WO2017030155A1

WO2017030155A1 - Dye composition, fluorescence sensor, and production method for fluorescence sensor

Info

Publication number: WO2017030155A1
Application number: PCT/JP2016/074053
Authority: WO
Inventors: 上村　哲也
Original assignee: 富士フイルム株式会社
Priority date: 2015-08-19
Filing date: 2016-08-18
Publication date: 2017-02-23
Also published as: JP6663433B2; KR102121760B1; JPWO2017030155A1; TWI693471B; TW201710785A; KR20180029064A

Abstract

Provided are: a dye composition with which it is possible to obtain a fluorescence sensor of exceptional detection sensitivity; a fluorescence sensor of exceptional detection sensitivity; and a production method for a fluorescence sensor of exceptional detection sensitivity. The dye composition is used to form an emission filter of a fluorescence sensor, and includes 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.

Description

Coloring composition, fluorescent sensor, and method for manufacturing fluorescent sensor

The present invention relates to a colored composition, a fluorescence sensor, and a method for producing the fluorescence sensor.

There is a fluorescence 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.
The inspection by the fluorescence sensor is performed by irradiating the sample with excitation light, transmitting the fluorescence generated from the sample through the emission filter, and observing the fluorescence transmitted through the emission filter.

For example, a filter using a red pigment is used as an emission filter of a fluorescent sensor. As the 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 chromophthaled 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 using a composition containing Color Index Pigment Red 144, polyvinyl alcohol, a surfactant, and water. Yes.

JP 60-129739 A Japanese Patent Laid-Open No. 10-239835

As a result of intensive studies on the fluorescence sensor by the present inventor, it was found that the emission filter using the color index pigment red 254 is likely to generate fluorescence due to excitation light, and the detection sensitivity of the fluorescence sensor is likely to decrease.

On the other hand,

Patent Documents

1 and 2 have no description or suggestion regarding a fluorescent sensor.

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

As a result of intensive studies on the coloring composition for forming the emission filter of the fluorescent sensor, the present inventor has found that the color index pigment red 144 and the color index pigment red 166 are pigments that are difficult to generate fluorescence by excitation light. It was. As a result of studies on the colored composition, the integrated intensity of fluorescence in the wavelength range of 600 to 700 nm when excited with light having a wavelength of 534 nm in a 3.0 μm-thick film formed using the colored composition, A colored composition having a value obtained by dividing a cured film containing Color Index Pigment Red 254, which will be described later, 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 is 0.5 or less. In this way, the inventors 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,
Including a red pigment, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent,
The integrated intensity of fluorescence in the wavelength range of 600 to 700 nm when excited with light having a wavelength of 534 nm in a film having a thickness of 3.0 μm formed using the coloring composition,
Divided by the integrated intensity of fluorescence in the wavelength range of 600 to 700 nm when cured with a 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. 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 radically 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 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 represents an integer of 1 to 500;
j and k each independently represents an integer of 2 to 8,
In the 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 from each other.
<10> A fluorescent sensor having an emission filter using the colored composition according to any one of <1> to <9>.
<11> The fluorescence sensor according to <10>, wherein the fluorescence sensor is used by irradiating a sample with excitation light.
<12> The fluorescence sensor according to <10> or <11>, wherein the fluorescence sensor is a DNA sensor.
<13> A method for producing a fluorescent sensor comprising a step of forming an emission filter using the colored composition according to any one of <1> to <9>.

ADVANTAGE OF THE INVENTION According to this invention, it is possible to provide the coloring composition which can obtain the fluorescence sensor excellent in the detection sensitivity, the fluorescence sensor excellent in the detection sensitivity, and the manufacturing method of the fluorescence sensor excellent in the detection sensitivity. became.

It is a schematic block diagram of one Embodiment of the fluorescence sensor of this invention. It is a schematic block diagram of other embodiment of the fluorescence sensor of this invention.

In this specification, the total solid content refers to the total mass of components obtained by removing the solvent from all components of the composition. Moreover, solid content means solid content in 25 degreeC.
In the notation of groups (atomic groups) in this specification, the notation that does not indicate substitution and non-substitution includes not only those having no substituent but also those 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).
“Radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, 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, “exposure” in this specification is not only exposure with a deep ultraviolet ray, an X-ray, EUV light, etc. typified by a mercury lamp or an excimer laser, but also drawing with a particle beam such as an electron beam or an ion beam. Are also included in the exposure.
In the present specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, “(meth) acryl” represents both and / or acryl and “(meth) acryloyl” “Represents both and / or acryloyl and methacryloyl, and“ (meth) allyl ”represents both and / or 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 this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value in a gel permeation chromatography (GPC) measurement. In this 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. 0.0 mm ID (inner diameter) × 15.0 cm) can be obtained 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 coloring compound that is difficult to dissolve in a solvent. Typically, it means a dye compound that exists in a dispersed state as particles in the composition. Here, an arbitrary solvent is mentioned with a solvent, For example, the solvent illustrated in the column of the solvent mentioned later is mentioned. The pigment used in the present invention preferably has a solubility at 25 ° C. of 0.1 g / 100 g Solvent or less, for example, in any of 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, which includes a red pigment, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent and is formed using a colored 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 having a wavelength of 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 divided by the integrated intensity of fluorescence in the wavelength range of 600 to 700 nm is 0.5 or less.
The cured film A contains 5% by mass of Color Index Pigment Red 254 having an average particle diameter of 50 nm, 1.5% by mass of a resin represented by Formula D-1, and 0% of a pigment derivative represented by Formula PZ-1. 0.075% by mass, 0.7% by mass of the polymerizable compound represented by Formula M-1, 4.925% by mass of the resin represented by Formula B-2, and represented by Formula I-1. A composition containing 0.3% by mass of a photopolymerization initiator and the balance being propylene glycol monomethyl ether acetate was applied on a glass substrate so that the film thickness after curing was 3.0 μm, After drying at 100 ° C., a cured film obtained by exposing the i-line with an exposure amount of 1000 mJ / cm ² is preferable. The weight average molecular weight of D-1 is 38000, and the numerical value written in each repeating unit (main chain) represents the content (mass ratio) of each repeating unit, and the numerical value written in the repeating part of the side chain. Indicates the number of repetitions of the repeating site. Further, the weight average molecular weight of B-2 is 12000, and the numerical value written together 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, it is possible to form an emission filter having low fluorescence with respect to excitation light by using the colored composition of (1) or (2).
In addition, the color index pigment red 144 and the color index pigment red 166 have particularly low fluorescence with respect to the excitation light, and also have excellent heat resistance, and therefore lower fluorescence with respect to the excitation light. Furthermore, an emission filter having excellent heat resistance can be formed.
And since the emission filter using the coloring composition of the present invention has low fluorescence with respect to excitation light, the fluorescence sensor having the emission filter using the coloring composition of the present invention has a fluorescence attributed to the emission filter. The detection sensitivity is small 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 the formula R-1 is preferable.

