TWI693471B - Coloring composition, fluorescent sensor and method of manufacturing fluorescent sensor - Google Patents

Abstract

The present invention provides a coloring composition capable of obtaining a fluorescent sensor with excellent detection sensitivity, a fluorescent sensor with excellent detection sensitivity, and a method of manufacturing a fluorescent sensor with excellent detection sensitivity. The coloring composition of the present invention is a coloring composition for forming an emission filter of a fluorescent sensor, and contains at least one red pigment, resin, and polymerizable compound selected from color index pigment red 144 and color index pigment red 166 , Photopolymerization initiator and solvent.

Description

Coloring composition, fluorescent sensor and method of manufacturing fluorescent sensor

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

There is a fluorescent sensor that reacts a sample such as deoxyribonucleic acid (DNA) with a reagent, and irradiates the sample with excitation light to fluoresce it generates. The light is detected and the sample is inspected.

For inspection using a fluorescent sensor, the sample is irradiated with excitation light, the fluorescent light generated by the sample is passed through an emission filter to transmit fluorescent light of a predetermined wavelength, and the fluorescent light transmitted through the emission filter is observed The inspection is carried out by light.

The emission filter of the fluorescent sensor is, for example, a filter using red paint. As a red pigment, color index pigment red 254 has been used conventionally.

On the other hand, Patent Document 1 describes that a red color filter for an image display device is manufactured using a composition containing chromophthal red BRN (color index pigment red 144) and a photosensitive resin .

In addition, Patent Document 2 describes that a red color filter for an image display device is manufactured using a composition containing a color index pigment red 144, polyvinyl alcohol, a surfactant, and water.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 60-129739

[Patent Document 2] Japanese Patent Laid-Open No. 10-239835

The inventor has conducted intensive research on the fluorescent sensor, and as a result, it has been learned that the emission filter using the color index pigment red 254 is likely to generate fluorescent light by the excitation light, and the detection sensitivity of the fluorescent sensor is easily reduced.

On the other hand, Patent Literature 1 and Patent Literature 2 have no description or suggestion regarding the fluorescent sensor.

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

The inventors conducted intensive studies on the coloring composition for forming the emission filter of the fluorescent sensor, and 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 . Furthermore, the coloring composition was studied, and as a result, it was found that by using the following coloring composition, a fluorescent sensor excellent in detection sensitivity can also be obtained, thereby completing the present invention. For the coloring composition, the Fluorescence in the range of 600nm to 700nm when excited by light with a wavelength of 534nm using a film with a thickness of 3.0μm formed by a colored composition The integrated intensity is divided by the integrated intensity of the fluorescence of the cured film described later containing the color index pigment red 254 in the wavelength range of 600 nm to 700 nm when excited by light with a wavelength of 534 nm at a value of 0.5 or less. The present invention provides the following.

<1> A coloring composition, which is a coloring composition for forming an emission filter of a fluorescent sensor, and contains a red pigment, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent, and the coloring composition will be used The integrated intensity of the fluorescent film in the wavelength range of 600 nm to 700 nm when the formed film with a thickness of 3.0 μm is excited by light with a wavelength of 534 nm is divided by the thickness of the color index pigment red 254 containing 40% by mass in the total solid content of 3.0 μm The cured film A has a value of 0.5 or less of the integrated intensity of fluorescence in the wavelength range of 600 nm to 700 nm when excited by light with a wavelength of 534 nm.

<2> A coloring composition, which is a coloring composition for forming an emission filter of a fluorescent sensor, and contains at least one red pigment selected from the group consisting of color index pigment red 144 and color index pigment red 166, resin, Polymerizable compound, photopolymerization initiator and solvent.

<3> The coloring composition as described in <1> or <2>, wherein the average particle diameter of the red pigment is 5 nm to 500 nm.

<4> The coloring composition according to any one of <1> to <3>, wherein the polymerizable compound is a polymerizable monomer.

<5> The coloring composition as described in <4>, wherein the polymerizable monomer has three or more radical polymerizable groups.

<6> The coloring composition as described in <4> or <5>, wherein the polymerizable monomer has an alkoxy group.

<7> The coloring composition according to <6>, wherein the polymerizable monomer has a chain containing two or more alkoxy groups as repeating units.

<8> The coloring composition according to any one of <1> to <7>, wherein the resin contains a graft copolymer.

<9> The coloring composition according to any one of <1> to <8>, wherein the resin includes a resin containing a repeating unit represented by any one of the following formula (1) to formula (4);

In formula (1) to formula (4), W ¹ , W ² , W ³ and W ⁴ each independently represent an oxygen atom or NH, and X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent hydrogen Atom or 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 Alkyl extension, R ⁴ represents a hydrogen atom or a monovalent organic group, n, m, p and q each independently represent an integer of 1 to 500, j and k each independently represent an integer of 2 to 8, in formula (3) , When p is 2~500, there are multiple R ³ may be the same as or different from each other, in formula (4), when q is 2~500, there are multiple X ⁵ and R ⁴ may be the same as each other different.

<10> A fluorescent sensor having an emission filter using the coloring composition as described in any one of <1> to <9>.

<11> The fluorescent sensor according to <10>, wherein the fluorescent sensor is used to irradiate a sample with excitation light.

<12> The fluorescent sensor according to <10> or <11>, wherein the fluorescent sensor is a DNA sensor.

<13> A method of manufacturing a fluorescent sensor, including the step of forming a transmission filter using the coloring composition as described in any one of <1> to <9>.

According to the present invention, it is possible to provide a method for producing a coloring composition of a fluorescent sensor with excellent detection sensitivity, a fluorescent sensor with excellent detection sensitivity, and a fluorescent sensor with excellent detection sensitivity.

1, 11: light source

2.12: Excitation filter

3: beam splitter

4.15: Objective lens

5.14: Sample holder

6, 16: transmit filter

7, 17: Department of eye contact

13: Mirror

100, 101: sample

FIG. 1 is a schematic configuration diagram of an embodiment of a fluorescent sensor of the present invention.

FIG. 2 is a schematic configuration diagram of another embodiment of the fluorescent sensor of the present invention.

In this specification, the total solid content refers to the total mass of components obtained by removing the solvent from the total composition of the composition. The solid content refers to the solid content at 25°C.

In the description of the group (atomic group) in the present specification, the description that does not describe substituted and unsubstituted includes a group having no substituent, and also includes a group having a substituent. For example, the term "alkyl" refers to not only an unsubstituted alkyl group (unsubstituted alkyl group) but also an substituted alkyl group (substituted alkyl group).

The "radiation" in this specification refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet, extreme ultraviolet (EUV), X-ray, or electron beam represented by an excimer laser. In addition, the light in the present invention refers to actinic rays or radiation. Unless otherwise specified, the term "exposure" in this specification refers not only to exposure using far-ultraviolet light, X-rays, EUV light, etc. represented by mercury lamps and excimer lasers, but also drawing by particle beams such as electron beams and ion beams Also included in the exposure.

In this specification, "(meth)acrylate" means either or both of acrylate and methacrylate, "(meth)acrylic acid" means either or both of acrylic acid and methacrylic acid, "(A "Acyl) acryl" means both or any one of acryl and methacryl, and "(meth)allyl" means either or both of allyl and methallyl.

In this specification, Me in the chemical formula represents methyl, Et represents ethyl, Pr represents propyl, Bu represents butyl, and Ph represents phenyl.

In this specification, the term "step" not only refers to an independent step, but even when it cannot be clearly distinguished from other steps, as long as the desired effect of the step can be achieved, it is also included in the term.

In this specification, the weight average molecular weight and the number average molecular weight are defined in terms of polystyrene conversion values measured by gel permeation chromatography (Gel Permeation Chromatography, GPC). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, by using HLC-8220 (manufactured by Tosoh), and using TSKgel Super AWM-H ( Tosoh (Tosoh) Co., Ltd., 6.0 mm ID (inner diameter) × 15.0 cm) as a column, using a 10 mmol/L lithium bromide N-methyl pyrrolidinone (NMP) solution as the dissolution liquid .

The pigment used in the present invention refers to an insoluble pigment compound that is not easily dissolved in a solvent. Typically, it refers to a pigment compound that exists in a dispersed state in the form of particles in the composition. Here, the solvent may include any solvent, and examples thereof include the solvents exemplified in the column of solvents described later. For the pigment used in the present invention, for example, for propylene glycol monomethyl ether acetate and water, the solubility at 25° C. is preferably 0.1 g/100 g or less (Solvent).

<coloring composition>

The coloring composition of the present invention is a coloring composition for forming a transmission filter of a fluorescent sensor, and is a coloring composition that satisfies the following requirements (1) or (2).

(1): Contains a red pigment, resin, polymerizable compound, photopolymerization initiator and solvent, and a film with a thickness of 3.0 μm formed by using the colored composition The integrated intensity of fluorescent light in the wavelength range of 600nm to 700nm at the time of light excitation of 534nm, divided by the light of 534nm in the thickness of the hardened film A with a thickness of 3.0μm containing 40% by mass of the color index pigment red 254 in the total solid content The value of the integrated intensity of fluorescence in the wavelength range of 600 nm to 700 nm during excitation is 0.5 or less.

For the cured film A, it is preferable to apply the following composition to the glass substrate so that the film thickness after curing becomes 3.0 μm, and after drying the coated film at 100° C., perform i at an exposure amount of 1000 mJ/cm ² A cured film obtained by radiation exposure, the composition containing 5 mass% of the color index pigment red 254 with an average particle diameter of 50 nm, 1.5 mass% of the resin represented by Formula D-1, and 0.075 mass% of the Formula PZ-1 Pigment derivative, 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 0.3% by mass of the photopolymerization initiator represented by formula I-1, And the rest is propylene glycol monomethyl ether acetate. In addition, the weight average molecular weight of D-1 is 38000, and the numerical value described with each repeating unit (main chain) indicates the content (mass ratio) of each repeating unit, and the numerical value described with the repeating site of the side chain indicates repetition The number of repetitions of the site. In addition, the weight average molecular weight of B-2 is 12,000, and the numerical value described together with each repeating unit (main chain) represents the content (mass ratio) of each repeating unit.

(2): Contains at least one red pigment selected from the group consisting of color index pigment red 144 and color index pigment red 166, resin, polymerizable compound, photopolymerization initiator, and solvent.

According to the present invention, by using the coloring composition of (1) or (2), an emission filter having low fluorescence with respect to excitation light can be formed.

In addition, the color index pigment red 144 and the color index pigment red 166 have particularly low fluorescence for excitation light, and further have excellent heat resistance, so that emission with lower fluorescence for excitation light and further excellent heat resistance can be formed filter.

Moreover, the emission filter using the coloring composition of the present invention has It has low fluorescence. Therefore, for a fluorescent sensor having an emission filter using the coloring composition of the present invention, the influence of fluorescence caused by the emission filter 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 red pigment. The red pigment is preferably a red pigment having an azo skeleton. The red pigment having an azo skeleton is preferably a compound having a structure represented by formula R-1.

In the formula, R ¹ to R ¹⁴ each independently represent a hydrogen atom or a halogen atom. The halogen atom may include a chlorine atom, a fluorine atom, a bromine atom, etc., preferably a chlorine atom.

