JP6663433B2 - Colored composition, fluorescent sensor, and method for manufacturing fluorescent sensor - Google Patents

Description

  The present invention relates to a coloring composition, a fluorescent sensor, and a method for manufacturing a fluorescent sensor.

2. Description of the Related Art There is a fluorescent sensor that inspects a sample by reacting a sample such as DNA (deoxyribonucleic acid) with a reagent, irradiating the sample with excitation light, and detecting fluorescence emitted from the sample.
Inspection by a fluorescent sensor is performed by irradiating the sample with excitation light, transmitting the fluorescence generated from the sample through the emission filter through a predetermined wavelength, and observing the fluorescence transmitted through the emission filter.

  As an emission filter of the fluorescent sensor, for example, a filter using a red pigment is used. As a red pigment, Color Index Pigment Red 254 has been conventionally used.

On the other hand, Patent Document 1 describes that a red color filter for an image display device is manufactured using a composition containing chromophthal red BRN (color index pigment red 144) and a photosensitive resin. .
Patent Document 2 describes that a red color filter for an image display device is manufactured by using a composition including a color index pigment red 144, polyvinyl alcohol, a surfactant, and water. I have.

JP-A-60-129739 JP-A-10-239835

  The present inventors have conducted intensive studies on the fluorescent sensor, and found that the emission filter using the color index pigment red 254 easily generates fluorescence by the excitation light, and the detection sensitivity of the fluorescent sensor is likely to be reduced.

  On the other hand, Patent Documents 1 and 2 do not describe or suggest a fluorescent sensor.

  Therefore, an object of the present invention is to provide a coloring composition capable of obtaining a fluorescent sensor having excellent detection sensitivity, a fluorescent sensor having excellent detection sensitivity, and a method for manufacturing a fluorescent sensor.

The present inventor has conducted intensive studies on a coloring composition for forming an emission filter of a fluorescent sensor, and as a result, has found that the color index pigment red 144 and the color index pigment red 166 are pigments that do not easily generate fluorescence by excitation light. Was. When the coloring composition was examined, the integrated intensity of the fluorescence in the wavelength range of 600 to 700 nm when the film having a thickness of 3.0 μm formed using the coloring composition was excited by light having a wavelength of 534 nm, For the cured film containing Color Index Pigment Red 254, a coloring composition having a value of 0.5 or less divided by the integrated intensity of fluorescence in a wavelength range of 600 to 700 nm when excited by light having a wavelength of 534 nm is used. In particular, they have found that a fluorescent sensor having excellent detection sensitivity can be obtained, and have completed the present invention. The present invention provides the following.
<1> A colored composition for forming an emission filter of a fluorescent sensor,
A red pigment, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent,
The integrated intensity of the fluorescence in the wavelength range of 600 to 700 nm when the film having a thickness of 3.0 μm formed using the coloring composition is excited with light having a wavelength of 534 nm,
The cured film A having a thickness of 3.0 μm and containing 40% by mass of Color Index Pigment Red 254 in the total solid content was divided by the integrated intensity of fluorescence in the wavelength range of 600 to 700 nm when excited with light having a wavelength of 534 nm. A colored composition having a value of 0.5 or less.
<2> A colored composition for forming an emission filter of a fluorescent sensor,
A coloring composition comprising at least one red pigment selected from Color Index Pigment Red 144 and Color Index Pigment Red 166, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent.
<3> The colored composition according to <1> or <2>, wherein the red pigment has an average particle size of 5 to 500 nm.
<4> The colored composition according to any one of <1> to <3>, wherein the polymerizable compound is a polymerizable monomer.
<5> The colored composition according to <4>, wherein the polymerizable monomer has three or more radical polymerizable groups.
<6> The colored composition according to <4> or <5>, wherein the polymerizable monomer has an alkyleneoxy group.
<7> The colored composition according to <6>, wherein the polymerizable monomer has a chain containing two or more alkyleneoxy groups as repeating units.
<8> The colored composition according to any one of <1> to <7>, wherein the resin contains a graft copolymer.
<9> the colored composition according to any one of <1> to <8>, wherein the resin includes a resin containing a repeating unit represented by any of the following formulas (1) to (4);
In Formulas (1) to (4), W ¹ , W ² , W ³ , and W ⁴ each independently represent an oxygen atom or NH;
X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom or a monovalent organic group,
Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group;
Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a monovalent organic group,
R ³ represents an alkylene group,
R ⁴ represents a hydrogen atom or a monovalent organic group,
n, m, p, and q each independently represent an integer of 1 to 500;
j and k each independently represent an integer of 2 to 8,
In Formula (3), when p is 2 to 500, a plurality of R ³ may be the same or different from each other;
In the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ may be the same or different.
<10> A fluorescent sensor having an emission filter using the coloring composition according to any one of <1> to <9>.
<11> The fluorescent sensor according to <10>, wherein the fluorescent sensor is used by irradiating the sample with excitation light.
<12> The fluorescent sensor according to <10> or <11>, wherein the fluorescent sensor is a DNA sensor.
<13> A method for manufacturing a fluorescent sensor, comprising a step of forming an emission filter using the coloring composition according to any one of <1> to <9>.

  According to the present invention, it is possible to provide a colored composition capable of obtaining a fluorescent sensor having excellent detection sensitivity, a fluorescent sensor having excellent detection sensitivity, and a method for producing a fluorescent sensor having excellent detection sensitivity. became.

It is a schematic structure figure of one embodiment of a fluorescence sensor of the present invention. It is a schematic structure figure of other embodiments of a fluorescence sensor of the present invention.

In the present specification, the term “total solids” refers to the total mass of components excluding the solvent from all components of the composition. The solid content means a solid content at 25 ° C.
In the notation of a group (atomic group) in the present specification, the notation not indicating substituted or unsubstituted includes not only a group having no substituent but also a group having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
The term “radiation” in this specification means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation. Unless otherwise specified, the term “exposure” in this specification means not only exposure using a deep ultraviolet ray such as a mercury lamp and an excimer laser, X-rays, and EUV light, but also drawing using an electron beam and an ion beam. Is also included in the exposure.
In the present specification, “(meth) acrylate” represents both or either acrylate and methacrylate, “(meth) acryl” represents both or any of acryl and methacryl, and “(meth) acryloyl” "" Represents both or any of acryloyl and methacryloyl, and "(meth) allyl" represents both or any of allyl and methallyl.
In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In the present specification, the term "step" is included not only in an independent step but also in the case where the intended action of the step is achieved even if it cannot be clearly distinguished from other steps. .
In the present specification, the weight average molecular weight and the number average molecular weight are defined as values in terms of polystyrene measured by gel permeation chromatography (GPC). In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation) and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) as a column. 0.0mmID (inner diameter) x 15.0 cm) can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.
The pigment used in the present invention means an insoluble dye compound that is hardly dissolved in a solvent. Typically, it refers to a dye compound that is present in the composition as particles dispersed therein. Here, the solvent includes any solvent, for example, the solvents exemplified in the section of the solvent described below. The pigment used in the present invention preferably has a solubility at 25 ° C. of 0.1 g / 100 g Solvent or less in both propylene glycol monomethyl ether acetate and water.

<Coloring composition>
The coloring composition of the present invention is a coloring composition for forming an emission filter of a fluorescent sensor, and satisfies the following requirement (1) or (2).
(1): A film having a thickness of 3.0 μm including a red pigment, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent, and formed using a coloring composition, is irradiated with light having a wavelength of 534 nm. The integrated intensity of fluorescence in the wavelength range of 600 to 700 nm when excited is excited by light of wavelength 534 nm of a cured film A having a thickness of 3.0 μm and containing 40% by mass of Color Index Pigment Red 254 in the total solid content. The value obtained by dividing by the integrated intensity of the fluorescence in the wavelength range of 600 to 700 nm is 0.5 or less.
The cured film A was composed of 5% by mass of a color index pigment red 254 having an average particle diameter of 50 nm, 1.5% by mass of a resin represented by the formula D-1, and 0% by mass of a pigment derivative represented by the formula PZ-1. 0.075 mass%, the polymerizable compound represented by the formula M-1 is 0.7 mass%, the resin represented by the formula B-2 is 4.925 mass%, and the compound is represented by the formula I-1. A composition containing 0.3% by mass of a photopolymerization initiator and the balance being propylene glycol monomethyl ether acetate is applied on a glass substrate so that the film thickness after curing becomes 3.0 μm. After drying at 100 ° C., it is preferable that the cured film is obtained by exposing i-line at an exposure amount of 1000 mJ / cm ² . In addition, the weight average molecular weight of D-1 is 38000, and the numerical value described together with each repeating unit (main chain) represents the content (mass ratio) of each repeating unit, and the numerical value described together with the repeating portion of the side chain. Indicates the number of repetitions of the repetition site. The weight-average molecular weight of B-2 is 12000, and the numerical value described with each repeating unit (main chain) represents the content (mass ratio) of each repeating unit.
(2): It contains at least one red pigment selected from Color Index Pigment Red 144 and Color Index Pigment Red 166, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent.

According to the present invention, by using the coloring composition of (1) or (2), it is possible to form an emission filter having low fluorescence with respect to excitation light.
Further, the color index pigment red 144 and the color index pigment red 166 have a particularly low fluorescence with respect to the excitation light, and further, are excellent in heat resistance, so that they have a lower fluorescence with respect to the excitation light. Thus, an emission filter having excellent heat resistance can be formed.
Further, since the emission filter using the coloring composition of the present invention has low fluorescence with respect to the excitation light, the fluorescent sensor having the emission filter using the coloring composition of the present invention has a fluorescent property caused by the emission filter. And the detection sensitivity is excellent.
Hereinafter, the present invention will be described in detail.