In the formula, R ¹ to R ¹⁴ each independently represents 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.
At least two of R ¹ to R ⁵ are preferably halogen atoms, and the rest are preferably hydrogen atoms. More preferably, two of R ¹ to R ⁵ are halogen atoms, and the rest are hydrogen atoms. In particular, R ¹ and R ⁴ are preferably halogen atoms, and R ² , R ³ and R ⁵ are preferably 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 preferred 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 all be hydrogen atoms, at least one of R ⁶ to R ⁹ may be a halogen atom, and the remaining may be a hydrogen atom. 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. It is preferable that at least one selected from Pigment Red 166 is included. C. I. Pigment red 144, and C.I. I. Since Pigment Red 166 has low fluorescence with respect to excitation light, an emission filter having low fluorescence with respect to excitation light can be formed.

In the present invention, the average particle size of the red pigment is preferably 5 to 1000 nm, more preferably 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 the red pigment tends to have low fluorescence with respect to excitation light by reducing the particle size of the red pigment. If the average particle diameter of the red pigment is within the above range, it is easy to form an emission filter having lower fluorescence with respect to excitation light.

In the present invention, the “average particle size” of the red pigment is an average particle size of secondary particles in which the 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 colored composition of the present invention, the content of the red pigment is preferably 10 to 90% by mass with respect to the total solid content of the colored composition. The lower limit is more preferably 20% by mass or more, and further preferably 30% by mass or more. The upper limit is more preferably 80% by mass or less, and still more preferably 70% by mass or less.
C. in the total mass of the red pigment. I. Pigment red 144, and C.I. I. The total content of CI Pigment Red 166 is preferably 50 to 100% by mass. The lower limit is more preferably 60% by mass or more, still more 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. It is also preferable that only the pigment red 166 is used. The red pigment is substantially C.I. I. Pigment red 144, and C.I. I. Pigment Red 166 alone is the case where C.I. I. Pigment red 144 and C.I. I. Pigment Red 166 is preferably contained in a total of 99% by mass or more, and 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 the pigment red 166 is contained, one or more of the following pigments can be selected and used so that the coloring composition satisfies the requirement (1) described above. The following pigments are C.I. I. Pigment red 144 and / or C.I. I. It can also be used in combination with Pigment Red 166.
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

-Refinement of pigment-
In the present invention, the red pigment is preferably a fine and sized pigment. Finer pigments are prepared by preparing a high-viscosity liquid composition together with a pigment, a water-soluble organic solvent, and water-soluble inorganic salts, and applying a stress using a wet pulverizer and grinding. Achieved.

Water-soluble organic solvents used in the pigment refinement process include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether , Propylene glycol, propylene glycol monomethyl ether acetate and the like.
Moreover, as long as it is adsorbed to the pigment by being used in a small amount and is not washed away in the waste water, the water solubility is low or other solvents that are not water soluble, such as 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 hydrocarbons, acetone, methyl ethyl ketone, methyl Isobutyl ketone, cyclohexanone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and the like may be used.
Only one type of solvent may be used in the pigment refinement step, or two or more types may be mixed and used as necessary.

Examples of the water-soluble inorganic salt used in the pigment refining step include sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate and the like.
The amount of the water-soluble inorganic salt used in the miniaturization step is preferably 1 to 50 times by mass of the pigment. A larger amount of the water-soluble inorganic salt has a grinding effect, but a more preferable amount is 1 to 10 times in terms of productivity. Moreover, it is preferable to use inorganic salts having a moisture content of 1% or less.
The amount of the water-soluble organic solvent used in the miniaturization step is preferably 50 to 300 parts by mass, more preferably 100 to 200 parts by mass with respect to 100 parts by mass of the pigment.

There are no particular restrictions on the operating conditions of the wet pulverizer in the pigment refinement process. However, in order to effectively carry out the grinding with the pulverizing media, the operating condition when the apparatus is a kneader is the rotational speed of the blade in the apparatus. Is preferably from 10 to 200 rpm, and a relatively large biaxial rotation ratio is preferable because of a high grinding effect. The operation time is preferably 1 to 8 hours together with the dry grinding time, and the internal temperature of the apparatus is preferably 50 to 150 ° C. Further, the water-soluble inorganic salt as a grinding medium preferably has a grinding particle size of 5 to 50 μm, a sharp particle size distribution, and a spherical shape.

<< Other chromatic colorants >>
The coloring composition of the present invention may contain a chromatic colorant other than the red pigment. Other chromatic colorants may be pigments or dyes. 1 type may be sufficient as another colorant, and 2 or more types may be sufficient as it.
Other chromatic colorants are preferably yellow pigments for the purpose of reducing 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 the white colorant and the black colorant. The chromatic colorant is preferably a colorant having a maximum absorption wavelength in the wavelength range of 400 to 700 nm. Further, “having a maximum absorption wavelength in the wavelength range of 400 to 700 nm” means having a wavelength exhibiting the maximum absorbance in the wavelength range of 400 to 700 nm in the absorption spectrum. For example, it is preferable that the absorption spectrum in the wavelength range of 350 to 1300 nm has a wavelength exhibiting the maximum absorbance in the wavelength range of 400 to 700 nm.

Examples of pigments include various conventionally known pigments. In consideration of the fact 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 considering the handling property, the average particle size of the pigment is 0.01 to 0.00. 1 μm is preferable, and 0.01 to 0.05 μm is more preferable.