Preferably, at least two of R ¹ to R ⁵ are halogen atoms, and the rest are hydrogen atoms. More preferably, two of R ¹ to R ⁵ are halogen atoms, and the rest are hydrogen atoms. It is particularly preferred that R ¹ and R ⁴ are halogen atoms, and R ² , R ³ and R ⁵ are hydrogen atoms.

Preferably, at least two of R ¹⁰ to R ¹⁴ are halogen atoms, and the rest are hydrogen atoms. More preferably, two of R ¹⁰ to R ¹⁴ are halogen atoms, and the rest are hydrogen atoms. More preferably, R ¹⁰ and R ¹³ are halogen atoms, and R ¹¹ , R ¹² and R ¹⁴ are hydrogen atoms.

R ⁶ ~ R ⁹ may be hydrogen atoms, also at least one of R ⁶ ~ R ⁹ is a halogen atom and the remaining is a hydrogen atom. When at least one of R ⁶ to R ⁹ represents a halogen atom, it is preferred that R ⁷ is a halogen atom, and the rest is a hydrogen atom or a halogen atom, and more preferably a hydrogen atom.

In the present invention, the red pigment preferably contains at least one selected from C.I. Pigment Red 144 and C.I. Pigment Red 166. C.I. Pigment Red 144 and C.I. Pigment Red 166 have low fluorescence for excitation light, so an emission filter with low fluorescence for excitation light can be formed.

In the present invention, the average particle diameter of the red pigment is preferably 5 nm to 1000 nm, and more preferably 5 nm to 500 nm. The upper limit is preferably 400 nm or less, more preferably 350 nm or less, and particularly preferably 300 nm or less. According to the study of the present inventors, it has been found that by reducing the particle size of the red pigment, there is a tendency for low fluorescence to the excitation light. If the average particle diameter of the red pigment is within the above range, it is easy to form an emission filter having further lower fluorescence for excitation light.

Furthermore, in the present invention, the "average particle size" of the red pigment is the average particle size related to the secondary particles of the primary particles of the red pigment, and is a value measured by a method such as dynamic light scattering method .

In the coloring composition of the present invention, the content of the red pigment is preferably 10% by mass to 90% by mass relative to the total solid content of the coloring 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, Furthermore, it is preferably 70% by mass or less.

In addition, the total content of C.I. Pigment Red 144 and C.I. Pigment Red 166 in the total mass of the red pigment is preferably 50% by mass to 100% by mass. The lower limit is more preferably 60% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more.

In addition, the red pigment preferably also contains substantially only C.I. Pigment Red 144 and C.I. Pigment Red 166. In addition, when the red pigment contains substantially only CI Pigment Red 144 and CI Pigment Red 166, it is preferable that the total amount of the red pigment contains 99% by mass or more of CI Pigment Red 144 and CI Pigment Red 166, more preferably 99.9 Mass% or more.

The present invention can also use the pigments shown below as red pigments. When the red pigment does not contain any one of C.I. Pigment Red 144 and C.I. Pigment Red 166, the coloring composition can be used by selecting one or more of the following pigments in such a manner that the coloring composition can satisfy the requirements of (1). In addition, the following pigments can also be used in combination with C.I. Pigment Red 144 and/or C.I. Pigment Red 166.

Color Index (CI) Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 9, CI Pigment Red 10, CI Pigment Red 14, CI Pigment Red 17, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 31, CI Pigment Red 38, CI Pigment Red 41, CI Pigment Red 48:1, CI Pigment Red 48:2, CI Pigment Red 48:3, CI Pigment Red 48:4, CI Pigment Red 49, CI Pigment Red 49:1, CI Pigment Red 49:2, CI Pigment Red 52:1, CI Pigment Red 52:2, CI Pigment Red 53: 1. CI Pigment Red 57:1, CI Pigment Red 60:1, CI Pigment Red 63:1, CI Pigment Red 66, CI Pigment Red 67, CI Pigment Red 81:1, CI Pigment Red 81:2, CI Pigment Red 81:3, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90, CI Pigment Red 105, CI Pigment Red 112, CI Pigment Red 119, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 155, CI Pigment Red 168, CI Pigment Red 169, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 184, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 200, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 210, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 246, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 270, CI Pigment Red 272, CI Pigment Red 279

-Miniaturization of pigments-

In the present invention, the red pigment is preferably a fine and granulated pigment. The miniaturization of the pigment is achieved by the following steps: the pigment, the water-soluble organic solvent and the water-soluble inorganic salt are used to prepare a high-viscosity liquid composition, and a wet pulverizer or the like is used to apply force and grind.

Examples of the water-soluble organic solvent used in the pigment miniaturization step include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, and diethylene glycol monomethyl alcohol Ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether acetate, etc.

In addition, as long as it is adsorbed to the pigment by a small amount of use and is not lost in the waste water, other solvents with low or no water solubility, 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, deca Dioxane, cyclohexane, methylcyclohexane, halogenated hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethyl formamide, dimethyl sulfoxide, N- Methylpyrrolidone, etc.

The solvent used for the pigment miniaturization step may be only one type, and two or more types may be mixed and used if necessary.

Examples of the water-soluble inorganic salt used in the pigment miniaturization step include sodium chloride, potassium chloride, calcium chloride, barium chloride, and sodium sulfate.

The use amount of the water-soluble inorganic salt in the miniaturization step is preferably 1 to 50 times by mass of the pigment. The water-soluble inorganic salt has a grinding effect when used in a large amount, but in terms of productivity, the more preferable amount is 1 to 10 times by mass. In addition, 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 parts by mass to 300 parts by mass, and more preferably 100 parts by mass to 200 parts by mass relative to 100 parts by mass of the pigment.

There are no particular restrictions on the operating conditions of the wet pulverizing device in the pigment refining step. In order to effectively grind the pulverizing medium, regarding the operating conditions when the device is a kneader, the blade in the device (blade) The rotation speed is preferably 10rpm~200rpm, and the grinding effect of the two-axis rotation ratio is relatively large Big and better. The operation time and the dry crushing time are preferably from 1 hour to 8 hours, and the internal temperature of the device is preferably from 50°C to 150°C. In addition, the water-soluble inorganic salt as the grinding medium preferably has a grinding particle size of 5 μm to 50 μm, a narrow particle size distribution, and a spherical shape.

<<Other Colored Colorants>>

The coloring composition of the present invention may contain colored colorants other than red pigments. Other colored colorants can be pigments or dyes. The other colorant may be one kind, or two or more kinds.

In order to reduce the transmittance at a wavelength of 300 nm to 400 nm, the other colored colorants are preferably yellow pigments. The yellow pigment is not particularly limited as long as it is commercially available.

In addition, in the present invention, the colored coloring agent refers to a coloring agent other than the white coloring agent and the black coloring agent. The colored coloring agent is preferably a coloring agent having a maximum absorption wavelength in the wavelength range of 400 nm to 700 nm. In addition, the term "having a maximum absorption wavelength in the range of 400 nm to 700 nm" refers to a wavelength that shows the maximum absorbance in the range of 400 nm to 700 nm in the absorption spectrum. For example, it is preferable that the absorption spectrum in the wavelength range of 350 nm to 1300 nm has a wavelength showing the maximum absorbance in the wavelength range of 400 nm to 700 nm.

The pigment may include various conventionally known pigments. In addition, if it is considered that high transmittance is preferred, it is preferable to use a pigment with an average particle diameter as small as possible, and also considering the operability, the average particle diameter of the pigment is preferably 0.01 μm to 0.1 μm, more It is preferably 0.01 μm to 0.05 μm.

Pigments include the following pigments. However, the present invention is not limited to these pigments.

CI Pigment Yellow 1, CI Pigment Yellow 2, CI Pigment Yellow 3, CI Pigment Yellow 4, CI Pigment Yellow 5, CI Pigment Yellow 6, CI Pigment Yellow 10, CI Pigment Yellow 11, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 18, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 32, CI Pigment Yellow 34, CI Pigment Yellow 35, CI Pigment Yellow 35:1, CI Pigment Yellow 36, CI Pigment Yellow 36:1, CI Pigment Yellow 37, CI Pigment Yellow 37:1, CI Pigment Yellow 40, CI Pigment Yellow 42, CI Pigment Yellow 43 , CI Pigment Yellow 53, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61, CI Pigment Yellow 62, CI Pigment Yellow 63, CI Pigment Yellow 65, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 77 , CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 86, CI Pigment Yellow 93, CI Pigment Yellow 94, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101 , CI Pigment Yellow 104, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 114, CI Pigment Yellow 115, CI Pigment Yellow 116, CI Pigment Yellow 117 , CI Pigment Yellow 118, CI Pigment Yellow 119, C.1. Pigment Yellow 120, CI Pigment Yellow 123, CI Pigment Yellow 125, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 137, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 147, CI Pigment Yellow 148, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 156, CI Pigment Yellow 161, CI Pigment Yellow 162, CI Pigment Yellow 164, CI Pigment Yellow 166, CI Pigment Yellow 167, CI Pigment Yellow 168, CI Pigment Yellow 169, CI Pigment Yellow 170, CI Pigment Yellow 171, CI Pigment Yellow 172, CI Pigment Yellow 173, CI Pigment Yellow 174, CI Pigment Yellow 175, CI Pigment Yellow 176, CI Pigment Yellow 177, CI Pigment Yellow 179, CI Pigment Yellow 180, CI Pigment Yellow 181, CI Pigment Yellow 182, CI Pigment Yellow 185, CI Pigment Yellow 187, CI Pigment Yellow 188, CI Pigment Yellow 193, CI Pigment Yellow 194, CI Pigment Yellow 199, CI Pigment Yellow 213, CI Pigment Yellow 214, etc.; CI Pigment Orange 2, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 16, CI Pigment Orange 17:1, CI Pigment Orange 31, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 48, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 52, CI Pigment Orange 55, CI Pigment Orange 59, CI Pigment Orange 60, CI Pigment Orange 61, CI Pigment Orange 62, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, etc.; CI Pigment Green 7, CI Pigment Green 10, CI Pigment Green 36, CI Pigment Green 37, CI Pigment Green 58, CI Pigment Green 59; CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 27, CI Pigment Violet 32, CI Pigment Violet 37, CI Pigment Violet 42; CI Pigment Blue 1, CI Pigment Blue 2, CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Blue 16, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64, CI Pigment Blue 66, CI Pigment Blue 79, CI Pigment Blue 80.

Dyes can be used, for example: Japanese Patent Laid-Open No. 64-90403, Japanese Patent Laid-Open No. 64-01102, Japanese Patent Laid-Open No. 1-04301 Newspaper, Japanese Patent Laid-Open No. 6-11614, Japanese Patent No. 2592207, US Patent No. 4808501, US Patent No. 5667920, US Patent No. 505950, Japanese Patent No. 5-333207, Japanese Patent The pigment disclosed in Japanese Patent Laid-Open No. 6-35183, Japanese Patent Laid-Open No. 6-51115, Japanese Patent Laid-Open No. 6-194828, and the like. If distinguished by chemical structure, pyrazole azo compounds, pyrrole methylene compounds, anilino azo compounds, triarylmethane compounds, anthraquinone compounds, benzylidene compounds, oxacyanine compounds, pyrazolo Triazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. In addition, dye polymers can also be used as dyes. Examples of the pigment polymer include compounds described in Japanese Patent Laid-Open No. 2011-213925 and Japanese Patent Laid-Open No. 2013-041097.