<Coloring composition>
<< red pigment >>
The coloring composition of the present invention contains a red pigment. The red pigment is preferably a red pigment having an azo skeleton. As the red pigment having an azo skeleton, a compound having a structure represented by Formula R-1 is preferable.
In the formula, R ^{1 to} R ¹⁴ each independently represent a hydrogen atom or a halogen atom. Examples of the halogen atom include a chlorine atom, a fluorine atom, and a bromine atom, and a chlorine atom is preferable.
Preferably, at least two of R ^{1 to} R ⁵ are a halogen atom, and the rest are hydrogen atoms. More preferably, two of R ^{1 to} R ⁵ are halogen atoms, and the rest are hydrogen atoms. In particular, it is preferred that R ¹ and R ⁴ are halogen atoms, and R ² , R ³ and R ⁵ are hydrogen atoms.
At least two of R ^{10 to} R ¹⁴ are preferably halogen atoms, and the rest are preferably hydrogen atoms. More preferably, two of R ^{10 to} R ¹⁴ are halogen atoms, and the rest are hydrogen atoms. In particular, it is preferable that R ¹⁰ and R ¹³ are halogen atoms, and R ¹¹ , R ¹² and R ¹⁴ are hydrogen atoms.
R ^{6 to} R ⁹ may be all hydrogen atoms, or at least one of R ^{6 to} R ⁹ may be a halogen atom, and the rest may be hydrogen atoms. When at least one of R ^{6 to} R ⁹ represents a halogen atom, R ⁷ is preferably a halogen atom, and the remainder is preferably a hydrogen atom or a halogen atom, and more preferably a hydrogen atom.

  In the present invention, the red pigment is C.I. I. Pigment Red 144 and C.I. I. Pigment Red 166 is preferable. C. I. Pigment Red 144 and C.I. I. Since Pigment Red 166 has low fluorescence for excitation light, an emission filter having low fluorescence for excitation light can be formed.

  In the present invention, the average particle size of the red pigment is preferably from 5 to 1000 nm, more preferably from 5 to 500 nm. The upper limit is preferably 400 nm or less, more preferably 350 nm or less, and particularly preferably 300 nm or less. According to the study of the present inventors, it has been found that by reducing the particle size of the red pigment, the red pigment tends to have low fluorescence with respect to excitation light. When the average particle size of the red pigment is in the above range, it is easy to form an emission filter having even lower fluorescence for excitation light.

  In the present invention, the `` average particle size '' of the red pigment is an average particle size of secondary particles in which primary particles of the red pigment are aggregated, and is a value measured by a method such as a dynamic light scattering method. is there.

In the coloring composition of the present invention, the content of the red pigment is preferably from 10 to 90% by mass based on the total solid content of the coloring composition. The lower limit is more preferably 20% by mass or more, and even more preferably 30% by mass or more. The upper limit is more preferably equal to or less than 80% by mass, and still more preferably equal to or less than 70% by mass.
In addition, C.I. I. Pigment Red 144 and C.I. I. Pigment Red 166 preferably has a total content of 50 to 100% by mass. The lower limit is more preferably 60% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more.
The red pigment is substantially C.I. I. Pigment Red 144 and C.I. I. Pigment Red 166 alone. Note that the red pigment is substantially C.I. I. Pigment Red 144 and C.I. I. Pigment Red 166 alone means that C.I. I. Pigment Red 144 and C.I. I. Pigment Red 166 is preferably 99% by mass or more, more preferably 99.9% by mass or more.

In the present invention, the following pigments can also be used as the red pigment. The red pigment is C.I. I. Pigment Red 144 and C.I. I. When none of Pigment Red 166 is contained, one or more of the following pigments can be selected and used so that the coloring composition satisfies the above requirement (1). The following pigments are C.I. I. Pigment Red 144 and / or C.I. I. Pigment Red 166 can be used in combination.
Color Index (CI) 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, 83,88,90,105,112,119,122,123,146,149,150,155,168,169,170,171,172,175,176,177,178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 270, 272, 279

-Pigment refinement-
In the present invention, it is preferable to use a fine and sized pigment as the red pigment. Pigment refining is performed by preparing a high-viscosity liquid composition together with a pigment, a water-soluble organic solvent, and a water-soluble inorganic salt, and applying a stress to the material using a wet pulverizer to grind it. Achieved.

Examples of the water-soluble organic solvent used in the pigment refining process include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. , Propylene glycol, propylene glycol monomethyl ether acetate, and the like.
Also, as long as it is adsorbed on the pigment by using a small amount and does not flow down into the wastewater, the water solubility is low or other solvents having no water solubility, for example, benzene, toluene, xylene, ethylbenzene, chlorobenzene, Nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, butyl acetate, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohexane, halogenated hydrocarbon, acetone, methyl ethyl ketone, methyl Isobutyl ketone, cyclohexanone, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone and the like may be used.
The solvent used in the pigment refining step may be only one kind, or may be used as a mixture of two or more kinds as necessary.

Examples of the water-soluble inorganic salt used in the pigment refining step include sodium chloride, potassium chloride, calcium chloride, barium chloride, and sodium sulfate.
The amount of the water-soluble inorganic salt used in the miniaturization step is preferably 1 to 50 times the mass of the pigment. The greater the amount of the water-soluble inorganic salt used, the more effective the grinding effect. However, the more preferred amount is 1 to 10 times by mass in terms of productivity. Further, it is preferable to use inorganic salts having a water content of 1% or less.
The amount of the water-soluble organic solvent used in the micronizing step is preferably from 50 to 300 parts by mass, more preferably from 100 to 200 parts by mass, per 100 parts by mass of the pigment.

  There are no particular restrictions on the operating conditions of the wet-type pulverizer in the pigment refining process.However, in order to effectively advance the grinding by the pulverizing media, the operating conditions when the apparatus is a kneader are determined by the number of rotations of the blades in the apparatus. Is preferably in the range of 10 to 200 rpm, and it is preferable that the rotation ratio of the two axes is relatively large because the grinding effect is large. The operation time is preferably 1 hour to 8 hours in combination with the dry pulverization time, and the internal temperature of the apparatus is preferably 50 to 150 ° C. Further, the water-soluble inorganic salt as a pulverizing medium preferably has a pulverized particle size of 5 to 50 μm, a sharp particle size distribution and a spherical shape.

<< other chromatic coloring agents >>
The coloring composition of the present invention may contain a chromatic colorant other than the red pigment. The other chromatic colorant may be a pigment or a dye. The other colorant may be one kind or two or more kinds.
As another chromatic colorant, a yellow pigment is preferable for the purpose of lowering the transmittance at a wavelength of 300 to 400 nm. The yellow pigment is not particularly limited as long as it is commercially available.
In the present invention, the chromatic colorant means a colorant other than a white colorant and a black colorant. The chromatic colorant is preferably a colorant having a maximum absorption wavelength in a wavelength range of 400 to 700 nm. Further, “having a maximum absorption wavelength in a wavelength range of 400 to 700 nm” means having a wavelength showing a maximum absorbance in a wavelength range of 400 to 700 nm in an absorption spectrum. For example, in an absorption spectrum in a wavelength range of 350 to 1300 nm, it is preferable to have a wavelength showing a maximum absorbance in a wavelength range of 400 to 700 nm.

  Examples of the pigment include various conventionally known pigments. Also, considering that the pigment preferably has a high transmittance, it is preferable to use a pigment having an average particle size as small as possible, and also considering the handling properties, the pigment has an average particle size of 0.01 to 0.1. 1 μm is preferable, and 0.01 to 0.05 μm is more preferable.

Examples of the pigment include the following. However, the present invention is not limited to these.
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175 176,177,179,180,181,182,185,187,188,193,194,199,213,214, etc.,
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, etc. ,
C. I. Pigment Green 7,10,36,37,58,59
C. I. Pigment Violet 1,19,23,27,32,37,42
C. I. Pigment Blue 1,2,15,15: 1,15: 2,15: 3,15: 4,15: 6,16,22,60,64,66,79,80

  Examples of the dye include, for example, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, JP-T-2592207, and U.S. Pat. U.S. Pat. No. 5,679,920, U.S. Pat. No. 505,950, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, and the like. The dyes used can be used. When classified into chemical structures, pyrazole azo compounds, pyromethene compounds, anilino azo compounds, triarylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. Can be used. Further, a dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP-A-2011-213925 and JP-A-2013-041097.

  When the coloring composition of the present invention contains another chromatic colorant, the content of the other chromatic colorant with respect to the total solid content in the coloring composition is preferably 1 to 60% by mass. The lower limit is more preferably 5% by mass or more, and even more preferably 10% by mass or more. The upper limit is more preferably 50% by mass or less.

<< Resin >>
The coloring composition of the present invention contains a resin. The resin is mixed, for example, for the purpose of dispersing the pigment in the composition or for the purpose of the binder. In addition, the resin mainly used for dispersing the pigment is also referred to as a dispersant. However, such a use of the resin is only an example, and the resin can be used for a purpose other than such a use.

  The weight average molecular weight (Mw) of the resin is preferably from 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 3,000 or more, more preferably 5,000 or more.

  The content of the resin is preferably 1 to 80% by mass of the total solids of the coloring composition. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less. The coloring composition of the present invention may include only one type of resin, or may include two or more types of resins. When two or more types are included, the total amount is preferably within the above range.

The coloring composition of the present invention can contain a dispersant as a resin.
The dispersant is preferably a resin having at least one selected from an acid group and a basic group, and more preferably a resin having an acid group. Examples of the acid group of the resin include a carboxy group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. Examples of the basic group of the resin include an amino group. In the present invention, a resin having neither an acid group nor a basic group can be used as the dispersant.

  When the resin has an acid group, the acid value of the resin is preferably from 30 to 300 mgKOH / g. The lower limit is more preferably 30 mgKOH / g or more, still more preferably 40 mgKOH / g or more, and still more preferably 50 mgKOH / g or more. The upper limit is more preferably 300 mgKOH / g or less, and still more preferably 200 mgKOH / g or less.

  In the present invention, the resin preferably contains a graft copolymer. In the present invention, the graft polymer can be preferably used as a red pigment dispersant. In the present invention, the term “graft copolymer” means a resin having a graft chain. The term “graft chain” refers to a portion from the base of the main chain of the polymer to the terminal of a group branched from the main chain.

  As the graft copolymer, a resin having a graft chain in which the number of atoms excluding hydrogen atoms is in the range of 40 to 10,000 is preferable. The number of atoms excluding hydrogen atoms per graft chain is preferably from 40 to 10,000, more preferably from 50 to 2,000, and still more preferably from 60 to 500.