The following can be mentioned as a pigment. 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 No. 64-90403, JP-A No. 64-91102, JP-A No. 1-94301, JP-A No. 6-11614, No. 2592207, and US Pat. No. 4,808,501. No. 5,667,920, U.S. Pat. No. 505950, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, etc. Can be used. When classified as chemical structures, pyrazole azo compounds, pyromethene compounds, anilinoazo 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. A dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A.

When the colored 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 colored composition is preferably 1 to 60% by mass. The lower limit is more preferably 5% by mass or more, and still 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 blended, for example, for the purpose of dispersing the pigment in the composition or the purpose of the binder. In addition, the resin mainly used for dispersing the pigment is also referred to as a dispersant. However, such use of the resin is merely an example, and the resin can be used for other purposes.

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

The resin content is preferably 1 to 80% by mass of the total solid content of the coloring composition. The lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more. The upper limit is preferably 70% by mass or less, and more preferably 60% by mass or less. The colored composition of the present invention may contain only one type of resin, or may contain 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 that the resin has include a carboxy group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. Examples of basic groups possessed by the resin include amino groups. Moreover, in this invention, resin which does not have an acid group and a basic group can also be used as a dispersing agent.

When the resin has an acid group, the acid value of the resin is preferably 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 even more preferably 50 mgKOH / g or more. The upper limit is more preferably 300 mgKOH / g or less, 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 dispersant for a red pigment. In the present invention, the graft copolymer means a resin having a graft chain. The graft chain means from the base of the main chain of the polymer to the end of the 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. Further, the number of atoms excluding hydrogen atoms per graft chain is preferably 40 to 10,000, more preferably 50 to 2000, and still more preferably 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. Of these, a (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 increase 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 from 5,000 to 100,000, more preferably from 10,000 to 50,000, still more preferably from 10,000 to 30,000. The number average molecular weight (Mn) of the graft copolymer is preferably 2500 to 50000, more preferably 5000 to 30000, and still more preferably 5000 to 15000.

As the macromonomer used when the graft copolymer is produced by radical polymerization, a known macromonomer can be used, which is a macromonomer AA-6 (polymethacrylic group whose terminal group is a methacryloyl group) manufactured by Toagosei Co., Ltd. Acid-6), AS-6 (polystyrene whose terminal group is a methacryloyl group), AN-6S (a copolymer of styrene and acrylonitrile whose terminal group is a methacryloyl group), AB-6 (polyester whose terminal group is a methacryloyl group) Butyl acrylate), PLACEL FM5 manufactured by Daicel Corporation (2-hydroxyethyl methacrylate with 5 molar equivalents of ε-caprolactone), FA10L (2-hydroxyethyl acrylate with 10 molar equivalents of ε-caprolactone), And a polyester-based macro described in JP-A-2-272009 And monomers.

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 represents an integer of 1 to 500;
j and k each independently represents an integer of 2 to 8,
In the 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 from each other.

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

In the 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 constraints. Further, a hydrogen atom or a methyl group is more preferable, and a methyl group is particularly preferable.

In the 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 (Y-1) to (Y-21) linking groups. . In the structures shown below, A and B represent binding sites with the left end group and the right end group in Formulas (1) to (4), respectively.

In the formulas (1) to (4), Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a monovalent organic group. 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 An amino group etc. are mentioned. 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 the 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. J and k in the formulas (1) and (2) are preferably integers of 4 to 6 and most preferably 5 from the viewpoints of dispersion stability and developability.

In the 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 from each other.

In formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited in terms of structure. R ⁴ preferably includes a hydrogen atom, an alkyl group, an aryl group, and 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 each other.

The graft polymer preferably contains at least one selected from a repeating unit represented by the following formula (1A) and a repeating unit represented by the following formula (2A) from the viewpoints of dispersion stability and developability. .

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 unit 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 5 to 95% by mass and more preferably 10 to 95% by mass with respect to the total mass of the graft resin.

The graft polymer may further have a repeating unit having a functional group capable of interacting with the pigment other than the graft chain and the acid group. The above-mentioned repeating unit having a functional group is not particularly limited in terms of 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 heterocyclic ring containing an N atom, and an amide group. Examples of the coordinating group and the reactive group include acetylacetoxy group, trialkoxysilyl group, isocyanate group, acid anhydride residue, acid chloride residue and the like. The graft polymer may or may not contain the above-mentioned repeating unit having a functional group.
The amount is preferably 0.1 to 50% by mass, more preferably 0.1 to 30% by mass, based on the total mass of the graft resin.

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, more preferably derived from a compound having a ClogP value of 1.2 to 8. It is a repeating unit.

ClogP values can be obtained from Daylight Chemical Information System, Inc. It is a value calculated by the program “CLOGP” available from This program provides the value of “computation logP” calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of a compound, which divides the chemical structure into substructures (fragments) and estimates the logP value of the compound by summing the logP contributions assigned to that fragment. Details thereof are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 is used.
A. J. et al. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P.A. G. Sammes, J.M. B. Taylor and C.M. A. Ramsden, Eds. , P. 295, Pergamon Press, 1990; Hansch & A. J. et al. Leo. Substituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A. J. et al. Leo. Calculating log Poc from structure. Chem. Rev. , 93, 1281-1306, 1993.

logP means the common logarithm of the partition coefficient P (Partition Coefficient), and quantitatively determines how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. It is a physical property value expressed as a numerical value, and is represented by the following formula.
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 logP value increases to a positive value across 0, the oil solubility increases. When the logP value increases to a negative value, the water solubility increases. There is a negative correlation with the water solubility of the organic compound. It is widely used as a parameter for estimating aqueous properties.

The graft copolymer preferably has one or more types of repeating units selected from repeating units derived from monomers represented by the following formulas (i) to (iii) as hydrophobic repeating units.

In the above formulas (i) to (iii), R ¹ , R ² , and R ³ each independently represents a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), or a carbon atom number of 1 to 6 An alkyl group (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 a hydrogen atom.