When the coloring composition of the present invention contains other colored color colorants, the content of the other colored color colorants is preferably 1% by mass to 60% by mass relative to the total solid content in the coloring composition. The lower limit is more preferably 5% by mass or more, and further 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 resin. The resin is prepared, for example, for the purpose of dispersing the pigment in the composition and the purpose of the binder. In addition, the resin mainly used to disperse the pigment is also called a dispersant. Among them, this use of resin is an example, and it can also be used for purposes other than this use.

The weight average molecular weight (Mw) of the resin is preferably 2,000~ 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 content of the resin is preferably 1% by mass 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 coloring composition of the present invention may contain only one kind of resin or two or more kinds. When two or more cases are included, the total amount is preferably within the above range.

The coloring composition of the present invention may contain a dispersant as a resin.

The dispersant is preferably a resin having at least one selected from acid groups and basic groups, and more preferably a resin having acid groups. Examples of the acid group included in the resin include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. Examples of the basic group possessed by the resin include amine groups. In addition, in the present invention, a resin having no acid group or basic group may be used as a dispersant.

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

In the present invention, the resin preferably contains a graft copolymer. In the present invention, the graft copolymer can be preferably used as a dispersant for red pigments. Furthermore, in the present invention, the graft copolymer refers to a resin having a graft chain. The graft chain refers to the end of the group branched from the main chain from the root of the polymer main chain.

The graft copolymer preferably has an atomic number other than hydrogen atoms of 40 Resin with graft chain in the range of ~10000. In addition, the number of atoms other than 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 resins, polyester resins, polyurethane resins, polyurea resins, polyamide resins, and polyether resins. Among them, (meth)acrylic resin is preferred.

In order to improve the interaction between the graft site and the solvent and thereby improve the dispersibility, the graft chain of the graft copolymer is preferably a graft chain having poly(meth)acrylic acid, polyester or polyether, more preferably With polyester or polyether graft chain.

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

The macromonomer used when producing a graft copolymer by radical polymerization can use a well-known macromonomer, and the macromonomer AA-6 (terminal group is a methacryl amide group) manufactured by Toyasei Corporation is mentioned. Polymethyl methacrylate), AS-6 (polystyrene with methacryloyl group as the terminal group), AN-6S (copolymer of styrene and acrylonitrile with methacryloyl group as the terminal group), AB-6 (polybutyl acrylate with a terminal methacryloyl group), Placcel FM5 (E-hex of 2-hydroxyethyl methacrylate) manufactured by Daicel Corporation Lactone 5 molar equivalent plus finished product), FA10L (2-hydroxyethyl acrylate epsilon-caprolactone 10 molar equivalent plus finished product), and the polyester-based monolith described in Japanese Patent Laid-Open No. 2-272009 Body etc.

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

In formula (1) to formula (4), W ¹ , W ² , W ³ and W ⁴ each independently represent an oxygen atom or NH, and X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent hydrogen Atom or 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 Alkyl extension, R ⁴ represents a hydrogen atom or a monovalent organic group, n, m, p and q each independently represent an integer of 1 to 500, j and k each independently represent an integer of 2 to 8, in formula (3) , When p is 2~500, there are multiple R ³ may be the same as or different from each other, in formula (4), when q is 2~500, there are multiple X ⁵ and R ⁴ may be the same as each other different.

In Formula (1) to Formula (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 Formula (1) to Formula (4), X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. From the point of view of limitations in synthesis, X ¹ , X ² , X ³ , X ⁴ and X ⁵ are each preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably each independently Hydrogen atom or methyl group, particularly preferably methyl group.

In Formula (1) to Formula (4), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a divalent linking group, and the linking is not particularly limited based on the structure. Specific examples of the divalent linking groups represented by Y ¹ , Y ² , Y ³ and Y ⁴ include the following linking groups (Y-1) to (Y-21). In the structures shown below, A and B refer to the bonding sites with the left terminal group and the right terminal group in formulas (1) to (4), respectively.

In Formula (1) to Formula (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, and specific examples include alkyl, hydroxyl, alkoxy, aryloxy, heteroaryloxy, alkylthioether, arylthioether, and heteroarylthioether Groups and amine groups. Among these groups, especially from the viewpoint of improving dispersibility, the organic groups represented by Z ¹ , Z ² , Z ³ and Z ⁴ are preferably groups having a stereoscopic repulsion effect, and are preferably independently C5-24 alkyl or alkoxy groups, among which branched alkyl groups having 5-24 carbon atoms, cyclic alkyl groups having 5-24 carbon atoms or alkyl groups having 5-24 carbon atoms are particularly preferred Oxy. In addition, the alkyl group contained in the alkoxy group may be linear, branched, or cyclic.

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

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

In formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group. The monovalent organic is not particularly limited in 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, it is preferably 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, more preferably a carbon number Straight-chain alkyl groups of 1 to 20, particularly preferably straight-chain alkyl groups having 1 to 6 carbon atoms. In 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 as or different from each other.

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

In the formula ^{(1A), X 1, Y} 1, Z 1 and n of formula X (1) is ^1, Y ^1, Z ¹ and n have the same meaning, the preferred range is also the same.

In formula ^{(2A), X 2, Y} 2, Z 2 and ^2, Y ² m of formula X (2) is, Z ² and m are the same meaning, the preferred range is also the same.

The graft copolymer preferably contains, in addition to the repeating units represented by Formula (1) to Formula (4) described above, a repeating unit having an acid group. Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group, and preferably a carboxyl group and a phenolic hydroxyl group. The content of the repeating unit having an acid group is preferably 5% to 95% by mass relative to the total mass of the grafted resin, and more preferably 10% to 95% by mass.

The graft copolymer may further contain a repeating unit having a functional group other than the graft chain and acid group that can interact with the pigment. The repeating unit having a functional group is not particularly limited in structure, and examples thereof include a repeating unit having a basic group, a repeating unit having a coordination group, and a repeating unit containing a reactive group.

Examples of basic groups include primary amine groups, secondary amine groups, tertiary amine groups, N atom-containing heterocycles, and amide groups. Examples of the coordinating group and reactive group include acetylacetoxy, trialkoxysilyl, isocyanate, anhydride residue, and acetyl chloride residue. The graft copolymer may contain the repeating unit having the functional group or may not contain the repeating unit having the functional group. In the case of containing the repeating unit having the functional group, relative to the total mass of the graft resin, It is preferably 0.1% by mass to 50% by mass, and more preferably 0.1% by mass to 30% by mass.

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

The ClogP value is a value calculated using the program "CLOGP" available from Daylight Chemical Information System, Inc. This program provides the value of "calculated logP" calculated by the fragment approach of Hansch and Leo (refer to the following document). The fragmentation method divides the chemical structure into partial structures (fragments) according to the chemical structure of the compound, and sums the logP help components assigned to the fragment, thereby estimating the logP value of the compound. The details are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 is used.

AJ Leo, "Comprehensive Medicinal Chemistry", Vol. 4, C. Hansch, PG Sammes, JB Taylor and CA Pull Edited by CARamsden (Eds.), p. 295, Pergamon Press (1990); C. Hansch & AJ Leo (C. Hansch & AJ Leo.) Substituent Constants For Correlation Analysis in Chemistry and Biology.", John Wiley &Sons; AJ Leo., "Calculation of the Hydrophobic Constants of Chemical Structures (Calculating log Poct from structure. Chem. Rev.)", 93, 1281-1306, 1993.

logP refers to the common logarithm of the partition coefficient P (Partition Coefficient). It is a quantitative value that indicates how a certain organic compound is distributed in the two-phase system equilibrium of oil (usually 1-octanol) and water. The following expression.

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 water phase.

If the value of logP increases with a positive value across 0, it means that the oil solubility increases. If it is negative and the absolute value increases, it means that the water solubility increases. It has a negative correlation with the water solubility of organic compounds and is widely used. As a parameter to estimate the hydrophilicity and hydrophobicity of organic compounds.

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

In the formulae (i) to (iii), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or the number of carbon atoms is 1 to 6 alkyl groups (eg methyl, ethyl, propyl, etc.). R ¹ , R ² and R ^{3 are more} preferably hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, and most preferably hydrogen atoms or methyl groups. R ² and R ^{3 are} particularly preferably hydrogen atoms.

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

L is a single bond or a divalent linking group. Examples of the divalent linking group include: divalent aliphatic groups (e.g., alkylene groups, substituted alkylene groups, alkenyl groups, substituted alkenyl groups, extender groups, substituted extender groups), divalent Aromatic groups (e.g. aryl groups, substituted aryl groups), divalent heterocyclic groups, oxygen atoms (-O-), sulfur atoms (-S-), imino groups (-NH-), substituted Imine group (-NR ³¹ -, where R ³¹ is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-) or a combination of these groups, etc.

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 oxyethylated structure or an oxypropylated structure. In addition, L may also contain a polyoxyalkylene structure repeatedly including two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene group 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 2-10.

Z can be exemplified by aliphatic groups (such as alkyl groups, substituted alkyl groups, unsaturated alkyl groups, and substituted unsaturated alkyl groups), aromatic groups (such as aryl groups, substituted aryl groups), and heterocyclic groups , Oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), substituted imino group (-NR ³¹ -, where R ³¹ is an aliphatic group, an aromatic group Or heterocyclic group), carbonyl (-CO-) or a combination of these groups.

The aliphatic group may also have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1-20, more preferably 1-15, and still more preferably 1-10. The aliphatic group further includes a ring-assembled hydrocarbon group and a cross-linked cyclic hydrocarbon group. Examples of the ring-assembled hydrocarbon group include dicyclohexyl, perhydronaphthyl, biphenyl, 4-cyclohexylphenyl, and the like. Examples of the cross-linked cyclic hydrocarbon ring include pinane, norbornane, norpinane, norbornane, and bicyclooctane ring (bicyclo[2.2.2]octane ring, bicyclo[3.2.1]octane ring, etc.) Equivalent bicyclic hydrocarbon ring, tricyclic [5.2.1.0 ^3,8 ] decane (homobledane), adamantane, tricyclic [5.2.1.0 ^2,6 ] decane, tricyclic [4.3.1.1 ^2,5 ] deca Tricyclic hydrocarbon rings such as mono-alkane rings, tetracyclic rings [4.4.0.1 ^2,5 .1 ^7,10 ]Dodecane, perhydro-1,4-methyl bridge-5,8-methyl bridge naphthalene rings Type hydrocarbon ring etc. In addition, cross-linked cyclic hydrocarbon rings also include condensed cyclic hydrocarbon rings, such as perhydronaphthalene (decalin) ring, perhydroanthracene ring, perhydrophenanthrene ring, perhydroacenaphthene ring, full hydrogen A condensed ring formed by condensing multiple 5- to 8-membered cycloalkane rings, such as a hydrogen ring, a perhydroindene ring, and a perhydroeprene ring. With regard to aliphatic groups, saturated aliphatic groups are superior to unsaturated aliphatic groups. In addition, the aliphatic group may have a substituent. Examples of the substituent include halogen atoms, aromatic groups and heterocyclic groups. Among them, the aliphatic group represented by Z does not have an acid group as a substituent.