Examples of the main chain structure of the graft copolymer include (meth) acrylic resin, polyester resin, polyurethane resin, polyurea resin, polyamide resin, and polyether resin. Among them, (meth) acrylic resin is preferable.
The graft chain of the graft copolymer is a graft chain having poly (meth) acrylic, polyester, or polyether in order to improve the interaction between the graft site and the solvent and thereby enhance the dispersibility. Is preferable, and a graft chain having polyester or polyether is more preferable.

  The weight average molecular weight (Mw) of the graft copolymer is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and still more preferably 10,000 to 30,000. The number average molecular weight (Mn) of the graft copolymer is preferably 2,500 to 50,000, more preferably 5,000 to 30,000, and still more preferably 5,000 to 15,000.

  As the macromonomer used for producing the graft copolymer by radical polymerization, a known macromonomer can be used, and a macromonomer AA-6 manufactured by Toagosei Co., Ltd. (polymethacryl having a methacryloyl group as a terminal group) Acid), AS-6 (polystyrene whose terminal group is a methacryloyl group), AN-6S (copolymer of styrene and acrylonitrile whose terminal group is a methacryloyl group), AB-6 (polystyrene whose terminal group is a methacryloyl group) Butyl acrylate), Daicel's Praxel FM5 (2-hydroxyethyl methacrylate added with 5 mol equivalents of ε-caprolactone), FA10L (2-hydroxyethyl acrylate added with 10 mol equivalents of ε-caprolactone), And polyester-based macromolecules described in JP-A-2-272009. Nomers and the like.

  In the present invention, as the resin, a graft copolymer containing a repeating unit represented by any of the following formulas (1) to (4) can also be used.

In Formulas (1) to (4), W ¹ , W ² , W ³ , and W ⁴ each independently represent an oxygen atom or NH;
X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom or a monovalent organic group,
Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group;
Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a monovalent organic group,
R ³ represents an alkylene group,
R ⁴ represents a hydrogen atom or a monovalent organic group,
n, m, p, and q each independently represent an integer of 1 to 500;
j and k each independently represent an integer of 2 to 8,
In Formula (3), when p is 2 to 500, a plurality of R ³ may be the same or different from each other;
In the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ may be the same or different.

In Formulas (1) to (4), W ¹ , W ² , W ³ , and W ⁴ each independently represent an oxygen atom or NH. Preferably, W ¹ , W ² , W ³ and W ⁴ are oxygen atoms.

In Formulas (1) to (4), X ¹ , X ² , X ³ , X ⁴ , and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. X ¹ , X ² , X ³ , X ⁴ , and X ⁵ are each independently preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms from the viewpoint of synthesis restrictions. Is more preferably a hydrogen atom or a methyl group, and a methyl group is particularly preferable.

In Formulas (1) to (4), Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group, and the linking group is not particularly limited in structure. Specific examples of the divalent linking group represented by Y ¹ , Y ² , Y ³ , and Y ⁴ include the following linking groups (Y-1) to (Y-21). . In the structures shown below, A and B each mean a binding site to the left terminal group and the right terminal group in Formulas (1) to (4).

In Formulas (1) to (4), Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a monovalent organic group. Although the structure of the monovalent organic group is not particularly limited, specifically, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and And an amino group. Among these, as the organic group represented by Z ¹ , Z ² , Z ³ , and Z ⁴ , those having a steric repulsion effect are particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 to 24 carbon atoms. Of these, a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is particularly preferable. The alkyl group contained in the alkoxy group may be linear, branched, or cyclic.

  In Formulas (1) to (4), n, m, p, and q are each independently an integer of 1 to 500. In the formulas (1) and (2), j and k each independently represent an integer of 2 to 8. In the formulas (1) and (2), j and k are preferably integers of 4 to 6, and most preferably 5, from the viewpoints of dispersion stability and developability.

In Formula (3), R ³ represents an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R ³ may be the same or different.

In the formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited in structure. R ⁴ is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and more preferably a hydrogen atom or an alkyl group. When R ⁴ is an alkyl group, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms is preferable. A chain alkyl group is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is particularly preferable. In the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ present in the graft copolymer may be the same or different.

From the viewpoint of dispersion stability and developability, the graft polymer preferably contains at least one selected from the repeating units represented by the following formula (1A) and the repeating units represented by the following formula (2A). .

Wherein ^(1A), X ^1, Y 1, ^{Z 1} and n are as defined ^{X 1,} Y 1, ^{Z 1} and n in Formula (1), and preferred ranges are also the same.
Wherein ^(2A), X ^2, Y 2, ^{Z 2} and m are as defined ^{X 2,} Y 2, ^{Z 2} and m in the formula (2), and preferred ranges are also the same.

  The graft polymer preferably contains a repeating unit having an acid group in addition to the repeating units represented by the above formulas (1) to (4). Examples of the acid group include a carboxy group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group, and a carboxy group and a phenolic hydroxyl group are preferable. The content of the repeating unit having an acid group is preferably from 5 to 95% by mass, more preferably from 10 to 95% by mass, based on the total mass of the graft resin.

  The graft polymer may further include a repeating unit having a functional group capable of forming an interaction with the pigment, other than the graft chain and the acid group. The repeating unit having a functional group described above is not particularly limited in structure, and examples thereof include a repeating unit having a basic group, a repeating unit having a coordinating group, and a repeating unit having a reactive group.

Examples of the basic group include a primary amino group, a secondary amino group, a tertiary amino group, a hetero ring containing an N atom, an amide group, and the like. Examples of the coordinating group and the reactive group include an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride residue, and an acid chloride residue. The graft polymer may or may not contain a repeating unit having a functional group as described above.
0.1-50 mass% is preferable with respect to the total mass of a graft resin, and 0.1-30 mass% is more preferable.

  The graft polymer preferably has a hydrophobic repeating unit in addition to the repeating units represented by the above formulas (1) to (4). The hydrophobic repeating unit is preferably a repeating unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, and more preferably derived from a compound having a ClogP value of 1.2 to 8. It is a repeating unit.

ClogP values are measured using Daylight Chemical Information System, Inc. This is a value calculated by the program “CLOGP” available from the company. This program provides the value of "calculated logP" calculated by the Hansch, Leo fragment approach (see literature below). The fragment approach is based on the chemical structure of a compound, estimating the logP value of a compound by dividing the chemical structure into substructures (fragments) and summing the logP contributions assigned to that fragment. The details are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 is used.
A. J. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P .; G. FIG. Sammes, J .; B. Taylor and C.I. A. Ramsden, Eds. , P. 295, Pergamon Press, 1990; Hansch & A. J. Leo. Substitute Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A. J. Leo. Calculating log Point from structure. Chem. Rev .. , 93, 1281-1306, 1993.

log P means a common logarithm of a partition coefficient P (Partition Coefficient), and quantitatively describes how an organic compound is distributed in an equilibrium of a two-phase system of an oil (generally, 1-octanol) and water. It is a physical property value expressed as a simple numerical value, and is represented by the following equation.
logP = log (Coil / Cwater)
In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the aqueous phase.
When the value of logP is increased to a positive value across 0, the oil solubility increases, and when the absolute value is increased to a negative value, the water solubility increases, and there is a negative correlation with the water solubility of the organic compound. It is widely used as a parameter for estimating water solubility.

  The graft copolymer preferably has, as a hydrophobic repeating unit, at least one repeating unit selected from repeating units derived from monomers represented by the following formulas (i) to (iii).

In the above formulas (i) to (iii), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine or the like) or a carbon atom having 1 to 6 carbon atoms. (For example, a methyl group, an ethyl group, a propyl group, etc.). R ¹ , R ² , and R ³ are more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and most preferably a hydrogen atom or a methyl group. R ² and R ³ are particularly preferably hydrogen atoms.

  X represents an oxygen atom (-O-) or an imino group (-NH-), and is preferably an oxygen atom.

L is a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (eg, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group) and a divalent aromatic group (eg, an arylene group) , A substituted arylene group), a divalent heterocyclic group, an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR ³¹ —, where R ³¹ Represents an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (—CO—), or a combination thereof.
L is preferably a single bond, a divalent linking group containing an alkylene group or an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. Further, L may include a polyoxyalkylene structure containing two or more oxyalkylene structures. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. Polyoxyethylene _{structure, - (OCH 2 CH 2)} n - it is represented, n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

Z represents an aliphatic group (eg, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, a substituted unsaturated alkyl group), an aromatic group (eg, an aryl group, a substituted aryl group), a heterocyclic group, an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR ³¹ —, where R ³¹ is an aliphatic group, an aromatic group or a heterocyclic group), carbonyl Group (—CO—) or a combination thereof.

The aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10. The aliphatic group further includes a ring-assembled hydrocarbon group and a crosslinked cyclic hydrocarbon group. Examples of the ring-assembled hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4-cyclohexyl. And a phenyl group. As the bridged cyclic hydrocarbon ring, for example, bicyclic such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) A tricyclic hydrocarbon ring such as a hydrocarbon ring, homobledan, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [4.3.1.1 ^2,5 ] undecane ring, tetracyclo [4 .4.0.1 ^2,5 . [ ^7,10 ] dodecane, tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring and the like. The bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring, for example, perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydroindene A condensed ring formed by condensing a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring is also included. As the aliphatic group, a saturated aliphatic group is more preferable than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group. However, the aliphatic group represented by Z does not have an acid group as a substituent.

  The number of carbon atoms of the aromatic group is preferably from 6 to 20, more preferably from 6 to 15, and even more preferably from 6 to 10. Further, the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group. However, the aromatic group represented by Z does not have an acid group as a substituent.

The heterocyclic group preferably has a 5- or 6-membered ring as a heterocyclic ring. Another heterocyclic ring, aliphatic ring or aromatic ring may be fused to the heterocyclic ring. Further, the heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an oxo group (＝ O), a thioxo group (＝ S), an imino group (＝ NH), a substituted imino group (＝ NR ³² , where R ³² is a fatty acid). Group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group. However, the heterocyclic group represented by Z does not have an acid group as a substituent.

In the above formula (iii), R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine or the like) or an alkyl group having 1 to 6 carbon atoms ( For example, a methyl group, an ethyl group, a propyl group, etc.), Z, or -LZ. Here, L and Z have the same meanings as described above. As R ⁴ , R ⁵ and R ⁶ , a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.