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. As the divalent linking group, a divalent aliphatic group (for example, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group), divalent aromatic group (for example, arylene group) , Substituted arylene group), divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR ³¹ —, where R ³¹ Are aliphatic groups, aromatic groups or heterocyclic groups), carbonyl groups (—CO—), or combinations thereof.
L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH ₂ CH ₂ ) _n —, and n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

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

The aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms in the aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-10. The aliphatic group further includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4-cyclohexyl. A phenyl group and the like are included. 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.) Hydrocarbon ring, homobredan, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclic hydrocarbon ring such as tricyclo [4.3.1.1 ^2,5 ] undecane ring, tetracyclo [4 .4.0.1 ^2,5 . 1 ^7,10 ] dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. The bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as 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. The aliphatic group is preferably a saturated aliphatic group rather 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 in the aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10. 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-membered or 6-membered ring as the heterocycle. Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring. Moreover, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R ³² , where R ³² is a fatty acid Aromatic 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 (eg, fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms ( For example, it represents a methyl group, an ethyl group, a propyl group, etc.), Z, or -LZ. Here, L and Z are as defined above. R ⁴ , R ⁵ and R ⁶ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

Examples of typical compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like. As examples of the compounds represented by formulas (i) to (iii), the compounds described in paragraph numbers 0089 to 0093 of JP2013-249417A can be referred to, and the contents thereof are incorporated in the present specification. It is.

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

The dispersant (resin) is also available as a commercial product, and specific examples thereof include “Disperbyk-101 (polyamideamine phosphate), 107 (carboxylic acid ester), 110, 111 (acid) manufactured by BYK Chemie. Group-containing copolymer), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer 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 (phthalosy) Nin derivatives), 6750 (azo pigment derivatives) ”,“ Ajisper PB821, PB822, PB880, PB881 ”manufactured by Ajinomoto Fine Techno Co., Ltd.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co., Ltd.,“ Polyflow No. 50E, No. .300 (acrylic copolymer) ”,“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyether ester), DA-703-50, manufactured by Enomoto Kasei Co., Ltd. DA-705, DA-725 ”,“ Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) ”manufactured by Kao Corporation,“ Homogenol L- 18 (polymer polycarboxylic acid) "," Emulgen 920, 930, 935, 985 ( "Reoxyethylene nonylphenyl ether)", "Acetamine 86 (stearylamine acetate)", "Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000" manufactured by Nippon Lubrizol Co., Ltd. , 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate) ”, MYS-IEX (poly) Oxyethylene monostearate), Kawaken Fine Chemical Co., Ltd. “Hinoact T-8000E”, Morishita Sangyo Co., Ltd. “EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFK” A polymer 400, EFKA polymer 401, EFKA polymer 450 "," Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 "manufactured by Sannopco Corporation," Adeka Pluronic L31, manufactured by ADEKA Corporation " F38, 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 Co., Ltd. Etc.

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

In the present invention, the resin may be a polymer having a carboxy group in the side chain. These polymers may be used as a dispersant or a binder. As a 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 include alkali-soluble phenolic resins such as novolak type resins, acidic cellulose derivatives having a carboxy group in the side chain, and polymers having a hydroxy group added with an acid anhydride. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is preferable. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Examples of vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene monomer 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. In addition, only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acids, and 2 or more types may be sufficient as it.

In the present invention, the resin includes benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) A multi-component copolymer comprising acrylate / (meth) acrylic acid / other monomers can be preferably used. Further, a copolymer of 2-hydroxyethyl (meth) acrylate, a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 2 -Hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene A macromonomer / benzyl methacrylate / methacrylic acid copolymer can also be preferably used.

The resin may be a compound represented by the following formula (ED1) and / or a compound represented by the general formula (1) of JP 2010-168539 A (hereinafter, these compounds may be referred to as “ether dimers”). It is also preferable to include a polymer (a) obtained by polymerizing a monomer component including

In the formula (ED), R ¹ and R ² each independently represents 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, and examples thereof include methyl, ethyl, 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, 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl; aryls such as benzyl An alkyl group substituted with a group; and the like. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance.

As a specific example of the ether dimer, for example, paragraph number 0317 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification. Only one type of ether dimer may be used, or two or more types may be used.

The resin may contain 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 represents a hydrogen atom or 1 to 20 carbon atoms that may contain a benzene ring. Represents an alkyl group. n represents an integer of 1 to 15.

In the above formula (X), the alkylene group of R ₂ preferably has 2 to 3 carbon atoms. 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 contain 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.

The resin can be referred to the description in paragraph numbers 0558 to 0571 of JP2012-208494A (paragraph numbers 0685 to 0700 in the corresponding US Patent Application Publication No. 2012/0235099), and the contents thereof are described in this specification. Incorporated into.
Further, the copolymer (B) described in paragraph Nos. 0029 to 0063 of JP 2012-32767 A and alkali-soluble resins used in Examples, paragraphs 0088 to 0098 of JP 2012-208474 A, The binder resin described in the description and the binder resin used in the examples, the binder resin described in paragraphs 0022 to 0032 of JP2012-137531A and the binder resin used in the examples, JP2013-024934A The binder resin described in paragraph Nos. 0132 to 0143 of the publication and the binder resin used in Examples, paragraph numbers 0092 to 0098 of JP 2011-242752 and the binder resin used in Examples, and JP 2012 Nos. -032770, paragraphs 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 may be used as the resin. The content of the resin having a polymerizable group is preferably 1 to 80% by mass of the total solid content 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 70% by mass or less, and more preferably 60% by mass or less.

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

The resin having a polymerizable group is preferably a polymer having a radical polymerizable group in the side chain. The resin having a polymerizable group preferably contains a repeating unit having a radically polymerizable group in the 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. The divalent linking group is selected from an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 12 carbon atoms, and —CO—, —OCO—, —O—, —NH—, and —SO ₂ —. And a group formed by combining one kind thereof. 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. A hydroxy group is preferred.

P ¹ represents a radical polymerizable group. Examples of the radically 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 the total repeating unit. The lower limit is more preferably 10% by mass or more, and still more preferably 15% by mass or more. The upper limit is more preferably 95% by mass or less, and still more preferably 90% by mass or less.