The number of carbon atoms of the aromatic group is preferably 6-20, more preferably 6-15, and still more preferably 6-10. In addition, the aromatic group may have a substituent. Examples of the substituent include halogen atoms, aliphatic groups, aromatic groups, and heterocyclic groups. Among them, the aromatic group represented by Z does not have an acid group as a substituent.

The heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocyclic ring. Other heterocycles, aliphatic rings or aromatic rings can also be condensed on the heterocycle. In addition, the heterocyclic group may have a substituent. Examples of the substituent include halogen atom, hydroxyl group, pendant oxygen group (=O), pendant thio group (=S), imino group (=NH), substituted imino group (=NR ³² , where R ³² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group. Among them, the heterocyclic group represented by Z does not have an acid group as a substituent.

In the formula (iii), R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) or an alkyl group having 1 to 6 carbon atoms ( (Eg methyl, ethyl, propyl, etc.), Z or -LZ. Here, L and Z have the same meaning as L and Z described 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 representative compounds represented by formula (i) to formula (iii) include radical polymerizable compounds selected from acrylates, methacrylates, styrenes, and the like. In addition, for examples of the compounds represented by formula (i) to formula (iii), refer to the compounds described in paragraph No. 0089 to paragraph No. 0993 of Japanese Patent Laid-Open No. 2013-249417, and these contents are incorporated into this document In the manual.

Specific examples of the graft copolymer include the following copolymers. In addition, the resin described in Paragraph No. 0072 to Paragraph No. 0094 of Japanese Patent Laid-Open No. 2012-255128 can be used.

The dispersant (resin) can also be obtained as a commercially available product. Specific examples of this include: "Disperbyk-101 (polyamide-amine phosphate)" manufactured by BYK Chemie. , Disperbyk (Disperbyk) -107 (carboxylate), Disperbyk (Disperbyk) -110, Disperbyk (Disperbyk) -111 (copolymer containing acid groups), Dispar Disperbyk-130 (polyamide), Disperbyk-161, Disperbyk-162, Di Disperbyk-163, Disperbyk-164, Disperbyk-165, Disperbyk-166, Disperbyk )-170 (Polymer Copolymer)", "BYK-P104, BYK-P105 (High Molecular Weight Unsaturated Polycarboxylic Acid)"; "Efka" manufactured by Efka (EFKA) Card (EFKA) 4047, Efka (EFKA) 4050~ Efka (EFKA) 4165 (polyurethane system), EFKA4330~ Efka (EFKA) 4340 (block copolymer), Efka (EFKA) 4400 ~ Efka (EFKA) 4402 (modified polyacrylate), Efka (EFKA) 5010 (polyesteramide), Efka (EFKA) 5765 (high molecular weight polycarboxylate), Efka (EFKA) 6220 (fatty acid polyester), Efka (EFKA) 6745 (phthalocyanine derivative), Efka (EFKA) 6750 (azo pigment derivative)"; Ajinomoto Precision Technology (Ajinomoto "Ajisper PB821, Ajisper PB822, Ajisper PB880, Ajisper PB880, Ajisper PB881" manufactured by Fine-techno Company; Kyoeisha Chemical Company Manufactured "Flowlen TG-710 (urethane oligomer)", "Polyflow No. 50E, Polyflow No. 300 (acrylic copolymer ")"; "Disparlon KS-860, Disparlon 873SN, Disparlon 874, Disparlon 874, Disparlon # 2150 (fat) Polycarboxylic acids), Disparlon #7004 (polyetherester), Disparlon DA-703-50, Disparlon DA-705, Disparon ( Disparlon) DA-725"; "Demol RN, Demol N (naphthalene sulfonate formaldehyde polycondensate), Demol) manufactured by Kao Corporation MS, Demol C, Demol SN-B (aromatic sulfonic acid formaldehyde polycondensate)", "Homogenol L-18 (high molecular polycarboxylic acid)", "Emulgen 920, Emulgen 930, Emulgen 935, Emulgen 985 (polyoxyethylene nonylphenyl ether)", "Acetamin 86( "Stearyl amine acetate)"; "Solsperse 5000 (phthalocyanine derivatives) manufactured by Librizol Japan (shares), Solsperse 22000 (azo) Pigment derivatives), Sonupas (Solsperse) 13240 (polyester amine), Sonupas (Solsperse) 3000, Sonupas (Solsperse) 17000, Sonupas (Solsperse) 27000 (having at the end Functional Polymer), Sonupas (Solsperse) 24000, Sonupas (Solsperse) 28000, Sonupas (Solsperse) 32000, Sonupas (Solsperse) 38500 (graft polymer)'' ; Nikko Chemical (Nikkol) T106 (polyoxyethylene sorbitan monooleate), Nikkor (Nikkol) MYS-IEX (polyoxyethylene monostearate) "Hinoact T-8000E" manufactured by Kawaken Fine Chemical Co., Ltd.; "EFKA-46, EFKA Efka" manufactured by Morishita Industry Co., Ltd. (EFKA)-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EF EFKA Polymer 450"; "Disperse-aid 6, Disperse-aid 8, Disperse-aid 8, Di Disperse-aid 15, Disperse-aid 9100"; "ADEKA" manufactured by ADEKA (shares) Adeka Pluronic L31, Adeka Pluronic F38, Adeka Pluronic L42, Adeka Pluronic L44, Adeka Pluronic L44 Pluronic) L61, Adeka Pluronic L64, Adeka Pluronic F68, Adeka Pluronic L72, Adeka Pluronic P95, Adeka Pluronic P95 Adeka Pluronic F77, Adeka Pluronic P84, Adeka Pluronic F87, Adeka Pluronic P94, Adeka Pluronic P94 ) L101, Adeka Pluronic P103, Adeka Pluronic F108, Adeka Pluronic L121, Adeka Pluronic P-123''; And "Ionet S-20" manufactured by Sanyo Chemicals Co., Ltd. etc.

These resins may be used alone or in combination of two or more.

In addition, the following materials can also be used as the resin: (meth)acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc. Resins with acid groups such as acidic cellulose derivatives with carboxylic acid and resins with acid anhydride added to polymers with hydroxyl groups. In addition, the N-substituted maleimide monomer copolymer described in Japanese Patent Laid-Open No. 10-300922 and the ether dimer copolymer described in Japanese Patent Laid-Open No. 2004-300204 may also be preferred Used as resin.

In addition, in the present invention, the resin can also be used in a polymer having a carboxyl group on the side chain Compound. These polymers can be used as dispersants, and can also be used as adhesives. Examples of the polymer having a carboxyl group in the side chain include: methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, phenolic Alkali-soluble phenol resins such as varnish-type resins, and acidic cellulose derivatives having a carboxyl group on the side chain, and polymers obtained by adding an acid anhydride to a polymer having a hydroxyl group. Particularly preferred is a copolymer of (meth)acrylic acid and other monomers copolymerizable therewith. Other monomers copolymerizable with (meth)acrylic acid include alkyl (meth)acrylate, aryl (meth)acrylate, vinyl compounds and the like. Examples of alkyl (meth)acrylate and aryl (meth)acrylate include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate Ester, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate , Toluene (meth)acrylate, naphthyl (meth)acrylate, cyclohexyl (meth)acrylate, etc., vinyl compounds include styrene, α-methylstyrene, vinyltoluene, methacrylic acid Glycidyl ester, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, etc. In addition, other monomers include N-substituted maleimide monomers described in Japanese Patent Laid-Open No. 10-300922 (for example, N-phenylmaleimide, N-cyclohexylmaleimide Wait). Furthermore, the other monomers copolymerizable with (meth)acrylic acid may be only one kind, or two or more kinds.

In addition, in the present invention, as the resin, benzyl (meth)acrylate/(meth)acrylic acid copolymer, benzyl (meth)acrylate/(meth)acrylic acid/(meth)acrylic acid can be preferably used Acid-2-hydroxyethyl copolymer, multi-component copolymer containing benzyl (meth)acrylate/(meth)acrylic acid/other monomers. In addition, it can also be preferably used: copolymerized with 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate described in Japanese Patent Laid-Open No. 7-140654 /Polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate/polymethyl methacrylate macromonomer/benzyl methacrylate/ Methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene giant monomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene giant monomer Body/benzyl methacrylate/methacrylic acid copolymer, etc.

It is also preferable that the resin contains a polymer (a) which contains a compound represented by the following formula (ED1) and/or the general formula (1) of Japanese Patent Laid-Open No. 2010-168539 The compound represented by the compound (hereinafter sometimes referred to as "ether dimer") is obtained by polymerizing monomer components.

In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a C 1-25 hydrocarbon group 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-propyl, isopropyl, and n Straight or branched alkyl groups such as butyl, isobutyl, third butyl, third pentyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, third butyl Cyclocyclic groups such as cyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; 1-methoxyethyl, 1- Alkyl substituted alkyl such as ethoxyethyl; aryl substituted alkyl such as benzyl. Among these groups, particularly in terms of heat resistance, preferred are substituents of primary or secondary carbons such as methyl, ethyl, cyclohexyl, and benzyl that are not easily detached by acid or heat.

For a specific example of the ether dimer, for example, refer to paragraph No. 0317 of Japanese Patent Laid-Open No. 2013-29760, and incorporate this content into this specification. The ether dimer may be only one kind, or two or more kinds.

The resin may contain a repeating unit derived from a compound represented by the following formula (X).

In formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a C 2-10 alkylene group, R ₃ represents a hydrogen atom or a C 1-20 alkyl group that may contain a benzene ring. n represents an integer from 1 to 15.

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

The resin can refer to the description of paragraph number 0558 to paragraph number 0571 of Japanese Patent Laid-Open No. 2012-208494 (corresponding paragraph number 0685 to paragraph number 0700 of the specification of US Patent Application Publication No. 2012/0235099). Into this manual.

Furthermore, the copolymer (B) described in paragraph No. 0029 to paragraph No. 0063 of Japanese Patent Laid-Open No. 2012-32767 and the alkali-soluble resin used in the examples, and Japanese Patent Laid-Open No. 2012-208474 Paragraph No. 0088 to the adhesive resin described in Paragraph No. 0098 and the adhesive resin used in the examples, the adhesive resin described in Paragraph No. 0022 to Paragraph No. 032 of Japanese Patent Laid-Open No. 2012-137531 and the examples Binder resin used, binder resin described in paragraph No. 0132 to paragraph No. 0143 of Japanese Patent Laid-Open No. 2013-024934 and binder resin used in Examples, paragraph of Japanese Patent Laid-Open No. 2011-242752 No. 0092 to paragraph number 0098 and the binder resin used in the examples, and the binder resin described in paragraph number 0030 to paragraph number 072 of Japanese Patent Laid-Open No. 2012-032770. Incorporate these contents into this manual.

In the present invention, a resin having a polymerizable group can also be used. The content of the polymerizable group-containing resin is preferably 1% by mass 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 on the side chain. The resin having a polymerizable group preferably contains a repeating unit having a radical polymerizable group on the side chain, and more preferably contains a repeating unit represented by formula (1) Of polymers.