  Examples of typical compounds represented by the formulas (i) to (iii) include radically polymerizable compounds selected from acrylates, methacrylates, styrenes, and the like. As examples of the compounds represented by the formulas (i) to (iii), the compounds described in paragraph numbers 0089 to 0093 of JP-A-2013-249417 can be referred to, and the contents thereof are incorporated in the present specification. It is.

Specific examples of the above graft copolymer include, for example, the following. Further, the resins described in paragraphs 0072 to 0094 of JP-A-2012-255128 can be used.

  The dispersant (resin) is also available as a commercial product, and specific examples thereof include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylate), 110, 111 (acid manufactured by BYK Chemie). Group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (high molecular weight copolymer) "," BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) " "EFKA 4047, 4050-4165 (polyurethane), EFKA 4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate) manufactured by EFKA , 6220 (fatty acid polyester), 6745 (phthalocyanine) Derivative), 6750 (azo pigment derivative), "Ajispar PB821, PB822, PB880, PB881" manufactured by Ajinomoto Fine-Techno, "Floren TG-710 (urethane oligomer)" manufactured by Kyoeisha Chemical Co., "Polyflow No. 50E, No. 300 (acrylic copolymer) "," Dispalon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, manufactured by Kusumoto Chemicals, Inc. DA-705, DA-725 ", Kao Corporation's" Demol RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "," Homogenol L- " 18 (polymeric polycarboxylic acid) "," Emulgen 920, 930, 935, 985 (Po Oxyethylene nonyl phenyl ether) "," acetamine 86 (stearylamine acetate) ", Nippon Lubrizol Co., Ltd." Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000, 22,000, 32,000, 38500 (graft type polymer) ", Nikko Chemicals Co., Ltd.," Nikkor T106 (polyoxyethylene sorbitan monooleate) ", MYS-IEX (polyoxy Ethylene monostearate), "Hinoact T-8000E" manufactured by Kawaken Fine Chemical Co., Ltd., "EFKA-46, EFKA-47, EFKA-47EA, EFKA-47EA, EFKA polymer 100, EFKA" manufactured by Morishita Sangyo Co., Ltd. Polymer 400, EFKA polymer 401, EFKA polymer 450 "," Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 "manufactured by San Nopco Co., Ltd.," ADEKA PLURONIC L31, F38 "manufactured by ADEKA Corporation. , L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 "and" Ionet S-20 "manufactured by Sanyo Chemical Industries, Ltd. Is mentioned.

These resins may be used alone or in combination of two or more.
Further, as a resin, (meth) acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and having a carboxylic acid in the side chain Resins having acid groups such as acidic cellulose derivatives and resins obtained by adding acid anhydrides to polymers having hydroxyl groups can also be used. Further, an N-substituted maleimide monomer copolymer described in JP-A-10-300922 and an ether dimer copolymer described in JP-A-2004-300204 can also be preferably used as the resin.

  In the present invention, as the resin, a polymer having a carboxy group in a side chain can also be used. These polymers may be used as a dispersant or a binder. As the polymer having a carboxy group in the side chain, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, Examples thereof include an alkali-soluble phenol resin such as a novolak resin, an acidic cellulose derivative having a carboxy group in a side chain, and a polymer obtained by adding an acid anhydride to a polymer having a hydroxy group. Particularly, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is preferable. Other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compounds. Examples of the alkyl (meth) acrylate and the aryl (meth) acrylate include 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, and cyclohexyl (meth) acrylate include styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene polymer Romonoma, polymethyl methacrylate macromonomer, and the like. Other monomers include N-substituted maleimide monomers (for example, N-phenylmaleimide, N-cyclohexylmaleimide, etc.) described in JP-A-10-300922. The other monomer copolymerizable with the (meth) acrylic acid may be only one kind or two or more kinds.

  In the present invention, the resin is a benzyl (meth) acrylate / (meth) acrylic acid copolymer, a benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, a benzyl (meth) acrylate. A) multi-component copolymer composed of acrylate / (meth) acrylic acid / other monomer can be preferably used. Further, copolymers of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, -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 A macromonomer / benzyl methacrylate / methacrylic acid copolymer can also be preferably used.

  The resin is a compound represented by the following formula (ED1) and / or a compound represented by the general formula (1) of JP-A-2010-168538 (hereinafter, these compounds may be referred to as “ether dimer”. It is also preferable to include a polymer (a) obtained by polymerizing a monomer component containing

In the 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 formula (ED1), 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. Examples thereof include methyl, ethyl and n-. Linear or branched alkyl groups such as propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, tert-butylcyclohexyl, dicyclo Alicyclic groups such as pentadienyl, tricyclodecanyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; aryls such as benzyl An alkyl group substituted with a group; Among these, particularly preferred are substituents of primary or secondary carbons such as methyl, ethyl, cyclohexyl, benzyl and the like which are hardly eliminated by an acid or heat, from the viewpoint of heat resistance.

  As a specific example of the ether dimer, for example, paragraph No. 0317 of JP-A-2013-29760 can be referred to, and the contents thereof are incorporated herein. The ether dimer may be only one kind or two or more kinds.

The resin may include a repeating unit derived from a compound represented by the following formula (X).
In the formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ has 1 to 20 carbon atoms which may contain a hydrogen atom or a benzene ring. Represents an alkyl group. n represents an integer of 1 to 15.

In the above formula (X), the number of carbon atoms of the alkylene group of R ₂ is preferably 2 to 3. The alkyl group of R ₃ has 1 to 20 carbon atoms, more preferably 1 to 10, and the alkyl group of R ₃ may include a benzene ring. Examples of the alkyl group containing a benzene ring represented by R ₃ include a benzyl group and a 2-phenyl (iso) propyl group.

As for the resin, the description in paragraphs 0558 to 0571 of JP-A-2012-208494 (paragraphs 0683 to 0700 of the corresponding U.S. Patent Application Publication No. 2012/0235099) can be referred to, and the contents thereof are described herein. Incorporated in
Further, the copolymer (B) described in paragraphs 0029 to 0063 of JP-A-2012-32767 and the alkali-soluble resin used in the examples, and the paragraphs 0088 to 0098 of JP-A-2012-208474. The binder resin described in the examples and the binder resin used in Examples, the binder resin described in Paragraph Nos. 0022 to 0032 of JP-A-2012-137331 and the binder resin used in the examples and JP-A-2013-024934 Binder resins described in paragraphs 0132 to 0143 of the publication and binder resins used in Examples, Binder resins used in paragraphs 0092 to 0098 of JP 2011-242752 and examples, JP 2012 JP-A-322770, paragraph numbers 0030 to 0072 It is also possible to use a binder resin according. These contents are incorporated herein.

  In the present invention, a resin having a polymerizable group can be used as the resin. The content of the resin having a polymerizable group is preferably from 1 to 80% by mass of the total solids of the coloring composition, and the lower limit is preferably 2% by mass or more, more preferably 3% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less.

  The weight average molecular weight of the resin having a polymerizable group is preferably from 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 3,000 or more, more preferably 5,000 or more.

As the resin having a polymerizable group, a polymer having a radical polymerizable group in a side chain is preferable. The resin having a polymerizable group preferably contains a repeating unit having a radical polymerizable group in a side chain, and more preferably a polymer having a repeating unit represented by the formula (1).
In the formula, R ¹ represents a hydrogen atom or an alkyl group, L ¹ represents a single bond or a divalent linking group, and P ¹ represents a radical polymerizable group.

The alkyl group represented by R ¹ is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. R ¹ is preferably a hydrogen atom or a methyl group.

L ¹ represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 12 carbon atoms, these and -CO -, - OCO -, - O -, - NH- and -SO ₂ - selected from And a group formed by combining one of the above. The alkylene group and the arylene group may have a substituent or may be unsubstituted. Examples of the substituent include a halogen atom, an alkyl group, an aryl group, a hydroxy group, a carboxy group, an alkoxy group, and an aryloxy group. Hydroxy groups are preferred.

P ¹ represents a radical polymerizable group. Examples of the radical polymerizable group include groups having an ethylenically unsaturated bond such as a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.

  In the resin having a polymerizable group, the content of the repeating unit having a radical polymerizable group in the side chain is preferably 5 to 100% by mass of all the repeating units. The lower limit is more preferably at least 10 mass%, even more preferably at least 15 mass%. The upper limit is more preferably equal to or less than 95% by mass, and still more preferably equal to or less than 90% by mass.

  The resin having a polymerizable group may contain another repeating unit in addition to the repeating unit represented by the above formula (1). Other repeating units may include a functional group such as an acid group. It may not contain a functional group.

Examples of the acid group include a carboxy group, a sulfonic acid group, and a phosphoric acid group. Only one type of acid group may be contained, or two or more types may be contained.
The proportion of the repeating unit having an acid group is preferably from 0 to 50% by mass of all the repeating units constituting the resin. The lower limit is more preferably 1% by mass or more, and still more preferably 3% by mass or more. The upper limit is more preferably equal to or less than 35% by mass, and still more preferably equal to or less than 30% by mass.

Other functional groups include lactones, acid anhydrides, amides, development promoting groups such as cyano groups, long-chain and cyclic alkyl groups, aralkyl groups, aryl groups, polyalkylene oxide groups, hydroxy groups, maleimide groups, amino groups, and the like. And can be appropriately introduced.
Further, it may contain a repeating unit derived from the above-mentioned ether dimer, a repeating unit derived from the compound represented by the formula (X) described in the above resin, and the like.

Specific examples of the resin having polymerizability will be shown, but the present invention is not limited thereto.

  Examples of commercially available resins having polymerizability include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co., Ltd.), Viscoat R-264, KS resist 106 (KS). All manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Praxel CF200 series (all manufactured by Daicel Corporation), Ebecryl3800 (manufactured by Daicel UCB), Accrecur RD-F8 ( Manufactured by Nippon Shokubai Co., Ltd.).

<< polymerizable compound >>
The coloring composition of the present invention contains a polymerizable compound. As the polymerizable compound, a known compound that can be cross-linked by a radical can be used. For example, a compound having a radical polymerizable group such as a group having an ethylenically unsaturated bond (radical polymerizable compound) is exemplified. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group, and a (meth) allyl group and a (meth) acryloyl group are preferable.