The resin having a polymerizable group may contain other repeating units in addition to the repeating unit represented by the above formula (1). Other repeating units may contain a functional group such as an acid group. It does not have to 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 included, or two or more types of acid groups may be included.
The ratio of the repeating unit having an acid group is preferably 0 to 50% by mass of all 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 35% by mass or less, and still more preferably 30% by mass or less.

Other functional groups include development promoting groups such as lactones, acid anhydrides, amides, cyano groups, long chain and cyclic alkyl groups, aralkyl groups, aryl groups, polyalkylene oxide groups, hydroxy groups, maleimide groups, amino groups, etc. Can be introduced as appropriate.
Moreover, the repeating unit derived from the ether dimer mentioned above, the repeating unit derived from the compound shown by Formula (X) demonstrated with the resin mentioned above, etc. may be included.

Although the specific example of resin which has polymerizability is shown, this invention is not limited to this.

Examples of commercially available resins having a polymerizable property include DYNAR NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co., Ltd.), Biscoat R-264, KS resist 106 (KS resist 106). All are manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Plaxel CF200 series (all manufactured by Daicel Corporation), Ebecryl 3800 (manufactured by Daicel UCB Corporation), Acrycure RD-F8 ( 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, the compound (radically polymerizable compound) which has radically polymerizable groups, such as group which has an ethylenically unsaturated bond, is mentioned. 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 a chemical form such as 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, and 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 1 to 80% by mass of the total solid content of the coloring composition, and the lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more. The upper limit is preferably 70% by mass or less, and more preferably 60% by mass or less.
The content of the polymerizable monomer is preferably 1 to 80% by mass of the total solid content 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 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less.
When a polymerizable monomer and a resin having a polymerizable group are used in combination, the mass ratio of the two is preferably polymerizable monomer: resin having a polymerizable group = 1: 1 to 20, more preferably 1: 1 to 15. Preferably, 1: 5 to 15 is more preferable.
The coloring composition of this invention may contain only 1 type of polymeric compounds, and may contain 2 or more types. 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 3 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 preferable.
Specific examples of these compounds include paragraph numbers [0095] to [0108] of JP-A-2009-288705, paragraph number 0227 of JP-A-2013-29760, and paragraph number 0254 of JP-A-2008-292970. Can be referred to, 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 (alkyleneoxy chain) containing two or more alkyleneoxy groups as repeating units. In the alkyleneoxy chain, the number of repeating units of the alkyleneoxy group is preferably 2 to 30, more preferably 2 to 20, and still more preferably 2 to 10.
The number of carbon atoms of the alkyleneoxy group is preferably 2 or more, more preferably 2 to 10, still more preferably 2 to 4, and particularly preferably 2. That is, an alkyleneoxy chain, particularly preferably an ethyleneoxy group, is preferably represented by “— ((CH ₂ ) _a —O) _b —”. 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 formulas (Z-4) and (Z-5), each E independently represents — ((CH ₂ ) _y CH ₂ O) — or — ((CH ₂ ) _y CH (CH ₃ ) O) —. Each represents independently an integer of 0 to 10, and each X independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxy group.
In the formula (Z-4), the total of acryloyl group and methacryloyl group is 3 or 4, each m independently represents an integer of 0 to 10, and at least one of m represents an integer of 1 to 10 The total of each m is an integer of 1 to 40.
In the formula (Z-5), the total number of acryloyl groups and methacryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and at least one of n represents an integer of 1 to 10 The total 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. The total 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 the formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. 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 formula (Z-4) or formula (Z-5), — ((CH ₂ ) _y CH ₂ O) — or — ((CH ₂ ) _y CH (CH ₃ ) O) — represents the oxygen atom side. A form in which the terminal of X is bonded to X is preferred.

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

Among the compounds represented by formula (Z-4) or formula (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.

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

In the present invention, as a polymerizable compound, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku) Co., Ltd.), dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; Nippon Kayaku) Co., Ltd., A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth) acryloyl groups are bonded via ethylene glycol and propylene glycol residues (for example, from Sartomer) Commercially available SR4 4, SR499) can be preferably used. These oligomer types can also be used. Alternatively, KAYARAD RP-1040, DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.), NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), etc. can be used.

The polymerizable compound may have an acid group such as a carboxy group, a sulfonic acid group, or 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. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development and dissolution characteristics are good, and if it is 40 mgKOH / g or less, it is advantageous in production and handling. Furthermore, the photopolymerization performance is good and the curability is excellent.

The polymerizable compound is also preferably a compound having a caprolactone structure.
Examples of the polymerizable compound having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and examples thereof include DPCA-20, DPCA-30, DPCA-60, DPCA-120 and the like.

Polymerizable compounds include urethane acrylates such as those described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. 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, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. Thus, a colored composition having an extremely excellent photosensitive speed can be obtained.
Commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

<< photopolymerization initiator >>
The coloring 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 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 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (eg, those having a triazine skeleton, those having an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives, etc. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, and the like. Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3333724, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US patents And the compounds described in the specification of No. 42122976.

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, oniums 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, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, oxime compound, triallylimidazole dimer, onium compound, benzophenone compound, acetophenone compound, trihalomethyltriazine compound, α -At least one compound selected from the group consisting of aminoketone compounds, oxime compounds, triallylimidazole dimer and benzophenone compounds is preferred.
As specific examples of the photopolymerization initiator, for example, paragraph numbers 0265 to 0268 of JP 2013-29760 A can be referred to, and the contents thereof are incorporated in the present specification.

As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine initiator described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all 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, compounds described in JP-A-2009-191179 in which the maximum absorption wavelength is matched with a wave light source such as 365 nm or 405 nm can also be used.
As the acylphosphine initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.

More preferred examples of the photopolymerization initiator include oxime compounds.
Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
Examples of oxime compounds that can be preferably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, -Acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2 -One, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
In addition, J.H. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photoscience Science and Technology (1995, pp. 202-232), JP-A 2000-66385, JP-A 2000-80068, JP-T 2004-534797. And the compounds described in JP-A-2006-342166.
As commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used. Further, TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arkles NCI-831 and Adeka Arkles NCI-930 (made by ADEKA) can also be used.