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 a C 1-3 alkyl group, preferably a methyl group. R ^{1 is} preferably a hydrogen atom or a methyl group.

L ¹ represents a single bond or a divalent linking group. Examples of the divalent linking group include: an alkylene group having 1 to 30 carbon atoms, an aryl group having 6 to 12 carbon atoms, and these groups are selected from -CO-, -OCO-, -O-, and -NH- And -SO ₂ -a combination of groups. The alkylene group and the aryl group may have a substituent or may be unsubstituted. Examples of the substituent include halogen atoms, alkyl groups, aryl groups, hydroxyl groups, carboxyl groups, alkoxy groups, and aryloxy groups. It is preferably a hydroxyl group.

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

The resin having a polymerizable group preferably has a content of repeating units having a radical polymerizable group on the side chain of 5 to 100% by mass of all repeating units. The lower limit is more preferably 10% by mass or more, and further preferably 15% by mass or more. The upper limit is more preferably 95% by mass or less, and further 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 formula (1). Other repeating units may also contain acid groups, etc. Functional group. It may not contain functional groups.

Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphate group. The acid group may contain only one kind or two or more kinds.

The ratio of the repeating unit having an acid group is preferably 0% by mass to 50% by mass of all repeating units constituting the resin. The lower limit is more preferably 1% by mass or more, and further preferably 3% by mass or more. The upper limit is more preferably 35% by mass or less, and further preferably 30% by mass or less.

Examples of other functional groups include lactone groups, acid anhydride groups, amide groups, cyano groups, and other development-promoting groups, long-chain alkyl groups and cyclic alkyl groups, aralkyl groups, aryl groups, polyalkylene oxide groups, hydroxyl groups, and horses. Laimide groups, amine groups, etc., can be appropriately introduced.

In addition, a repeating unit derived from the ether dimer or a repeating unit derived from the compound represented by the formula (X) described in the resin may be included.

Specific examples of the resin having a polymerizable group are shown, but the present invention is not limited thereto.

Examples of commercially available resins having a polymerizable group include: Dejanal (Dainal) NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer), Diamond-Shamrock Co., Ltd. ( Diamond Shamrock Co., Ltd.), Biscoat R-264, KS Resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (For example, ACA230AA), Placcel CF200 series (all made by Daicel), Ebecryl 3800 (made by Daicel UCB), Acrylic (Acrycure) RD-F8 (manufactured by Japan Catalyst Co., Ltd.), etc.

<<Polymerizing 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 free radicals can be used. For example, a compound (radical polymerizable compound) having a radical polymerizable group such as a group containing an ethylenic unsaturated bond can be cited. Examples of the group containing an ethylenic unsaturated bond include a vinyl group, (meth)allyl group, (meth)acryloyl group and the like, preferably (meth)allyl group and (meth)acryloyl group.

In the present invention, the polymerizable compound may be, for example, any one of the following chemical forms: monomers, prepolymers, that is, dimers, trimers, and oligomers, or mixtures of these, and polymers of these, etc. . It is preferably a monomer.

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% by mass 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% by mass 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.

In addition, when the polymerizable monomer is used in combination with a resin having a polymerizable group, the quality of the two is preferably a polymerizable monomer: a resin having a polymerizable group = 1:1 to 20, more preferably 1: 1~15, preferably 1:5~15.

The coloring composition of the present invention may contain only one kind of polymerizable compound, or two or more kinds. When two or more cases are included, the total amount is preferably within the above range.

(Polymerizable monomer)

In the present invention, the polymerizable monomer is preferably a compound having three or more radical polymerizable groups, more preferably a compound having three to fifteen radical polymerizable groups, and still more preferably three to six A radical polymerizable compound.

For the specific compounds, refer to paragraph number [0095] to paragraph number [0108] of Japanese Patent Laid-Open No. 2009-288705, paragraph number 0227 of Japanese Patent Laid-Open No. 2013-29760, and Japanese Patent Laid-Open No. 2008-292970 The compounds described in Paragraph No. 0254 to Paragraph No. 0257 of Japanese Patent Gazette are incorporated into this specification.

The polymerizable monomer is preferably a compound having an alkoxy group, and more preferably a compound having a chain (an alkoxy chain) containing two or more alkoxy groups as a repeating unit. The number of repeating units of the alkoxy extension chain is preferably 2 to 30, more preferably 2 to 20, and further preferably 2 to 10.

The carbon number of the alkoxy group is preferably 2 or more, more preferably 2 to 10, further preferably 2 to 4, particularly preferably 2. That is, particularly preferred is ethoxylated.

The alkoxy chain is preferably represented by "-((CH ₂ ) _a -O) _b -". In the formula, a is preferably 2 or more, more preferably 2 to 10, further preferably 2 to 4, 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 alkoxy group, for example, at least one selected from the group of compounds represented by the following formula (Z-4) or formula (Z-5) may be used.

In formula (Z-4) and formula (Z-5), E independently represents -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)-, y Each independently represents an integer of 0 to 10, and X independently represents an acryl group, a methacryl group, a hydrogen atom, or a carboxyl group.

In the formula (Z-4), the total number of acryl and methacryl groups is three or four, m independently represents an integer of 0 to 10, and at least one of m represents an integer of 1 to 10, each m The total of is an integer from 1 to 40.

In formula (Z-5), the total number of propenyl and methacryl groups is five or six, n independently represents an integer of 0 to 10, and at least one of n represents an integer of 1 to 10, each n The total of is an integer from 1 to 60.

In formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. In addition, 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 formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. In addition, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.

In addition, -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)- in formula (Z-4) or formula (Z-5) is preferably an oxygen atom The end of the side is bonded to the form of X.

The compound represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more. It is particularly preferred that in the formula (Z-5), all six Xs are in the form of acryl groups.

The compound represented by formula (Z-4) or formula (Z-5) can be synthesized by the following procedure as a previously known procedure: by ring-opening addition of ethylene oxide or propylene oxide with pentaerythritol or dipentaerythritol The step of reacting to bond the ring-opening skeleton, and the step of reacting the terminal hydroxyl group of the ring-opening skeleton with (meth)acryloyl chloride to introduce the (meth)acryloyl group. Each step is a well-known step, those skilled in the art A member can easily synthesize the compound represented by formula (Z-4) or formula (Z-5).

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

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

Examples of commercially available products having a polymerizable compound having an alkoxy group include tetrafunctional propylene having four ethoxy groups manufactured by Sartomer Co., Ltd. SR-494 of acid ester, DPCA-60 as a six-functional acrylate having six pentanyloxy groups manufactured by Nippon Kayaku Co., Ltd., and TPA- as a trifunctional acrylate having three isobutoxy groups 330 etc.

In the present invention, the polymerizable compound can be preferably used: dipentaerythritol triacrylate (commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (city The products are KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol penta(meth)acrylate (commercially available products are KAYARAD D-310; Japanese Pharmaceutical Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; Nippon Kayaku Co., Ltd., A-DPH-12E; Shin Nakamura Chemical Industry Co., Ltd. )), and the structure in which the (meth)acryloyl groups of these compounds are bonded via ethylene glycol residues and propylene glycol residues (for example, SR454 and SR499 commercially available from Sartomer). The oligomer type of these compounds can also be used. In addition, KAYARAD RP-1040, KAYARAD DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.), NK ester (NK Ester) A-TMMT (pentaerythritol tetraacrylate) can also be used , Xinzhongcun Chemical Industry Co., Ltd.), etc.

The polymerizable compound may have acid groups such as carboxyl groups, sulfonic acid groups, and phosphoric acid groups. Examples of commercially available products include M-305, M-510, and M-520 manufactured by East Asia Synthetic Co., Ltd.

The preferred acid value of the polymerizable compound having an acid group is 0.1 mgKOH/g~40 mgKOH/g, particularly preferably 5 mgKOH/g~30 mgKOH/g. If polymerizable If the acid value of the substance 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 terms of manufacturing or handling. Furthermore, the photopolymerization performance is good and the curability is excellent.

Regarding polymerizable compounds, compounds having a caprolactone structure are also preferred.

Examples of the polymerizable compound having a caprolactone structure include DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc. commercially available from Nippon Kayaku (KAYARAD) DPCA series. .

The polymerizable compound is also preferably as described in Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765. Of acrylic urethanes, or Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, Japanese Patent Publication No. 62-39418 Carbamate compounds with an ethylene oxide skeleton. In addition, by using Japanese Patent Laid-Open No. 63-277653, Japanese Patent Laid-Open No. 63-260909, and Japanese Patent Laid-Open No. 1-105238, it has an amine group structure or a sulfide structure in the molecule. The addition of polymerizable compounds, can obtain a coloring composition with very excellent photosensitivity.

Commercially available products include: urethane oligomer UAS-10, urethane oligomer UAB-140 (manufactured by Shanyang Guoce Pulp Company), UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.) , DPHA-40H (manufactured by Nippon Kayaku), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Kyoeisha Chemical Co., Ltd.) Manufacturing) etc.

<<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, it is preferable to have sensitivity to light in the ultraviolet range to the visible range.

When a radically polymerizable compound is used as a polymerizable compound, the photopolymerization initiator is preferably a photoradical polymerization initiator.

In addition, the photopolymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 in the range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton and those having an oxadiazole skeleton), amide phosphine compounds such as amide phosphine oxide, hexaarylbiimidazole, oxime derivatives, etc. Oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, etc. Examples of halogenated hydrocarbon compounds having a triazine skeleton include compounds described in "Bull. Chem. Soc. Japan" (42, 2924 (1969)) by Wakabayashi et al., and description in British Patent No. 1384892 Compounds, compounds described in Japanese Patent Laid-Open No. 53-133428, compounds described in the specification of German Patent No. 3337024, FC Schaefer (FC Schaefer) et al. "Journal of Organic Chemistry (J. Org. Chem.) (29, 1527 (1964)), the compound described in Japanese Patent Laid-Open No. 62-58241, the Japanese Patent Laid-Open Compounds described in Hei 5-281728, compounds described in Japanese Patent Laid-Open No. 5-34920, compounds described in US Patent No. 4212976, and the like.

In addition, from the viewpoint of exposure sensitivity, a compound selected from the group consisting of a trihalogenated methyl triazine compound, a benzyl dimethyl ketal compound, an α-hydroxyketone compound, and an α is preferred -Aminoketone compounds, acetylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives Compounds, cyclopentadiene-benzene-iron complexes and their salts, halogenated methyloxadiazole compounds, 3-aryl-substituted coumarin compounds.

The photopolymerization initiator is a trihalogenated methyltriazine compound, α-aminoketone compound, acetylphosphine compound, phosphine oxide compound, oxime compound, triarylimidazole dimer, onium compound, benzophenone compound, benzene The ketone compound is preferably at least one compound selected from the group consisting of trihalide methyltriazine compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds.

For a specific example of the photopolymerization initiator, for example, refer to paragraph No. 0265 to paragraph No. 0268 of Japanese Patent Laid-Open No. 2013-29760, and this content is incorporated into this specification.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Laid-Open No. 10-291969, and an acylphosphine-based initiator described in Japanese Patent No. 4225898 can also be used.

Hydroxyacetophenone-based initiators can be used: IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IGNACURE (IRGACURE)-127 (trade name: all manufactured by BASF).