In the present invention, the polymerizable compound may be in any of chemical forms such as, for example, a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a multimer thereof. Monomers are preferred.
The monomer type polymerizable compound (polymerizable monomer) preferably has a molecular weight of 100 to 3,000. The upper limit is preferably 2000 or less, more preferably 1500 or less. The lower limit is preferably 150 or more, and more preferably 250 or more.

The content of the polymerizable compound is preferably from 1 to 80% by mass of the total solids of the coloring composition, and the lower limit is preferably at least 5% by mass, more preferably at least 10% by mass. The upper limit is preferably at most 70% by mass, more preferably at most 60% by mass.
The content of the polymerizable monomer is preferably 1 to 80% by mass of the total solids of the coloring composition, and the lower limit is preferably 2% by mass or more, and more preferably 3% by mass or more. The upper limit is preferably equal to or less than 70% by mass, more preferably equal to or less than 60% by mass, and still more preferably equal to or less than 50% by mass.
When a polymerizable monomer and a resin having a polymerizable group are used in combination, the mass ratio of the polymerizable monomer and the resin having a polymerizable group is preferably from 1: 1 to 20 and more preferably from 1: 1 to 15. Preferably, 1: 5 to 15 is more preferable.
The coloring composition of the present invention may include only one type of the polymerizable compound, or may include two or more types of the polymerizable compound. When two or more types are included, the total amount is preferably within the above range.

(Polymerizable monomer)
In the present invention, the polymerizable monomer is preferably a compound having three or more radical polymerizable groups, more preferably a compound having 3 to 15 or more radical polymerizable groups, and a compound having 3 to 6 or more radical polymerizable groups. Is more preferred.
Examples of these specific compounds include paragraphs [0095] to [0108] of JP-A-2009-288705, paragraph 0227 of JP-A-2013-29760, and paragraph 0254 of JP-A-2008-292970. To 0257, the contents of which are incorporated herein.

The polymerizable monomer is preferably a compound having an alkyleneoxy group, and more preferably a compound having a chain containing two or more alkyleneoxy groups as a repeating unit (alkyleneoxy chain). The alkyleneoxy chain preferably has 2 to 30 alkyleneoxy groups, more preferably 2 to 20, more preferably 2 to 10.
The carbon number of the alkyleneoxy group is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 4, and particularly preferably 2. That is, particularly preferred alkyleneoxy chain ethyleneoxy group, _{"- ((CH 2) a -O} ) b - " is preferably represented by. In the formula, a is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 4, and particularly preferably 2. b is preferably 2 to 30, more preferably 2 to 20, and still more preferably 2 to 10.

  In the present invention, as the polymerizable compound having an alkyleneoxy group, for example, at least one selected from the group of compounds represented by the following formula (Z-4) or (Z-5) can also be used.

In the formulas (Z-4) and (Z-5), E is independently-((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O)-. Wherein y independently represents an integer of 0 to 10, and X each independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxy group.
In the formula (Z-4), the total number of the acryloyl group and the methacryloyl group is 3 or 4, and m independently represents an integer of 0 to 10, and at least one of m represents an integer of 1 to 10. , Each m is an integer of 1 to 40.
In the formula (Z-5), the total of the acryloyl group and the methacryloyl group is 5 or 6, and n independently represents an integer of 0 to 10, and at least one of n represents an integer of 1 to 10. , The sum of each n is an integer of 1 to 60.

In the formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Further, the sum of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
In Formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. In addition, 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 the formula (Z-4) or the formula (Z-5),-((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O)- Is preferred that the terminal of is bonded to X

  The compound represented by the formula (Z-4) or (Z-5) may be used alone or in combination of two or more. In particular, in the formula (Z-5), a form in which all six Xs are acryloyl groups is preferable.

  The compound represented by the formula (Z-4) or the formula (Z-5) can be obtained by a ring-opening addition reaction of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol, which is a conventionally known process. The compound can be synthesized from a step of bonding a ring-opening skeleton and a step of reacting, for example, (meth) acryloyl chloride with a terminal hydroxyl group of the ring-opening skeleton to introduce a (meth) acryloyl group. Each step is a well-known step, and those skilled in the art can easily synthesize the compound represented by the formula (Z-4) or (Z-5).

  Among the compounds represented by the formula (Z-4) or (Z-5), a pentaerythritol derivative and / or a dipentaerythritol derivative are more preferable.

Specific examples of the polymerizable monomer having an alkyleneoxy group include the following compounds. M-2 is a mixture of the compound of the left formula and the compound of the right formula in a mass ratio of 7: 3.

  Commercially available polymerizable compounds having an alkyleneoxy group include, for example, SR-494 which is a tetrafunctional acrylate having four ethyleneoxy groups manufactured by Sartomer, and six pentyleneoxy groups manufactured by Nippon Kayaku Co., Ltd. Examples include DPCA-60, which is a hexafunctional acrylate, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy groups.

  In the present invention, as the polymerizable compound, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; Nippon Kayaku) Co., Ltd.), dipentaerythritol penta (meth) acrylate (Kayarad D-310 as a commercial product; Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (Kayarad DPHA as a commercial product; Nippon Kayaku) (A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and propylene glycol residues (for example, from Sartomer Co., Ltd.) Commercially available, SR454 SR499) can be preferably used. These oligomer types can also be used. In addition, KAYARAD RP-1040, DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.), NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like can also be used.

  The polymerizable compound may have an acid group such as a carboxy group, a sulfonic acid group, and a phosphoric acid group. Examples of commercially available products include M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.

  The preferred acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, particularly preferably 5 to 30 mgKOH / g. When the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the developing dissolution characteristics are good, and when the acid value is 40 mgKOH / g or less, it is advantageous in production and handling. Furthermore, the photopolymerization performance is good and the curability is excellent.

A compound having a caprolactone structure is also a preferred embodiment of the polymerizable compound.
The polymerizable compound having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, for example, DPCA-20, DPCA-30, DPCA-60, and DPCA-120.

Polymerizable compounds include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, and urethane acrylates. Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Further, use of addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277563, JP-A-63-260909, and JP-A-1-105238. This makes it possible to obtain a coloring composition having a very high photosensitive speed.
Commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku), and UA-306H UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.).

<< Photopolymerization initiator >>
The colored composition of the present invention preferably contains a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to light rays in the ultraviolet region to the visible region are preferable.
When a radically polymerizable compound is used as the polymerizable compound, the photopolymerization initiator is preferably a photoradical polymerization initiator.
The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 in the range of about 300 nm to 800 nm (more preferably, 330 nm to 500 nm).

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton and those having an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, and the like. Examples of halogenated hydrocarbon compounds having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), the compound described in British Patent No. 1388492, the compound described in JP-A-53-133428, the compound described in German Patent No. 3337024, F.I. C. J. Schaefer et al. Org. Chem. Compounds described in 29, 1527 (1964), compounds described in JP-A-62-58241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, U.S. Pat. And the compounds described in Japanese Patent No. 4212976.

  Further, from the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium Compounds selected from the group consisting of compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds are preferred.

The photopolymerization initiator is a trihalomethyltriazine compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, an oxime compound, a triallylimidazole dimer, an onium compound, a benzophenone compound, an acetophenone compound, and a trihalomethyltriazine compound, α -At least one compound selected from the group consisting of aminoketone compounds, oxime compounds, triallylimidazole dimers, and benzophenone compounds is preferred.
As specific examples of the photopolymerization initiator, for example, Paragraph Nos. 0265 to 0268 of JP-A-2013-29760 can be referred to, and the contents thereof are incorporated herein.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be suitably used. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and an acylphosphine-based initiator described in Japanese Patent No. 4225988 can be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (all trade names: manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which the maximum absorption wavelength is matched to a wave light source such as 365 nm or 405 nm can also be used.
As the acylphosphine-based initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names, both manufactured by BASF) can be used.

An oxime compound is more preferably used as the photopolymerization initiator.
As specific examples of the oxime compound, the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-80068, and the compounds described in JP-A-2006-342166 can be used.
In the present invention, examples of the oxime compound that can be suitably used include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyimiminobtan-2-one, -Acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2 -One, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
Also, J.I. C. S. Perkin II (1979) pp. 1653-1660); C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995, pp. 202-232), JP-A-2000-66385, JP-A-2000-80068, and JP-T-2004-534797. And the compounds described in JP-A-2006-342166.
As commercial products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used. Further, TR-PBG-304 (manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), Adeka Aquel's NCI-831 and Adeka Aquel's NCI-930 (manufactured by ADEKA) can also be used.

As the oxime compounds other than those described above, compounds described in JP-T-2009-519904 in which an oxime is linked to the N-position of a carbazole ring, and U.S. Pat. Compounds, compounds described in JP-A-2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced into a dye site, ketoxime compounds described in International Publication WO2009 / 131189, triazine skeleton and oxime skeleton A compound described in U.S. Pat. JP, 2014-137466, A paragraph number 0076 0079 may be used, such as compounds described in.
Preferably, for example, paragraphs 0274 to 0275 of JP-A-2013-29760 can be referred to, and the contents thereof are incorporated in the present specification.
Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferable. The N-O bond of the oxime may be an (E) -form oxime compound, a (Z) -form oxime compound, or a mixture of (E) -form and (Z) -form. .

In Formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In the formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Further, these groups may have one or more substituents. Further, the above-mentioned substituent may be further substituted with another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, an aryl group, and the like.
In Formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the substituents described above.
In Formula (OX-1), as the divalent organic group represented by A, an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, and an alkynylene group are preferable. These groups may have one or more substituents. Examples of the substituent include the substituents described above.

The oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has an absorption wavelength in the wavelength region of 360 nm to 480 nm, and particularly preferably has high absorbance at 365 nm and 405 nm.
The oxime compound has a molar extinction coefficient at 365 nm or 405 nm of preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, and more preferably from 5,000 to 200,000 from the viewpoint of sensitivity. It is particularly preferred that it is 2,000.
The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

Specific examples of the oxime compound preferably used in the present invention are shown below, but the present invention is not limited thereto.

  In the present invention, an oxime compound having a fluorine atom can be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include compounds described in JP-A-2010-262028, compounds 24 and 36 to 40 described in JP-T-2014-500852, and JP-A-2013-164471. (C-3). This content is incorporated herein.