Further, as 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 the carbazole ring, and those described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety Compounds, compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced into the dye moiety, ketoxime compounds described in International Publication WO2009 / 131189, triazine skeleton and oxime skeleton In the same molecule, a compound described in JP2009-221114A having a maximum absorption at 405 nm and good sensitivity to a g-ray light source, Paragraph No. 0076 of JP 2014-137466 A 0079 may be used, such as compounds described in.
Preferably, for example, paragraph numbers 0274 to 0275 of JP 2013-29760 A can be referred to, the contents of which are incorporated herein.
Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The oxime N—O bond may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .

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. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by 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, and an aryl group.
In the 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 above-described substituents.
In the formula (OX-1), the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.

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

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

The content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and further preferably 1 to 20% by mass with respect to 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 contain only one type of photopolymerization initiator, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<< Pigment derivative >>
The colored 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.

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

As the pigment derivative, quinoline, benzimidazolone, and isoindoline pigment derivatives are particularly preferable, and quinoline and benzimidazolone pigment derivatives are more preferable. 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 represents —SO ₃ H or a salt thereof, —CO ₂ H or a salt thereof, or —N (Rpa) (Rpb);
Rpa and Rpb each independently represent an alkyl group or an aryl group, and Rpa and Rpb may be linked to each other to form a ring;
t represents an integer of 1 to 5;

Rp1 represents an alkyl group having 1 to 5 carbon atoms or an aryl group,
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, the plurality of Rp2s may be the same as or different from each other;
* Represents a connecting portion with B.

Rp1 is preferably a methyl group or a phenyl group, and more preferably a methyl group.
Rp2 is preferably a halogen atom, and 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 straight chain, 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 part 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), particularly as B, is excellent in dispersibility. To preferred.

In the formula (PZ), as the alkylene group and arylene group represented by D, for example, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, decylene group, cyclopropylene group, cyclobutylene group, Examples include a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a cyclodecylene group, a phenylene group, and a naphthylene group. Among these, as D, a linear alkylene group is preferable, and a linear alkylene group having 1 to 5 carbon atoms is more preferable.

In the formula (PZ), when E represents —N (Rpa) (Rpb), examples of the alkyl group and aryl group in Rpa and Rpb include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, sec -Butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, octyl group, decyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclodecyl group, phenyl group, A naphthyl group etc. can be mentioned. As Rpa and Rpb, a linear or branched alkyl group is particularly preferable, and a linear or branched alkyl group having 1 to 5 carbon atoms is most preferable.
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 includes an alkali such as a lithium atom, a sodium atom, or a potassium atom Metal, ammonium, tetraalkylammonium and the like are preferable.
T is preferably 1 or 2.

Specific examples of the pigment derivative include the following.

The content of the pigment derivative is preferably 1 to 50% by mass, more preferably 3 to 30% by mass, based on the total mass of the pigment. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.

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

Examples of the organic solvent include the following.
Examples of esters include 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 oxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), 3-alkyloxy Propionic acid alkyl esters (for example, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy) Methyl cypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (for example, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate) Etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy-2-methylpropion Methyl and 2-alkyloxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, pyruvin Acid propi , Methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like. Examples of ethers include 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 Examples thereof include monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like. Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone. Examples of aromatic hydrocarbons include toluene and xylene.

An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
When two or more organic solvents are used in combination, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxypropionic acid 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 10 to 95% by mass with respect to the total amount of the colored composition. The lower limit is more preferably 20% by mass or more, and further 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.
Polymerization inhibitors 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 primary cerium salt and the like. Of these, paramethoxyphenol is preferred.
The content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the colored composition.

<< Surfactant >>
The colored 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 including a fluorosurfactant in the above composition, the liquid properties (particularly fluidity) when prepared as a coating liquid can be further improved, and the uniformity of coating thickness and liquid saving can be further improved. it can.
That is, in the case of forming a film using a coating liquid to which a composition containing a fluorosurfactant is applied, the interfacial tension between the coated surface and the coating liquid decreases, and the wettability to the coated surface is reduced. It improves and the applicability | paintability to a to-be-coated surface improves. For this reason, it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

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

Examples of the fluorosurfactant include MegaFuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC -101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S393, K393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA) etc. are mentioned. A block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A-2011-89090.
The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or 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 3,000 to 50,000, for example, 14,000. Moreover, the fluoropolymer which has an ethylenically unsaturated group in a side chain can also be used as a fluorine-type surfactant. Specific examples include compounds described in JP-A 2010-164965, paragraphs 0050 to 0090 and 0289 to 0295, such as MegaFac RS-101, RS-102, and RS-718K manufactured by DIC.
Moreover, the following compound can also be used for a fluorine-type surfactant.

Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1) Solsperse 20000 (manufactured by Nippon Lubrizol Corporation), and the like. Also, NCW-101, NCW-1001, NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. can be used.

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

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

Examples of silicone-based surfactants include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torresilicone SH21PA, Torree Silicone SH28PA, Torree Silicone SH29PA, Torree Silicone SH30PA, Torree Silicone SH8400 (above, Toray Dow Corning Co., Ltd.) )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4442 (above, manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (above, manufactured by Shin-Etsu Silicone Co., Ltd.) , BYK307, BYK323, BYK330 (above, manufactured by BYK Chemie) and the like.

Only one type of surfactant may be used, or two or more types may be combined.
The content of the surfactant is preferably 0.001 to 2.0% by mass and more preferably 0.005 to 1.0% by mass with respect to the total solid content of the coloring composition.

<< Other ingredients >>
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 developability improver, other fillers, antioxidants and anti-aggregation agents can be contained.

Depending on the raw materials used, the composition may contain metal elements, but from the standpoint of suppressing defects, the content of Group 2 elements (calcium, magnesium, etc.) in the colored composition is 50 ppm or less. And is preferably controlled to 0.01 to 10 ppm. The total amount of the inorganic metal salt in the coloring composition is preferably 100 ppm or less, and more preferably controlled to 0.5 to 50 ppm.

