored curable composition according to claim 6 or 7 on a support, and exposing the colored curable composition layer through a mask. The manufacturing method of the color filter for solid-state image sensors including a process and the process of developing the colored curable composition layer after exposure, and forming a colored pattern. The color filter for solid-state image sensors manufactured by the manufacturing method of the color filter for solid-state image sensors of Claim 8 . The solid-state image sensor provided with the color filter for solid-state image sensors of Claim 9 .