  The content of the photopolymerization initiator is preferably from 0.1 to 50% by mass, more preferably from 0.5 to 30% by mass, and still more preferably from 1 to 20% by mass, based on the total solid content of the coloring composition. is there. Within this range, better sensitivity and pattern formability can be obtained. The coloring composition may include only one type of photopolymerization initiator, or may include two or more types. When two or more types are included, the total amount is preferably within the above range.

<< Pigment derivative >>
The coloring composition of the present invention preferably contains a pigment derivative. The pigment derivative is preferably a compound having a structure in which a part of an organic pigment is substituted with an acidic group, a basic group or a phthalimidomethyl group. The pigment derivative is preferably a pigment derivative having an acidic group or a basic group from the viewpoint of dispersibility and dispersion stability.

As organic pigments for constituting the pigment derivative, diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments And isoindoline pigments, isoindolinone pigments, quinophthalone pigments, sulene pigments, metal complex pigments and the like.
The acidic group contained in the pigment derivative is preferably a sulfonic acid group, a carboxylic acid group and a salt thereof, more preferably a carboxylic acid group and a sulfonic acid group, and particularly preferably a sulfonic acid group. As the basic group of the pigment derivative, an amino group is preferable, and a tertiary amino group is particularly preferable.

  As the pigment derivative, quinoline-based, benzimidazolone-based and isoindoline-based pigment derivatives are particularly preferred, and quinoline-based and benzimidazolone-based pigment derivatives are more preferred. The pigment derivative is preferably a pigment derivative having the following structure.

In the formula (PZ), A represents a structure selected from the following formulas (PA-1) to (PA-3);
B represents a single bond or a (t + 1) -valent linking group;
C represents a single _{bond, -NH -, - CONH -,} - CO 2 -, - SO 2 NH -, - O -, - S-, or, -SO ₂ - represents,
D represents a single bond, an alkylene group, or an arylene group,
E is, -SO ₃ H or salts thereof, -CO ₂ H or a salt thereof, or represents -N (Rpa) (Rpb),
Rpa and Rpb each independently represent an alkyl group or an aryl group; Rpa and Rpb may be linked to each other to form a ring;
t represents an integer of 1 to 5;

Rp1 represents an alkyl group or an aryl group having 1 to 5 carbon atoms,
Rp2 represents a halogen atom, an alkyl group or a hydroxy group,
Rp3 represents a single _{bond, -NH -, - CONH -,} - CO 2 -, - SO 2 NH -, - O -, - S-, or, -SO ₂ - represents,
s represents an integer of 0 to 4, and when s is 2 or more, a plurality of Rp2s may be the same as or different from each other;
* Represents a connection with B.

Rp1 is preferably a methyl group or a phenyl group, and more preferably a methyl group.
Rp2 is preferably a halogen atom, more preferably a chlorine atom.

In the formula (PZ), examples of the (t + 1) -valent linking group represented by B include an alkylene group, an arylene group, and a heteroarylene group. Examples of the alkylene group include linear, branched, and cyclic.
The (t + 1) -valent linking group is particularly preferably a linking group represented by the following structural formulas (PA-4) to (PA-9). * Represents a connecting portion with A and C.

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

  In the formula (PZ), examples of the alkylene group and the arylene group represented by D include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a decylene group, a cyclopropylene group, a cyclobutylene group, Examples thereof include a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a cyclodecylene group, a phenylene group, and a naphthylene group. Among them, D is preferably a straight-chain alkylene group, and more preferably a straight-chain alkylene group having 1 to 5 carbon atoms.

In the formula (PZ), when E represents —N (Rpa) (Rpb), examples of the alkyl group and the aryl group in Rpa and Rpb include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a sec group. -Butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, octyl group, decyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclodecyl group, phenyl group, Examples include a naphthyl group. As Rpa and Rpb, a linear or branched alkyl group is particularly preferred, and a linear or branched alkyl group having 1 to 5 carbon atoms is most preferred.
In the formula (PZ), when E represents a salt of —SO ₃ H or a salt of —CO ₂ H, the atom or atomic group forming the salt is an alkali such as a lithium atom, a sodium atom, and a potassium atom. Preferred are metals, ammonium, tetraalkylammonium and the like.
The above t is preferably 1 or 2.

The following are specific examples of the pigment derivative.

  The content of the pigment derivative is preferably from 1 to 50% by mass, more preferably from 3 to 30% by mass, based on the total mass of the pigment. One kind of the pigment derivative may be used alone, or two or more kinds thereof may be used in combination.

<< Solvent >>
The coloring composition of the present invention can contain a solvent. Examples of the solvent include an organic solvent. The solvent is not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition, but is preferably selected in consideration of the coatability and safety of the composition.

Examples of the organic solvent include, for example, the following.
As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl Alkyl oxyacetates (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxy Alkyl propionates (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy) Methyl cypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl esters of 2-alkyloxypropionic acid (for example, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate) (E.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy-2-methylpropion Methyl and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, pyruvate Acid propyl , Methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like. As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like can be mentioned. Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and the like. Examples of the aromatic hydrocarbons include toluene, xylene, and the like.

The organic solvent may be used alone or in combination of two or more.
When two or more organic solvents are used in combination, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, and 3-methoxypropionic acid are used. It is a mixed solution composed of two or more selected from methyl, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.
In the present invention, the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.

  The content of the solvent is preferably from 10 to 95% by mass based on the total amount of the coloring composition. The lower limit is more preferably 20% by mass or more, and even more preferably 30% by mass or more. The upper limit is more preferably 90% by mass or less.

<< polymerization inhibitor >>
The coloring composition of the present invention may contain a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the curable compound during the production or storage of the coloring composition.
Examples of the polymerization inhibitor include hydroquinone, paramethoxyphenol, di-tert-butyl-paracresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2, 2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine cerium salt and the like. Among them, paramethoxyphenol is preferable.
The content of the polymerization inhibitor is preferably 0.01 to 5% by mass based on the total solid content of the coloring composition.

<< Surfactant >>
The coloring composition of the present invention may contain various surfactants from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

By adding a fluorine-based surfactant to the composition, the liquid properties (particularly, fluidity) when prepared as a coating liquid are further improved, and the uniformity of the coating thickness and the liquid saving property are further improved. it can.
That is, when a film is formed using a coating solution to which a composition containing a fluorine-based surfactant is applied, the interface tension between the surface to be coated and the coating solution is reduced, and the wettability to the surface to be coated is reduced. This improves the applicability to the surface to be applied. Therefore, it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

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

Examples of the fluorine-based surfactant include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, and F479. F482, F554, F780, RS-72-K (manufactured by DIC Corporation), Florado FC430, FC431, and FC171 (manufactured by Sumitomo 3M Limited), Surflon S-382, SC -101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (all manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA) and the like. A block polymer can also be used as the fluorinated surfactant, and specific examples include, for example, compounds described in JP-A-2011-89090.
The fluorinated surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and has 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group and propyleneoxy group) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.
The weight average molecular weight of the above compound is preferably from 3,000 to 50,000, for example, 14,000. Further, a fluorinated polymer having an ethylenically unsaturated group in a side chain can be used as a fluorinated surfactant. Specific examples include compounds described in paragraphs [0050] to [0090] and paragraphs [0289] to [0295] of JP-A-2010-164965, such as Megafac RS-101, RS-102, and RS-718K manufactured by DIC.
The following compounds can also be used as the fluorine-based surfactant.

  Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl 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), Rusupasu 20000 (manufactured by Nippon Lubrizol Corporation), and the like. Further, NCW-101, NCW-1001, and NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. can also be used.

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

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

  Examples of the silicone-based surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (Toray Dow Corning Inc.) )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all made by Momentive Performance Materials), KP341, KF6001, KF6002 (all made by Shin-Etsu Silicone Co., Ltd.) , BYK307, BYK323, and BYK330 (all manufactured by Big Chemie).

One surfactant may be used alone, or two or more surfactants may be used in combination.
The content of the surfactant is preferably from 0.001 to 2.0% by mass, more preferably from 0.005 to 1.0% by mass, based on the total solid content of the coloring composition.

<< other components >>
The coloring composition of the present invention includes a thermal polymerization initiator such as an azo compound or a peroxide compound, a thermal polymerization component, an ultraviolet absorber such as alkoxybenzophenone, a plasticizer such as dioctyl phthalate, and a low molecular weight organic carboxylic acid. Various additives such as a developing property improver, a filler, an antioxidant, and an anti-agglomeration agent can be contained.

  The metal element may be contained in the composition depending on the raw materials used, but from the viewpoint of suppressing the occurrence of defects, the content of the Group 2 element (calcium, magnesium, etc.) in the coloring composition should be 50 ppm or less. Is preferably controlled to 0.01 to 10 ppm. Further, the total amount of the inorganic metal salt in the coloring composition is preferably 100 ppm or less, more preferably 0.5 to 50 ppm.

<Preparation method of coloring composition>
The coloring composition of the present invention can be prepared by mixing the above-mentioned components.
In preparing the coloring composition, each component may be blended together, or each component may be dissolved and dispersed in a solvent and then blended sequentially. In addition, the charging order and the working conditions at the time of compounding are not particularly limited. For example, the composition may be prepared by simultaneously dissolving and dispersing all the components in a solvent. If necessary, each component may be appropriately prepared as two or more solutions / dispersions and used at the time of use (at the time of application). ) May be mixed to prepare a composition.

  Also, if necessary, a red pigment is dispersed together with other components such as a resin, an organic solvent, and a pigment derivative to prepare a pigment dispersion, and the obtained pigment dispersion is mixed with other components of the coloring composition. It is preferable to prepare it.

In the production of the coloring composition, it is preferable to filter with a filter for the purpose of removing foreign substances and reducing defects. The filter can be used without any particular limitation as long as it has been conventionally used for filtration and the like. For example, a fluororesin such as polytetrafluoroethylene (PTFE), a polyamide resin such as nylon (eg, nylon-6, nylon-6,6), and a polyolefin resin such as polyethylene and polypropylene (PP) (high density, ultra high molecular weight) (Including polyolefin resin). Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred.
The pore size of the filter is suitably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. Within this range, it is possible to reliably remove fine foreign matter that hinders preparation of a uniform and smooth composition in a subsequent step. It is also preferable to use a fibrous filter medium. Examples of the filter medium include a polypropylene fiber, a nylon fiber and a glass fiber. , TPR005, etc.) and SHPX type series (SHPX003, etc.) filter cartridges.