<Method for preparing colored composition>
The coloring composition of the present invention can be prepared by mixing the aforementioned components.
In preparing the coloring composition, each component may be blended at once, or may be blended sequentially after each component is dissolved and dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (at the time of application). ) May be mixed to prepare a composition.

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 resulting 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 or reducing defects. Any filter can be used without particular limitation as long as it has been conventionally used for filtration. For example, fluororesin such as polytetrafluoroethylene (PTFE), polyamide resin such as nylon (eg nylon-6, nylon-6,6), polyolefin resin such as polyethylene and polypropylene (PP) (high density, ultra high molecular weight) And a filter using a material such as polyolefin resin). Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
The pore size of the filter is suitably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, more preferably about 0.05 to 0.5 μm. By setting it as this range, it becomes possible to remove reliably the fine foreign material which inhibits preparation of a uniform and smooth composition in a post process. Further, it is also preferable to use a fiber-shaped filter medium, and examples of the filter medium include polypropylene fiber, nylon fiber, glass fiber, and the like. , TPR005, etc.) and SHPX type series (SHPX003 etc.) filter cartridges can be used.

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.
Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, selected from various filters provided by Nippon Pole Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Japan Integris Co., Ltd. (formerly Nihon Microlith Co., Ltd.) can do.
As the second filter, a filter formed of the same material as the first filter described above can be used.
For example, the filtering by the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.

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

<Emission filter>
The emission filter of the present invention uses the above-described colored composition of the present invention. The emission filter of the present invention is preferably used as an emission filter of a fluorescent sensor.

In the emission filter of the present invention, the integral intensity of fluorescence in the 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 film thickness of the emission filter of the present invention is preferably 10,000 to 50,000 nm, and more preferably 10,000 to 35,000 nm.
In the emission filter of the present invention, the transmittance 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.
In the emission filter of the present invention, the transmittance in the wavelength range of 550 to 600 nm is preferably 40% or more, more preferably 45% or more, and further preferably 50% or more.

<Fluorescence sensor>
Next, the fluorescence 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 colored composition of the present invention.
Examples of the fluorescence sensor include those used by irradiating a sample with excitation light. The sample is not particularly limited, and examples include samples that generate fluorescence when irradiated with excitation light. Examples thereof 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.

An embodiment of the fluorescence sensor of the present invention will be described with reference to FIG. The fluorescent sensor of the present invention is not limited to the following embodiment.
The fluorescence sensor shown in FIG. 1 is a drop-type fluorescence 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 direction 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 ultrahigh pressure mercury lamp, a chemical lamp, a xenon lamp, an ultraviolet light emitting diode (ultraviolet LED), an excimer laser generator, or the like can be used.
The excitation filter 2 can be appropriately selected depending on the type of target excitation light. For example, when light with a wavelength of 534 nm is used as excitation light, it is preferable to use a filter that transmits light with a wavelength of 534 nm and blocks light with other wavelengths.
The excitation light is reflected by the beam splitter 3, passes through the objective lens 4, and irradiates the sample 100 on the sample holder 5. When the sample 100 is irradiated with excitation light, fluorescence generated from the sample and 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 including 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 out of the light traveling 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 excitation light, the influence of fluorescence caused by the emission filter can be suppressed, and the detection sensitivity is excellent.

Another embodiment of the fluorescence 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 shown 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 shown 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 applied to the sample 101 on the sample holder 14. When the sample 101 is irradiated with excitation light, fluorescence generated from the sample and 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.

<Method for manufacturing fluorescent sensor>
The manufacturing method of the fluorescence sensor of this invention has the process of forming an emission filter using the coloring composition of this invention.
Specifically, using the colored composition of the present invention, it 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 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. There is no limitation in particular as a support body. Examples thereof include transparent substrates such as glass, silicon wafers, and polymer resins (such as epoxy resins). As a method for applying the composition onto the support, various methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like can be used.

The colored composition layer formed on the support may be pre-baked. 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. For example, the lower limit may be 50 ° C. or higher, and may be 80 ° C. or higher. The pre-bake time is preferably 10 seconds to 300 seconds, more preferably 40 to 250 seconds, and still more preferably 80 to 220 seconds. Drying can be performed with a hot plate, oven, or the like.

Next, the colored composition layer formed on the support is cured by curing. As the curing process, an exposure process is preferable.
As radiation (light) that can be used for exposure, ultraviolet rays such as g-line and i-line are preferable (particularly preferably i-line). Irradiation dose (exposure dose), for example, preferably 0.03 ~ 2.5J / cm ^2, more preferably 0.05 ~ 1.0J / cm ^2, most preferably 0.08 ~ 0.5J / cm ² .
The oxygen concentration at the time of exposure can be appropriately selected. In addition to being performed in the atmosphere, 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 in a high oxygen atmosphere (for example, 22% by volume, 30% by volume, 50% by volume) with an oxygen concentration exceeding 21% by volume. Further, the exposure illuminance can be set as appropriate, and can usually be selected from the range of 1000 W / m ² to 100,000 W / m ² (eg, 5000 W / m ² , 15000 W / m ² , 35000 W / m ² ). . 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 the exposure process, a heat treatment (post-bake) can be further performed. Post-baking is a heat treatment after development for complete film curing. In the case of performing post-baking, the post-baking temperature is preferably 100 to 240 ° C., for example. From the viewpoint of film curing, 200 to 230 ° C. is more preferable. Post-baking can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, etc., so that the film after development is in the above-mentioned condition. .

In this way, an emission filter can be manufactured. A fluorescence sensor can be manufactured by incorporating the emission filter thus obtained into the fluorescence sensor.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Unless otherwise specified, “part” and “%” are based on mass. In the following, 1 inch is 2.54 cm.

(Measurement method of average particle diameter of pigment)
The average particle diameter 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 colored 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 (a weight average molecular weight of 38000, a numerical value written together with each repeating unit (main chain) represents the content (mass ratio) of each repeating unit. Indicates the number of repetitions of the repeating part.)

D-2: The following structure (weight average molecular weight 20000, the numerical value written in each repeating unit (main chain) represents the content (mass ratio) of each repeating unit. The numerical value written in the repeating part of the side chain is Indicates the number of repetitions of the repeating part.)