Aminoacetophenone-based initiators can be used as commercially available products IRGACURE-907, IRGACURE-369 and IRGACURE-379EG (trade names: all BASF ( BASF) manufactured by the company). As the aminoacetophenone-based initiator, a compound described in Japanese Patent Laid-Open No. 2009-191179 whose maximum absorption wavelength matches a wave light source such as 365 nm or 405 nm can also be used.

Acylphosphine-based initiators can be used as commercial products, IRGACURE-819 or DAROCUR-TPO (trade names: all manufactured by BASF).

The photopolymerization initiator may more preferably include oxime compounds.

As specific examples of the oxime compound, the compounds described in Japanese Patent Laid-Open No. 2001-233842, the compounds described in Japanese Patent Laid-Open No. 2000-80068, and the compounds described in Japanese Patent Laid-Open No. 2006-342166 can be used.

In the present invention, examples of the oxime compound that can be preferably used include, for example, 3-benzyloxyiminobutane-2-one, 3-ethoxyiminobutane-2-one, 3 -Propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one , 2-benzyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one, and 2-ethoxycarbonyl Oxyimino-1-benzene Propane-1-one and so on.

Also listed are: "British Chemical Society Journal, Perkins II (JCSPerkin II)" (1979) pp.1653-1660, "British Chemical Society Journal, Perkins II (JCSPerkin II)" "(1979) pp.156-162, "Journal of Photopolymer Science and Technology" (1995, pp.202-232), Japanese Patent Laid-Open No. 2000-66385, Compounds described in each of Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2004-534797, and Japanese Patent Laid-Open No. 2006-342166, etc.

Among commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) can also be preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), Adeka Arkls NCI-831 and Adeka Arkls NCI-930 (Made by ADEKA).

In addition, oxime compounds other than those described above can also be used: compounds described in Japanese Patent Laid-Open No. 2009-519904 in which the oxime is linked to the N position of the carbazole ring, and a hetero substituent is introduced into the benzophenone site The compound described in US Patent No. 7626957, the compound described in Japanese Patent Laid-Open No. 2010-15025 and the compound disclosed in US Patent Publication 2009-292039, and the international publication WO2009/131189 The described ketoxime compound, the compound described in US Patent No. 7556910 containing a triazine skeleton and an oxime skeleton in the same molecule, has a maximum absorption at 405 nm and is good for a g-ray light source The compound described in Japanese Patent Laid-Open No. 2009-221114 and the compound described in Paragraph No. 0076-Paragraph No. 0079 of Japanese Patent Laid-Open No. 2014-137466, etc.

Preferably, for example, refer to paragraph number 0274 to paragraph number 0275 of Japanese Patent Laid-Open No. 2013-29760, and incorporate this content into this specification.

Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). In addition, the oxime may have an oxime compound whose N-O bond is (E), an oxime compound of (Z), or a mixture of (E) and (Z).

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 non-metallic atomic group.

Examples of the monovalent non-metallic atomic group include an alkyl group, an aryl group, an acetyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. In addition, these groups may also have more than one substituent. In addition, the substituents described above may be further substituted with other substituents.

Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an oxyoxy group, an acetyl group, an alkyl group, an aryl group, and the like.

In the formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, Arylcarbonyl or heterocyclic carbonyl. These groups may also have more than one substituent. The substituent may be exemplified by the substituents described above.

In the formula (OX-1), the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkyl group, or a fast group. These groups may also have more than one substituent. The substituent may be exemplified by the substituents described above.

The oxime compound preferably has a maximum absorption wavelength in the wavelength range of 350 nm to 500 nm, more preferably has an absorption wavelength in the wavelength range of 360 nm to 480 nm, and particularly preferably has high absorbance at 365 nm and 405 nm.

Regarding the oxime compound, from the viewpoint of sensitivity, the molar absorption coefficient at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000.

The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to use an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using ethyl acetate solvent at a concentration of 0.01 g/L. Determination.

Specific examples of oxime compounds that can be preferably used in the present invention are shown below, but the present invention is not limited to these specific examples.

The present invention can also use an oxime compound having a fluorine atom as a photopolymerization initiator Initial agent. Specific examples of the oxime compound having a fluorine atom include compounds described in Japanese Patent Laid-Open No. 2010-262028, Compound 24 and Compounds 36 to 40 described in Japanese Patent Laid-Open No. 2014-500852, and Japanese Patent No. The compound (C-3) and the like described in Japanese Patent Publication No. 2013-164471 are disclosed. Incorporate this content into this manual.

The content of the photopolymerization initiator relative to the total solid content of the coloring composition is preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass to 30% by mass, and further preferably 1% by mass to 20% by mass. Within this range, better sensitivity and pattern formability can be obtained. The coloring composition may contain only one kind of photopolymerization initiator or two or more kinds. When two or more cases are included, the total amount is preferably within the above range.

<<Pigment Derivatives>>

The coloring composition of the present invention preferably contains a pigment derivative. The pigment derivative is preferably a compound having a structure in which a part of an organic pigment is substituted with an acid group, a basic group, or phthalimide methyl group. From the viewpoint of dispersibility and dispersion stability, the pigment derivative is preferably a pigment derivative having an acidic group or a basic group.

Examples of organic pigments used to constitute pigment derivatives include diketopyrrolopyrrole-based pigments, azo-based pigments, phthalocyanine-based pigments, anthraquinone-based pigments, quinacridone-based pigments, dioxazine-based pigments, and violet Perinone pigments, perylene pigments, thioindigo pigments, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, threne pigments, metal complex compounds Pigments, etc.

In addition, the acidic group of the pigment derivative is preferably a sulfonic acid group, a carboxylic acid group and The salt thereof is more preferably a carboxylic acid group and a sulfonic acid group, and particularly preferably a sulfonic acid group. The basic group possessed by the pigment derivative is preferably an amine group, particularly preferably a tertiary amine group.

Pigment derivatives are particularly preferably quinoline-based, benzimidazolone-based, and isoindoline-based pigment derivatives, and further preferably quinoline-based and benzimidazolone-based pigment derivatives. In addition, the pigment derivative is preferably a pigment derivative having the following structure.

In formula (PZ), A represents a structure selected from the following formula (PA-1) to formula (PA-3), B represents a single bond or (t+1) valent linking group, and C represents a single bond, -NH -, -CONH-, -CO ₂ -, -SO ₂ NH-, -O-, -S- or -SO ₂ -, D represents a single bond, alkylene or aryl, and E represents -SO ₃ H or Its salt, -CO ₂ H or its salt, or -N(Rpa)(Rpb), Rpa and Rpb independently represent an alkyl group or an aryl group, Rpa and Rpb can also be connected to each other to form a ring, t represents 1~5 An integer of

Rp ₁ represents an alkyl or aryl group having 1 to 5 carbon atoms, Rp ₂ represents a halogen atom, an alkyl group or a hydroxyl group, Rp ₃ represents a single bond, -NH-, -CONH-, -CO ₂ -, -SO ₂ NH- , -O-, -S-, or -SO ₂ -, s represents an integer of 0 to 4, and when s is 2 or more, a plurality of Rp ₂ may be the same as or different from each other, and * represents a connection portion with B.

Rp _{1 is} preferably methyl or phenyl, more preferably methyl.

Rp _{2 is} preferably a halogen atom, more preferably a chlorine atom.

In the formula (PZ), the (t+1)-valent linking group represented by B includes, for example, an alkylene group, an aryl group, and a heteroaryl group. The alkylene group includes straight chain, branched, and cyclic.

The (t+1) valent linking group is particularly preferably a linking group represented by the following structural formula (PA-4) to structural formula (PA-9). ＊Indicates the connection with A and C.

In the structural formula (PA-4) to the structural formula (PA-9), especially the pigment derivative having the linking group represented by the structural formula (PA-5) or the structural formula (PA-8) as B is more excellent in dispersibility , It is better.

In the formula (PZ), the alkylene and aryl groups represented by D include, for example, methylene, ethyl, propyl, butyl, pentyl, hexyl, decyl, and cyclic Propyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl Base, phenylene, naphthyl, etc. Among these groups, D is preferably a linear alkylene group, and more preferably a linear alkylene group having 1 to 5 carbon atoms.

In the formula (PZ), when E represents -N(Rpa)(Rpb), the alkyl and aryl groups of Rpa and Rpb include, for example, methyl, ethyl, propyl, isopropyl, butyl, Second butyl, third butyl, pentyl, isopentyl, neopentyl, hexyl, octyl, decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl Base, phenyl, naphthyl, etc. Rpa and Rpb are particularly preferably straight-chain or branched alkyl groups, and most preferably straight-chain or branched alkyl groups having 1 to 5 carbon atoms.

In the formula (PZ), when E represents a salt of -SO ₃ H or a salt of -CO ₂ H, the salt-forming atom or atomic group is preferably an alkali metal such as a lithium atom, sodium atom, potassium atom, ammonium, Alkyl ammonium etc.

The t is preferably 1 or 2.

Specific examples of pigment derivatives include the following compounds.

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

<<Solvent>>

The coloring composition of the present invention may 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 or the applicability of the composition, and is preferably selected in consideration of the applicability and safety of the composition.

Examples of organic solvents include the following solvents.

Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, Butyl butyrate, methyl lactate, ethyl lactate, alkyl alkoxyacetate (e.g. methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g. methyl methoxyacetate , Ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkoxypropionic acid alkyl esters (such as 3-alkoxy Methyl propionate, ethyl 3-alkoxypropionate, etc. (e.g. methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethyl Ethyloxypropionate, etc.)), 2-alkoxypropionic acid alkyl esters (eg 2-alkoxypropionic acid methyl ester, 2-alkoxypropionic acid ethyl ester, 2-alkoxypropionic acid Propyl ester, etc. (e.g. methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxy Ethyl propionate)), 2-alkoxy-2-methylpropionic acid methyl ester and 2-alkoxy-2-methylpropionic acid ethyl ester (eg 2-methoxy-2-methylpropionic acid Methyl ester, 2-ethoxy-2-methyl ethyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxo Methyl butyrate, ethyl 2-oxobutyrate, etc. Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylenedioxide Alcohol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone. Examples of aromatic hydrocarbons include toluene and xylene.

One type of organic solvent may be used alone, or two or more types may be used in combination.

When two or more organic solvents are used in combination, it is particularly preferable to include the 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, ethyl cellosolve acetic acid. Ester, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol A mixed solution of two or more of alcohol acetate, propylene glycol methyl ether and propylene glycol methyl ether acetate.

In the present invention, the organic solvent preferably has a peroxide content rate of 0.8 mmol/L or less, and more preferably contains substantially no peroxide.

The content of the solvent is preferably 10% by mass to 95% by mass relative to the total amount of the coloring 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.

Examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butyl catechol, benzoquinone, 4,4' -Thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenyl Hydroxylamine cerium salt, etc. Among them, p-methoxyphenol is preferred.

The content of the polymerization inhibitor is preferably 0.01% by mass to 5% by mass relative to the total solid content of the coloring composition.

<<Surface Active Agent>>

From the viewpoint of further improving coatability, the coloring composition of the present invention may contain various surfactants. As the surfactant, various surfactants such as a fluorine-based surfactant, a non-ionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.