When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more.
Further, first filters having different hole diameters within the above-described range may be combined. The pore diameter here can refer to the nominal value of the filter manufacturer. Commercially available filters are selected from various filters provided by, for example, Nippon Pall Co. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd. (former Nippon Microlith Co., Ltd.) or Kitz Micro Filter Co., Ltd. can do.
As the second filter, a filter formed of the same material as that of the above-described first filter can be used.
For example, the filtering by the first filter may be performed only with the dispersion liquid, and the second filtering may be performed after mixing other components.

<Physical properties of coloring composition>
The coloring composition of the present invention is formed by using the coloring composition of the present invention, and has a film having a thickness of 3.0 μm and has an integrated intensity of fluorescence in a wavelength range of 600 to 700 nm when excited by light having a wavelength of 534 nm, The value obtained by dividing the above-described cured film A having a thickness of 3.0 μm by the integrated intensity of the fluorescence in the wavelength range of 600 to 700 nm when excited by light having a wavelength of 534 nm is preferably 0.5 or less, It is more preferably at most 3, more preferably at most 0.2, particularly preferably at most 0.1.

<Emission filter>
The emission filter of the present invention is formed using the above-described coloring composition of the present invention. The emission filter of the present invention is preferably used as an emission filter of a fluorescence sensor.

In the emission filter of the present invention, the integrated intensity of fluorescence in a wavelength range of 600 to 700 nm when excited with light having a wavelength of 534 nm is preferably 0.5 to 0.0001, more preferably 0.3 to 0.001. preferable.
The thickness of the emission filter of the present invention is preferably from 10,000 to 50,000 nm, more preferably from 10,000 to 35,000 nm.
The transmittance of the emission filter of the present invention in the wavelength range of 400 to 450 nm is preferably 20% or less, more preferably 10% or less, and even more preferably 5% or less.
The transmittance of the emission filter of the present invention in the wavelength range of 550 to 600 nm is preferably 40% or more, more preferably 45% or more, and even more preferably 50% or more.

<Fluorescence sensor>
Next, the fluorescent sensor of the present invention will be described.
The fluorescent sensor of the present invention is not particularly limited as long as it has an emission filter using the coloring composition of the present invention.
Examples of the fluorescent sensor include a sensor which is used by irradiating a sample with excitation light. The sample is not particularly limited, and examples include a sample that emits fluorescence when irradiated with excitation light. Examples include proteins, nucleic acids (DNA (deoxyribonucleic acid), RNA (ribonucleic acid), etc.), cells, microorganisms, and the like.
The fluorescent sensor of the present invention can be preferably used as a DNA sensor.

One embodiment of the fluorescent sensor of the present invention will be described with reference to FIG. Note that the fluorescent sensor of the present invention is not limited to the following embodiments.
The fluorescent sensor shown in FIG. 1 is a drop-type fluorescent sensor. The fluorescent sensor shown in FIG. 1 includes a light source 1, an excitation filter 2, a beam splitter 3, an objective lens 4, a sample holder 5, an emission filter 6, and an eyepiece 7. The emission filter 6 is composed of the coloring composition of the present invention. The arrows in the figure indicate the traveling directions of light (excitation light, fluorescence, etc.).

In the fluorescence sensor shown in FIG. 1, light emitted from the light source 1 is limited to light having an excitation wavelength by the excitation filter 2 and becomes excitation light.
The light source 1 is not particularly limited. For example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, a xenon lamp, an ultraviolet light emitting diode (ultraviolet LED), an excimer laser generator, and the like can be used.
The excitation filter 2 can be appropriately selected depending on the type of the desired excitation light. For example, when light having a wavelength of 534 nm is used as excitation light, it is preferable to use a filter that transmits light having a wavelength of 534 nm and blocks light having other wavelengths.
The excitation light is reflected by the beam splitter 3 and passes through the objective lens 4 to irradiate the sample 100 on the sample holder 5. When the sample 100 is irradiated with the excitation light, the fluorescence generated from the sample and the excitation light scattered by the sample are guided to the beam splitter 3 through the objective lens 4. Of the light guided to the beam splitter 3, light containing a fluorescent component travels straight through the beam splitter 3 and is guided to the emission filter 6. The emission filter 6 transmits only the target fluorescence wavelength of the light that has traveled straight through the beam splitter 3, and guides the target fluorescence wavelength to the eyepiece 7. The fluorescence guided to the eyepiece can be observed with the naked eye, a camera, or the like.
In the fluorescence sensor of the present invention, since the emission filter 6 has low fluorescence with respect to the excitation light, the effect of the fluorescence caused by the emission filter can be suppressed, and the detection sensitivity is excellent.

Another embodiment of the fluorescent sensor of the present invention will be described with reference to FIG.
The fluorescence sensor shown in FIG. 2 is a transmission type fluorescence sensor. The fluorescent sensor illustrated in FIG. 2 includes a light source 11, an excitation filter 12, a mirror 13, a sample holder 14, an objective lens 15, an emission filter 16, and an eyepiece 17. The emission filter 16 is composed of the coloring composition of the present invention.
In the fluorescence sensor illustrated in FIG. 2, light emitted from the light source 11 is limited to light having an excitation wavelength by the excitation filter 12 and becomes excitation light. The excitation light is reflected by the mirror 13 and irradiates the sample 101 on the sample holder 14. When the sample 101 is irradiated with excitation light, the fluorescence generated from the sample and the excitation light scattered by the sample are guided to the emission filter 16 through the objective lens 15. The emission filter 16 transmits only the target fluorescence wavelength and guides the target fluorescence wavelength to the eyepiece 17. The fluorescence guided to the eyepiece can be observed with the naked eye, a camera, or the like.

<Production method of fluorescent sensor>
The method for manufacturing a fluorescent sensor of the present invention includes a step of forming an emission filter using the coloring composition of the present invention.
Specifically, the colored composition of the present invention can be produced through a step of forming a colored composition layer on a support and a step of curing the colored composition layer. Further, a step of forming a pattern may be further performed. Hereinafter, each step will be described.

  First, a colored composition layer is formed on a support using the colored composition of the present invention. The support is not particularly limited. A transparent substrate such as glass, a silicon wafer, and a polymer resin (such as an epoxy resin) may be used. As a method for applying the composition on the support, various methods such as slit coating, ink jetting, spin coating, casting coating, roll coating, and screen printing can be used.

  The coloring composition layer formed on the support may be prebaked. When performing prebaking, the prebaking temperature is preferably 150 ° C or lower, more preferably 120 ° C or lower, and even more preferably 110 ° C or lower. The lower limit may be, for example, 50 ° C. or higher, and may be 80 ° C. or higher. The prebake time is preferably from 10 seconds to 300 seconds, more preferably from 40 to 250 seconds, and still more preferably from 80 to 220 seconds. Drying can be performed on a hot plate, an oven, or the like.

Next, the coloring composition layer formed on the support is cured by performing a curing treatment. As the curing treatment, an exposure treatment is preferable.
As radiation (light) that can be used for exposure, ultraviolet rays such as g-rays and i-rays are preferably used (particularly preferably i-rays). Irradiation dose (exposure dose), for example, preferably 0.03~2.5J / cm ^2, more preferably 0.05~1.0J / cm ^2, and most preferably 0.08~0.5J / cm ² .
The oxygen concentration at the time of exposure can be appropriately selected. In addition to performing the treatment in the air, for example, in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, substantially oxygen-free) ), Or under a high oxygen atmosphere having an oxygen concentration exceeding 21% by volume (for example, 22% by volume, 30% by volume, 50% by volume). The exposure intensity is can be set appropriately, usually ^{1000W / m 2 ~100000W / m 2} ( ^{e.g., 5000W / m 2, 15000W /} m 2, 35000W / m 2) can be selected from the range of . Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / ^{m 2} at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / ^{m 2.}

  After performing the exposure processing, a heat treatment (post-bake) can be further performed. Post baking is a heat treatment after development to complete the curing of the film. When performing post-baking, the post-baking temperature is preferably, for example, 100 to 240 ° C. From the viewpoint of film curing, 200 to 230 ° C is more preferable. Post-baking can be performed on the film after development in a continuous manner or a batch manner using a heating means such as a hot plate, a convection oven (hot-air circulation type dryer), or a high frequency heater so that the above conditions are satisfied. .

  Thus, an emission filter can be manufactured. By incorporating the emission filter thus obtained into a fluorescent sensor, a fluorescent sensor can be manufactured.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist of the present invention. Unless otherwise specified, “parts” and “%” are based on mass. In the following, one inch is 2.54 cm.

(Method for measuring average particle size of pigment)
The average particle size of the pigment was measured by a dynamic light scattering method. Specifically, it was measured using DLS-8000 series (manufactured by Otsuka Electronics).

(Raw materials used)
The components used in the coloring compositions of Examples and Comparative Examples are as follows.
-Red pigment PR144: C.I. I. Pigment Red 144
PR166: C.I. I. Pigment Red 166
PR254: C.I. I. Pigment Red 254
・ Resin (Resin 1)
D-1: The following structure (weight-average molecular weight: 38000, the numerical value described along with each repeating unit (main chain) represents the content (mass ratio) of each repeating unit. Indicates the number of repetitions of the repeat site.)
D-2: The following structure (weight-average molecular weight: 20,000, the numerical value described for each repeating unit (main chain) represents the content (mass ratio) of each repeating unit. Indicates the number of repetitions of the repeat site.)
D-3: The following structure (weight-average molecular weight: 24000, the numerical value described in addition to each repeating unit (main chain) represents the content (mass ratio) of each repeating unit. Indicates the number of repetitions of the repeat site.)
(Resin 2)
B-1: The following structure (the weight-average molecular weight is 11,000, and the numerical value described with each repeating unit (main chain) represents the content (mass ratio) of each repeating unit.)
B-2: The following structure (weight-average molecular weight: 12,000, and the numerical value described with each repeating unit (main chain) represents the content (mass ratio) of each repeating unit.)
B-3: The following structure (the weight-average molecular weight is 40000, and the numerical value described with each repeating unit (main chain) represents the content (mass ratio) of each repeating unit.)
-Pigment derivative PZ-1: the following structure
-Polymerizable compounds M-1 to M-3: The following structures. M-2 is a mixture of the compound of the left formula and the compound of the right formula in a mass ratio of 7: 3. N of M-3 is 1-3, and the sum of four n is 12 or less.
M-4: NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
-Photopolymerization initiators I-1 and I-2: The following structure
-Surfactant W-1: the following mixture (Mw = 14000, 10% PGMEA solution)
W-2: The following structure

(Preparation of coloring composition)
Evaluation was performed using the coloring compositions of the components shown in Table 1.
(Composition ratio)
Pigment: 5% by mass
Resin (Resin 1): 1.5% by mass
Pigment derivative: 0.075% by mass
Polymerization initiator: 0.3% by mass
Polymerizable compound: 0.7% by mass
Resin (Resin 2): 4.925% by mass
Surfactant: 0.001% by mass
Solvent (propylene glycol monomethyl ether acetate (PGMEA)): balance

  The coloring composition was prepared by mixing a pigment, a resin 1, and a pigment derivative to prepare a pigment dispersion, and blending the remaining components with the pigment dispersion to produce a coloring composition having the above composition.