D-3: The following structure (weight average molecular weight 24000, the numerical value written together in each repeating unit (main chain) represents the content (mass ratio) of each repeating unit. The numerical value written in the repeating part of the side chain is Indicates the number of repetitions of the repeating part.)

(Resin 2)
B-1: The following structure (the weight average molecular weight is 11,000, and the numerical value written in each repeating unit (main chain) represents the content (mass ratio) of each repeating unit.)

B-2: The following structure (the weight average molecular weight is 12000, and the numerical value written in each repeating unit (main chain) represents the content (mass ratio) of each repeating unit.)

B-3: The following structure (weight average molecular weight 40000, the numerical value written in 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 in M-3 is 1 to 3, and the total of four n is 12 or less.

M-4: NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator I-1 to 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)
It evaluated using the coloring composition of the component 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 mass%
Surfactant: 0.001% by mass
Solvent (propylene glycol monomethyl ether acetate (PGMEA)): remainder

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

(Fluorescence intensity measurement)
Each colored composition was applied onto a glass substrate to form a colored composition layer. The film thickness was adjusted so that the transmittance at a wavelength of 500 nm of the cured film was 5%.
Next, after prebaking 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.
With respect to the obtained cured film, the integrated intensity of fluorescence in the wavelength range of 600 to 700 nm was measured using F4500 manufactured by Hitachi High-Tech, under the conditions of excitation wavelength of 534 nm, excitation slit of 5 nm, fluorescence slit of 5 nm, and photomultiplier voltage of 950 V. In measuring the fluorescence intensity, a 530 nm bandpass filter was used on the light source side to suppress stray light, and a sharp cut filter was used on the detection side to suppress scattered light. Using the integrated value of 600 to 700 nm of the obtained fluorescence spectrum, a value divided by the result of the colored composition of Comparative Example 1 was calculated as the fluorescence intensity ratio.

(Dispersion stability evaluation)
Each coloring composition was stored in a thermostat at 50 ° C., and the spectrum was measured after one week. The spectrum of 400 to 800 nm before and after storage was measured, and the wavelength with the largest spectral fluctuation before and after storage was judged under the following conditions.
5: Spectral fluctuation is less than 1% before and after storage 4: Spectral fluctuation is more than 1% and less than 3% before and after storage 3: Spectral fluctuation is more than 3% before and after storage and less than 5% 2: Spectral fluctuation is 5 before and after storage % And below 10% 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, and light resistance was measured. The spectrum of 400 to 800 nm before and after the treatment was measured, and the wavelength with the largest spectral fluctuation before and after the treatment was judged under the following conditions.
5: Spectral fluctuation is 1% or less before and after treatment 4: Spectral fluctuation is more than 1% before and after treatment and 3% or less 3: Spectral fluctuation is more than 3% before and after treatment and 5% or less 2: Spectral fluctuation is 5 before and after treatment % And below 10% 1: Spectral fluctuation exceeds 10% before and after treatment

(Resolution evaluation)
Exposure was performed by placing a photomask having a pattern on the substrate for measuring fluorescence intensity during exposure. Thereafter, development processing was performed with a 2.5 mass% TMAH (tetramethylammonium hydroxide) aqueous solution. The limit size of the pattern shape that can be produced after development was determined under the following conditions.
5: Limit resolution is 1.4 μm or less 4: Limit resolution exceeds 1.4 μm and 1.7 μm or less 3: Limit resolution exceeds 1.7 μm and 2 μm or less 2: Limit resolution exceeds 2 μm and 3 μm or less 1: No lithographic properties

(Residue defect evaluation)
The number of defects in the solid film was measured on the substrate whose fluorescence intensity was measured using ComPlus manufactured by Applied Materials. The measurement results were judged under the following conditions. Garbage judged to be derived from a material of 1 μm or more was judged as a solid film defect.
The number of defects per 5: 8 inch wafer is 100 or less and the number of defects per 4: 8 inch wafer is more than 100 and 300 or less. The number of defects per 3: 8 inch wafer is more than 300 and 500 or less. 2: 8 The number of defects per inch wafer exceeds 500 and is 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. Moreover, 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 has poor detection sensitivity.
Further, when the cured films of Examples 1 to 38 and Comparative Examples 1 to 5 were incorporated as an emission filter of a fluorescence sensor and the sample was irradiated with excitation light having a wavelength of 534 nm, fluorescence was detected. Examples 1 to 38 The detection sensitivity was superior to those of Comparative Examples 1-5.

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

A coloring composition for forming an emission filter of a fluorescent sensor,
Including a red pigment, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent,
The integrated intensity of fluorescence in the wavelength range of 600 to 700 nm when excited with light having a wavelength of 534 nm in a 3.0 μm-thick film formed using the colored composition,
Divided by the integrated intensity of fluorescence in the wavelength range of 600 to 700 nm when cured with a 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. A colored composition having a value of 0.5 or less.
A coloring 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.
The colored composition according to claim 1 or 2, wherein the red pigment has an average particle diameter of 5 to 500 nm.
The colored composition according to any one of claims 1 to 3, wherein the polymerizable compound is a polymerizable monomer.
The colored composition according to claim 4, wherein the polymerizable monomer has three or more radical polymerizable groups.
The colored composition according to claim 4 or 5, wherein the polymerizable monomer has an alkyleneoxy group.
The colored composition according to claim 6, wherein the polymerizable monomer has a chain containing two or more alkyleneoxy groups as repeating units.
The colored composition according to any one of claims 1 to 7, wherein the resin contains a graft copolymer.
The colored composition according to any one of claims 1 to 8, 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 represents an integer of 1 to 500;
j and k each independently represents an integer of 2 to 8,
In the 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 from each other.
A fluorescent sensor having an emission filter using the colored composition according to any one of claims 1 to 9.
The fluorescence sensor according to claim 10, wherein the fluorescence sensor is used by irradiating a sample with excitation light.
The fluorescence sensor according to claim 10 or 11, wherein the fluorescence sensor is a DNA sensor.
A method for producing a fluorescent sensor, comprising a step of forming an emission filter using the colored composition according to any one of claims 1 to 9.