By including a fluorine-based surfactant in the composition, the liquid characteristics (particularly fluidity) when the coating liquid is prepared are further improved, and the uniformity or liquidity of the coating thickness can be further improved.

That is, when a coating liquid using a composition containing a fluorine-based surfactant is used for film formation, the interfacial tension between the coated surface and the coating liquid decreases, and the wettability of the coated surface is improved , The applicability to the coated surface is improved. Therefore, a film with a uniform thickness and a small thickness unevenness can be more preferably formed.

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

Examples of the fluorine-based surfactants are Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141 , Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, Megafac F482, Megafac F554, Megafac F780 , Megafac (Megafac) RS-72-K (above made by DIC), Fluorad FC430, Fluorad FC431, Fluorad FC171 (above) (Made for Sumitomo 3M Co., Ltd.), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Sand Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon ) KH-40 (above manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), etc. As the fluorine-based surfactant, a block polymer may be used, and specific examples thereof include compounds described in Japanese Patent Laid-Open No. 2011-89090.

As the fluorine-based surfactant, a fluorine-containing polymer compound can also be preferably used. The fluorine-containing polymer compound contains a repeating unit derived from a (meth)acrylate compound having a fluorine atom, and is derived from having two or more (Preferably five or more) repeating units of the (meth)acrylate compound of the alkoxy group (preferably ethoxy group, propylene group), the following compounds may also be used as the fluorine-based The surfactant is exemplified.

The weight average molecular weight of the compound is preferably 3,000 to 50,000, such as 14,000. In addition, a fluorine-containing polymer having an ethylenically unsaturated group on the side chain can also be used as a fluorine-based surfactant. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Laid-Open No. 2010-164965, for example, Megafac RS-101 and Mega Method manufactured by DIC Corporation. (Megafac) RS-102, Megafac RS-718K, etc.

In addition, the fluorine-based surfactant can also use the following compounds.

Specific examples of nonionic surfactants include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates of these (eg, propoxylated glycerin, ethoxylated glycerin) Etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurel Ester, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, Pluronic L31, Pluronic L61, Pluronic manufactured by BASF) (Pluronic) L62, Pluronic 10R5, Pluronic 17R2, Pluronic 25R2, Tetronic 304, special Tetronic 701, Tetronic 704, Tetronic 901, Tetronic 904, Tetronic 150R1), Solsperse 20000 (Japan Lubrizol (made by Librizol Japan), etc. In addition, NCW-101, NCW-1001, NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. can also be used.

Specific examples of the cationic surfactants include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Industries Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (methyl) Acrylic (co)polymer Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (produced by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yushang Co., Ltd.) etc.

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

Examples of silicone surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (the above is Toray-Dow corning), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (the above is Momentive Performance Materials) (Manufactured), KP341, KF6001, KF6002 (above manufactured by Shinetsu silicone Co., Ltd.), BYK 307, BYK 323, BYK 330 (above BYK Chemical (Made by BYK Chemie) etc.

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

The content of the surfactant relative to the total solid content of the coloring composition is preferably 0.001% by mass to 2.0% by mass, and more preferably 0.005% by mass to 1.0% by mass.

<<Other Ingredients>>

The coloring composition of the present invention may contain thermal polymerization initiators such as azo compounds or peroxide compounds, thermal polymerization components, ultraviolet absorbers such as alkoxybenzophenone, and plastics such as dioctyl phthalate. Various additives such as developing agents, low-molecular-weight organic carboxylic acids, and other developing agents, other fillers, antioxidants, and anti-agglomerating agents.

In some cases, metal elements are included in the composition due to the raw materials used, but from the viewpoint of suppressing the occurrence of defects, the content of the Group 2 elements (calcium, magnesium, etc.) in the colored composition is preferably 50 ppm or less It is better to control within 0.01ppm~10ppm. In addition, the total amount of inorganic metal salts in the coloring composition is preferably 100 ppm or less, and more preferably controlled within 0.5 ppm to 50 ppm.

<Preparation method of coloring composition>

The coloring composition of the present invention can be prepared by mixing the above-mentioned components.

When preparing the coloring composition, the components may be formulated together, or the components may be dissolved and dispersed in a solvent and formulated sequentially. In addition, the order of input and operating conditions during deployment are not particularly restricted. For example, all the ingredients can be dissolved and dispersed in In the preparation of the composition in the agent, if necessary, each component may be appropriately prepared into two or more solutions and dispersions in advance, and these solutions and dispersions are mixed to prepare the composition during use (during application).

In addition, it is preferable to disperse the red pigment together with other components such as resin, organic solvent, pigment derivative, etc. as necessary to prepare a pigment dispersion liquid, and prepare the pigment dispersion liquid by mixing with other components of the coloring composition.

When manufacturing a colored composition, in order to remove foreign substances, reduce defects, etc., it is preferable to perform filtration using a filter. The filter can be used without particular limitation as long as it is a filter that has been conventionally used in filtration applications and the like. Examples include filters using the following materials: fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (for example, nylon-6, nylon-6,6), polyethylene, and polypropylene (Polypropylene) , PP) and other polyolefin resins (including high-density, ultra-high molecular weight polyolefin resins) and so on. Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferred.

The pore size of the filter is suitably about 0.01 μm to 7.0 μm, preferably about 0.01 μm to 3.0 μm, and more preferably about 0.05 μm to 0.5 μm. By setting it as this range, the fine foreign material which hinders the preparation of a uniform and smooth composition in the subsequent steps can be reliably removed. In addition, it is also preferable to use a fibrous filter material, and examples of the filter material include polypropylene fiber, nylon fiber, and glass fiber. Specifically, SBP type series (SBP008, etc.) and TPR type manufactured by Roki Techno can be used. Filter cartridges of series (TPR002, TPR005, etc.) and SHPX type series (SHPX003, etc.).

When using filters, different filters can also be combined. At this time, the filtering by the first filter may be performed only once, or may be performed twice or more.

In addition, the first filters having different pore sizes may be combined within the above range. The pore size here can refer to the nominal value of the filter manufacturer. Commercially available filters are available from, for example, Japan Pall Co., Ltd. (DFA4201NXEY, etc.), Adantec Toyo Co., Ltd., Entegris Japan Co., Ltd. (original) Choose from a variety of filters provided by Japan Microris Co., Ltd. or Kitz Micro Filter Co., Ltd.

As the second filter, a filter formed of the same material as the first filter can be used.

For example, the filtration by the first filter may be performed only with the dispersion liquid, and after mixing other components, the second filtration may be performed.

<Physical Properties of Coloring Composition>

The coloring composition of the present invention is preferably obtained by dividing the integrated intensity of fluorescence in the wavelength range of 600 nm to 700 nm when a film having a thickness of 3.0 μm formed by using the coloring composition of the present invention is excited by light having a wavelength of 534 nm, divided by The value of the integrated intensity of the fluorescence of the cured film A with a thickness of 3.0 μm at a wavelength of 600 nm to 700 nm when excited by light with a wavelength of 534 nm is 0.5 or less, more preferably 0.3 or less, further preferably 0.2 or less, particularly preferably Below 0.1.

<transmit filter>

The transmission filter of the present invention uses the coloring composition of the present invention described above Made. The transmission filter of the present invention is preferably used as a transmission filter of a fluorescent sensor.

The emission filter of the present invention preferably has an integrated intensity of fluorescent light having a wavelength in the range of 600 nm to 700 nm when excited by light having a wavelength of 534 nm of 0.5 to 0.0001, more preferably 0.3 to 0.001.

The film thickness of the transmission filter of the present invention is preferably from 10,000 nm to 50,000 nm, and more preferably from 10,000 nm to 35,000 nm.

The transmission filter of the present invention preferably has a transmittance in the range of wavelengths of 400 nm to 450 nm of 20% or less, more preferably 10% or less, and still more preferably 5% or less.

The transmission filter of the present invention preferably has a transmittance of 40% or more in the wavelength range of 550 nm to 600 nm, more preferably 45% or more, and still more preferably 50% or more.

<fluorescence sensor>

Next, the fluorescent sensor of the present invention will be described.

The fluorescent sensor of the present invention is not particularly limited as long as it has a structure including an emission filter using the coloring composition of the present invention.

The fluorescent sensor may include a user who emits excitation light to a sample. The sample is not particularly limited, and examples include samples that generate fluorescence by irradiating excitation light. Examples include proteins, nucleic acids (DNA (deoxyribonucleic acid), ribonucleic acid (RNA), etc.), cells, and microorganisms.

The fluorescent sensor of the present invention can be preferably used as a DNA sensor.

An embodiment of the fluorescent sensor of the present invention will be described using FIG. 1. Furthermore, the fluorescent sensor of the present invention is not limited to the following embodiments.

The fluorescent sensor shown in FIG. 1 is a drop-type fluorescent sensor. Figure 1 The fluorescent sensor has a light source 1, an excitation filter 2, a beam splitter 3, an objective lens 4, a sample holder 5, a transmission filter 6, and an eyepiece 7. The transmission filter 6 includes the coloring composition of the present invention. The arrows in the figure indicate the traveling direction of light (excitation light, fluorescent light, etc.).

In the fluorescent sensor shown in FIG. 1, the light irradiated from the light source 1 is limited to the light of the excitation wavelength by the excitation filter 2 to become the excitation light.

The light source 1 is not particularly limited. For example, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, chemical lamps, xenon lamps, ultraviolet light-emitting diodes (ultraviolet LEDs), excimer laser generators, etc. can be used.

The excitation filter 2 can be appropriately selected according to the type of target excitation light. For example, when using light with a wavelength of 534 nm as the excitation light, it is preferable to use a filter that transmits light with a wavelength of 534 nm and blocks light of other wavelengths.

The excitation light is reflected by the spectroscope 3 and passes through the objective lens 4 to irradiate the sample 100 on the sample holder 5. When the sample 100 is irradiated with excitation light, the fluorescence generated by the sample and the excitation light scattered by the sample are introduced into the beam splitter 3 through the objective lens 4. Among the light introduced into the dichroic mirror 3, the light containing the fluorescent component is straightened in the dichroic mirror 3 and then introduced into the emission filter 6. In the emission filter 6, only the wavelength of the target fluorescent light is transmitted through the light traveling straight through the dichroic mirror 3, and the wavelength of the target fluorescent light is introduced into the eyepiece section 7. The fluorescent light introduced into the eyepiece portion can be observed by naked eye observation or camera.

Since the fluorescence sensor of the present invention has low fluorescence for the excitation light, it can suppress the influence of fluorescence caused by the emission filter and detect the sense Degree is excellent.

2, another embodiment of the fluorescent sensor of the present invention will be described.

The fluorescent sensor shown in FIG. 2 is a transmissive fluorescent 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 transmission filter 16 includes the coloring composition of the present invention.

In the fluorescent sensor shown in FIG. 2, the light irradiated from the light source 11 is limited to the light of the excitation wavelength by the excitation filter 12 and becomes the excitation light. The excitation light is reflected by the mirror 13 and irradiates the sample 101 on the sample holder 14. When the sample 101 is irradiated with excitation light, the fluorescence generated by the sample and the excitation light scattered by the sample are introduced into the emission filter 16 through the objective lens 15. In the transmission filter 16, only the wavelength of the target fluorescent light is transmitted, and the wavelength of the target fluorescent light is introduced into the eyepiece portion 17. The fluorescent light introduced into the eyepiece portion can be observed by naked eye observation or camera.