(Fluorescence intensity measurement)
Each coloring composition was applied on a glass substrate to form a coloring composition layer. The film thickness was adjusted so that the transmittance of the cured film at a wavelength of 500 nm was 5%.
Next, after pre-baking at 100 ° C. for 2 minutes, exposure was performed under the condition of 1000 mJ / cm ² , and post-baking was performed at 220 ° C. for 5 minutes to produce a cured film.
For the obtained cured film, the integrated intensity of fluorescence in the wavelength range of 600 to 700 nm was measured using Hitachi High-Tech F4500 under the conditions of an excitation wavelength of 534 nm, an excitation slit of 5 nm, a fluorescence slit of 5 nm, and a photovoltage of 950 V. The fluorescence intensity was measured using a 530 nm bandpass filter on the light source side to suppress stray light and a sharp cut filter on the detection side to suppress scattered light. Using the integrated value of the obtained fluorescence spectrum at 600 to 700 nm, a value obtained by dividing by the result of the coloring composition of Comparative Example 1 was calculated as a fluorescence intensity ratio.

(Dispersion stability evaluation)
Each colored composition was stored in a thermostat at 50 ° C., and the spectrum was measured one week later. The spectrum at 400 to 800 nm before and after storage was measured, and the wavelength at which the spectral variation before and after storage was the maximum was determined under the following conditions.
5: Spectral variation is 1% or less before and after storage 4: Spectral variation is more than 1% and 3% or less before and after storage 3: Spectral variation is more than 3% and 5% or less before and after storage 2: Spectral variation is 5 before and after storage % And 10% or less 1: Spectral fluctuation exceeds 10% before and after storage

(Light resistance evaluation)
The substrate on which the fluorescence intensity was measured was irradiated with an illuminance of 1.0 × 10 ⁵ lux for 50 hours using a xenon lamp to measure light resistance. The spectrum at 400 to 800 nm before and after the treatment was measured, and the wavelength at which the spectral fluctuation before and after the treatment was the largest was determined under the following conditions.
5: Spectral variation is 1% or less before and after processing 4: Spectral variation is more than 1% and 3% or less before and after processing 3: Spectral variation is more than 3% and 5% or less before and after processing 2: Spectral variation is 5 before and after processing % And 10% or less 1: Spectral fluctuation exceeds 10% before and after processing

(Resolution evaluation)
A photomask having a pattern at the time of exposure was mounted on a substrate for measuring the fluorescence intensity, and exposure was performed. Thereafter, development processing was performed with a 2.5% by mass aqueous solution of TMAH (tetramethylammonium hydroxide). The critical size of the pattern shape that can be produced after development was determined under the following conditions.
5: The critical resolution is 1.4 μm or less 4: The critical resolution is more than 1.4 μm and 1.7 μm or less 3: The critical resolution is more than 1.7 μm and 2 μm or less 2: The critical resolution is more than 2 μm and 3 μm or less 1: No litho

(Residual defect evaluation)
The number of defects in the solid film of the substrate whose fluorescence intensity was measured was measured by ComPlus manufactured by Applied Materials. The measurement results were determined under the following conditions. Dust judged to be derived from a material of 1 μm or more was judged as a solid film defect.
5: The number of defects per 8 inch wafer is 100 or less 4: The number of defects per 8 inch wafer is more than 100 and 300 or less 3: The number of defects per 8 inch wafer is more than 300 and 500 or less 2: 8 The number of defects per inch wafer exceeds 500 and 1000 or less The number of defects per 1/8 inch wafer exceeds 1000

As shown in the above table, in the examples, the fluorescence intensity ratio was small. Further, the fluorescence sensor using the cured film of the example as an emission filter was excellent in detection sensitivity.
On the other hand, the fluorescence sensor using the cured film of the comparative example as an emission filter was inferior in detection sensitivity.
The cured films of Examples 1 to 38 and Comparative Examples 1 to 5 were incorporated as emission filters of a fluorescence sensor, and the sample was irradiated with excitation light having a wavelength of 534 nm to perform fluorescence detection. Had better detection sensitivity than Comparative Examples 1 to 5.

Reference Signs List 1 light source, 2 excitation filter, 3 beam splitter, 4 objective lens, 5 sample holder, 6 emission filter, 7 eyepiece, 11 light source, 12 excitation filter, 13 mirror, 14 sample holder, 15 objective lens, 16 emission filter, 17 Eyepiece

Claims (20)

Fluorescent light that irradiates a sample that generates fluorescence by being irradiated with the excitation light with excitation light, transmits light containing the fluorescence generated from the sample through an emission filter, and detects light containing the fluorescence transmitted through the emission filter. A sensor, a colored composition for forming the emission filter ,
Color index pigment red 144, and a red pigment containing at least one selected from color index pigment red 166 , a resin, a polymerizable compound, a photopolymerization initiator, and a solvent,
The resin comprises a resin having a carboxyl group in a side chain,
The integrated intensity of fluorescence in a wavelength range of 600 to 700 nm when a film having a thickness of 3.0 μm and formed using the coloring composition is excited by light having a wavelength of 534 nm,
The cured film A having a thickness of 3.0 μm and containing 40% by mass of Color Index Pigment Red 254 in the total solid content was divided by the integrated intensity of fluorescence in the wavelength range of 600 to 700 nm when excited with light having a wavelength of 534 nm. A colored composition having a value of 0.5 or less. Fluorescent light that irradiates a sample that generates fluorescence by being irradiated with the excitation light with excitation light, transmits light containing the fluorescence generated from the sample through an emission filter, and detects light containing the fluorescence transmitted through the emission filter. A sensor, a colored composition for forming the emission filter ,
Color index pigment red 144, and a red pigment containing at least one selected from color index pigment red 166 , a resin, a polymerizable compound, a photopolymerization initiator, and a solvent,
The photopolymerization initiator is an oxime compound,
The integrated intensity of fluorescence in a wavelength range of 600 to 700 nm when a film having a thickness of 3.0 μm and formed using the coloring composition is excited by light having a wavelength of 534 nm,
The cured film A having a thickness of 3.0 μm and containing 40% by mass of Color Index Pigment Red 254 in the total solid content was divided by the integrated intensity of fluorescence in the wavelength range of 600 to 700 nm when excited with light having a wavelength of 534 nm. A colored composition having a value of 0.5 or less. Fluorescent light that irradiates a sample that generates fluorescence by being irradiated with the excitation light with excitation light, transmits light containing the fluorescence generated from the sample through an emission filter, and detects light containing the fluorescence transmitted through the emission filter. A sensor, a colored composition for forming the emission filter ,
Color Index Pigment Red 144, and a red pigment containing at least one selected from Color Index Pigment Red 166, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent,
The total content of the color index pigment red 144 and the color index pigment red 166 in the total mass of the red pigment is 99.9% by mass or more,
A coloring composition, wherein the resin contains a resin having a carboxyl group in a side chain.   The coloring composition according to claim 3, wherein the content of the color index pigment red 144 in the total mass of the red pigment is 99.9% by mass or more.   The coloring composition according to any one of claims 1 to 4, wherein the red pigment has an average particle size of 5 to 500 nm.   The coloring composition according to any one of claims 1 to 5, wherein the polymerizable compound is a polymerizable monomer.   The coloring composition according to claim 6, wherein the polymerizable monomer has three or more radical polymerizable groups.   The coloring composition according to claim 6, wherein the polymerizable monomer has an alkyleneoxy group.   The coloring composition according to claim 8, wherein the polymerizable monomer has a chain containing two or more alkyleneoxy groups as a repeating unit.   The coloring composition according to any one of claims 1 to 9, wherein the resin includes a graft copolymer. The average particle size of the red pigment is 5 to 500 nm,
The coloring composition according to any one of claims 1 to 9, wherein the resin includes a graft copolymer. The coloring composition according to any one of claims 1 to 11, wherein the resin comprises a resin containing a repeating unit represented by any of the following formulas (1) to (4);
In Formulas (1) to (4), W ¹ , W ² , W ³ , and W ⁴ each independently represent an oxygen atom or NH;
X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom or a monovalent organic group,
Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group;
Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a monovalent organic group,
R ³ represents an alkylene group,
R ⁴ represents a hydrogen atom or a monovalent organic group,
n, m, p, and q each independently represent an integer of 1 to 500;
j and k each independently represent an integer of 2 to 8,
In Formula (3), when p is 2 to 500, a plurality of R ³ may be the same or different from each other;
In the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ may be the same or different.   The coloring composition according to any one of claims 1 to 12, wherein the resin includes a resin having a polymerizable group in a side chain.   The coloring composition according to claim 1, wherein the photopolymerization initiator is an oxime compound.   The coloring composition according to any one of claims 1 to 14, wherein the red pigment has an average particle size of 5 to 300 nm.   The coloring composition according to any one of claims 1 to 15, further comprising a fluorine-based surfactant. Fluorescent sensors having emission filter using the coloring composition according to any one of claims 1-16. The fluorescence sensor according to claim 17 , wherein the fluorescence sensor is used by irradiating a sample with excitation light. The fluorescent sensor according to claim 17 , wherein the fluorescent sensor is a DNA sensor. Method for producing a fluorescent sensor including a step of forming a emission filter using the coloring composition according to any one of claims 1-16.