<Manufacturing method of fluorescent sensor>

The manufacturing method of the fluorescent sensor of the present invention includes the step of forming a transmission filter using the coloring composition of the present invention.

Specifically, it can also be manufactured through the steps of forming a coloring composition layer on the support using the coloring composition of the present invention, and hardening the coloring composition layer. In addition, a step of forming a pattern may be further performed. Hereinafter, each step will be described.

First, use the coloring composition of the present invention to form a coloring set on a support Adult layer. The support is not particularly limited. Examples include transparent substrates such as glass, silicon wafers, and polymer resins (such as epoxy resin). Various methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, and screen printing method can be used for the application method of the composition on the support.

The coloring composition layer formed on the support may also be pre-baked. In the case of pre-baking, the pre-baking temperature is preferably 150° C. or lower, more preferably 120° C. or lower, and further preferably 110° C. or lower. For example, the lower limit may be 50°C or higher, or 80°C or higher. The pre-baking time is preferably 10 seconds to 300 seconds, more preferably 40 seconds to 250 seconds, and further preferably 80 seconds to 220 seconds. Drying can be performed using a hot plate, an oven, or the like.

Then, the coloring composition layer formed on the support is hardened and cured. The hardening process is preferably an exposure process.

For the radiation (light) that can be used during exposure, ultraviolet rays such as g-rays and i-rays are preferably used (i-rays are particularly preferably used). Irradiation amount (exposure amount), for example, is preferably ^{0.03J / cm 2 ~ 2.5J / cm} 2, more preferably ^{0.05J / cm 2 ~ 1.0J / cm} 2, most preferably 0.08J / cm ² ~ 0.5J / cm ² .

The oxygen concentration at the time of exposure can be appropriately selected, and in addition to being performed in the atmosphere, for example, under a low-oxygen environment with an oxygen concentration of 19% by volume or less (eg, 15% by volume, 5% by volume, substantially oxygen-free) The exposure may be performed under a high-oxygen environment with an oxygen concentration exceeding 21% by volume (for example, 22% by volume, 30% by volume, and 50% by volume). Further, exposure illuminance can be set appropriately, usually selected from the range of ² ~ ^100000W / m ² (e.g. ^{5000W / m 2, 15000W / m} 2, 35000W / m 2) of 1000W / m. The oxygen concentration and the exposure illuminance can also be appropriately combined. For example, the oxygen concentration can be set to 10% by volume and the illuminance is 10,000 W/m ² , the oxygen concentration is 35% by volume and the illuminance is 20,000 W/m ^2, or the like.

After the exposure treatment, heat treatment (post-baking) may be further performed. Post-baking is heat treatment after development to completely harden the film. In the case of performing post-baking, the post-baking temperature is preferably 100°C to 240°C, for example. From the viewpoint of film hardening, it is more preferably 200°C to 230°C. The post-baking can be performed on the developed film in a continuous or batch mode using a heating mechanism such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater so that the conditions are as described above.

In this way, a transmission filter can be manufactured. The fluorescent sensor can be manufactured by incorporating the emission filter obtained in the above-mentioned manner into the fluorescent sensor.

[Example]

Hereinafter, the present invention will be described more specifically by examples, but the present invention is not limited to the following examples as long as the gist is not exceeded. Furthermore, unless otherwise specified, "parts" and "%" are the quality standards. In addition, hereinafter, 1 inch is 2.54 cm.

(Measurement method of average particle diameter of pigment)

The average particle diameter of the pigment is measured by dynamic light scattering method. Specifically, it was measured using DLS-8000 series (manufactured by Otsuka Electronics).

(Using raw materials)

The components used in the coloring compositions of Examples and Comparative Examples are the following components.

. Red paint

PR144: C.I. Pigment Red 144

PR166: C.I. Pigment Red 166

PR254: C.I. Pigment Red 254

. Resin

(Resin 1)

D-1: The following structure (weight average molecular weight 38000, the numerical value described together with each repeating unit (main chain) represents the content (mass ratio) of each repeating unit. The numerical value described together with the repeating part of the side chain represents repetition (Number of repetitions of the part)

D-2: The following structure (weight-average molecular weight of 20,000, the value described with each repeating unit (main chain) represents the content (mass ratio) of each repeating unit. The value described with the repeating portion of the side chain represents repeating (Number of repetitions of the part)

D-3: The following structure (weight average molecular weight 24000, the numerical value described together with each repeating unit (main chain) indicates the content (mass ratio) of each repeating unit. The numerical value described together with the repeating part of the side chain indicates repeating (Number of repetitions of the part)

(Resin 2)

B-1: The following structure (weight-average molecular weight 11,000, the value described with each repeating unit (main chain) indicates the content (mass ratio) of each repeating unit)

B-2: The following structure (weight-average molecular weight 12000, the value described with each repeating unit (main chain) indicates the content (mass ratio) of each repeating unit)

B-3: The following structure (weight-average molecular weight of 40,000, the numerical value described together with each repeating unit (main chain) indicates the content (mass ratio) of each repeating unit)

. Pigment derivatives

PZ-1: The following structure

. Polymerizable compound

M-1~M-3: The following structure. Furthermore, M-2 is a compound of the left formula and a compound of the right formula The compound is a 7:3 mixture in mass ratio. The n of M-3 is 1 to 3, and the total of four n is 12 or less.

M-4: NK ester (NK Ester) A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)

. Photopolymerization initiator

I-1~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)

The coloring composition of the components shown in Table 1 was used for evaluation.

(Composition ratio)

界面活性劑：0.001質量%溶劑(丙二醇單甲醚乙酸酯(Propylene Glycol Monomethyl Ether Acetate，PGMEA))：剩餘部分

Surfactant: 0.001% by mass solvent (Propylene Glycol Monomethyl Ether Acetate (PGMEA)): remaining part

Regarding the coloring composition, the pigment, the resin 1 and the pigment derivative are mixed to prepare a pigment dispersion liquid, and the remaining components are mixed in the pigment dispersion liquid to produce a coloring composition of the above composition.

(Determination of Fluorescence Intensity)

Each coloring composition is coated on a glass substrate to form a coloring composition layer. membrane The thickness is adjusted so that the transmittance of the cured film at a wavelength of 500 nm becomes 5%.

Then, after pre-baking at 100°C for 2 minutes, exposure was performed under the condition of 1000 mJ/cm ² , and post-baking was performed at 220°C for 5 minutes to produce a cured film.

For the obtained cured film, F4500 manufactured by Hitachi High-tech Co., Ltd. was used, and the wavelength was measured under the conditions of an excitation wavelength of 534 nm, an excitation slit of 5 nm, a fluorescent slit of 5 nm, and a photomultiplier voltage of 950 V. The integrated intensity of fluorescence in the range of 600nm to 700nm. In addition, when measuring the fluorescence intensity, in order to suppress the stray light, a 530 nm bandpass filter is used on the light source side, and a sharp wave filter is used on the detection side for measurement to suppress the scattered light. Using the integrated value of 600 nm to 700 nm of the obtained fluorescence spectrum, the value obtained by dividing the result of the coloring composition of Comparative Example 1 was calculated as the fluorescence intensity ratio.

(Evaluation of dispersion stability)

Each coloring composition was stored in a thermostat at 50°C and the spectrum was measured one week later. The spectrum of 400 nm to 800 nm before and after storage was measured, and the wavelength with the largest spectral change before and after storage was determined under the following conditions.

5: Spectral variation is less than 1% before and after storage

4: Spectral variation before and after storage exceeds 1% and is below 3%

3: Spectral variation before and after storage exceeds 3% and is below 5%

2: Spectral variation before and after storage exceeds 5% and is below 10%

1: Spectral change exceeds 10% before and after storage

(Light resistance evaluation)

The substrate whose fluorescence intensity was measured was irradiated at 1.0×10 ⁵ lux for 50 hours using a xenon lamp to measure light resistance. The spectrum of 400 nm to 800 nm before and after the treatment was measured, and the wavelength with the largest spectral change before and after the treatment was determined under the following conditions.

5: Spectral variation is less than 1% before and after processing

4: Spectral variation before and after processing exceeds 1% and is below 3%

3: Spectral variation before and after processing exceeds 3% and is below 5%

2: Spectral variation exceeds 5% before and after processing and is below 10%

1: Spectral variation exceeds 10% before and after processing

(Analytic evaluation)

On the substrate for measuring the fluorescence intensity, a mask with a pattern is placed for exposure during exposure. Thereafter, development processing was performed with a 2.5% by mass TMAH (tetramethylammonium hydroxide) aqueous solution. The limit size of the pattern shape that can be produced after development is judged under the following conditions.

5: The limit resolution is below 1.4μm

4: The limit resolution exceeds 1.4 μm and is below 1.7 μm

3: The limit resolution exceeds 1.7 μm and is less than 2 μm

2: The limit resolution exceeds 2 μm and is less than 3 μm

1: No lithography

(Evaluation of residue defects)

For a substrate whose fluorescence intensity was measured, the number of defects of the entire film was measured using ComPlus manufactured by Applied Material. Determine the measurement result under the following conditions. Judging from 1μm or more as a source of material The garbage is judged as a defect of the whole film.

5: The number of defects around the 8-inch wafer is less than 100

4: The number of defects around the 8-inch wafer exceeds 100 and is less than 300

3: The number of defects around the 8-inch wafer exceeds 300 and is less than 500

2: The number of defects around the 8-inch wafer exceeds 500 and is less than 1000

1: The number of defects around the 8-inch wafer exceeds 1000

As shown in the table, the fluorescent intensity ratio of the examples is small. In addition, the fluorescent sensor using the cured film of the embodiment as an emission filter is excellent in detection sensitivity.

On the other hand, the detection sensitivity of the fluorescent sensor using the cured film of the comparative example as an emission filter is poor.

In addition, the cured films of Examples 1 to 38 and Comparative Examples 1 to 5 were incorporated as emission filters of fluorescent sensors, and the samples were irradiated with excitation light with a wavelength of 534 nm to perform fluorescent detection. As a result, Examples 1 to 38 have better detection sensitivity than Comparative Examples 1 to 5.

1‧‧‧Light source

2‧‧‧ Excitation filter

3‧‧‧Spectroscope

4‧‧‧Objective

5‧‧‧Sample holder

6‧‧‧Transmission filter

7‧‧‧ Eye department

100‧‧‧Sample

Claims (14)

A coloring composition, which is a coloring composition for forming an emission filter of a fluorescent sensor, and contains a red pigment, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent. The coloring composition will be used The integrated intensity of the fluorescent film in the wavelength range of 600 nm to 700 nm when the film formed with a thickness of 3.0 μm is excited by light with a wavelength of 534 nm divided by the thickness of 3.0 μm, which contains 40% by mass of the color index pigment red 254 in the total solid content The value of the integrated intensity of fluorescence of the cured film A at a wavelength of 600 nm to 700 nm when excited by light with a wavelength of 534 nm is 0.5 or less, and the total mass of the red pigment contains 99% by mass or more of CI pigment red 144 and CI Pigment Red 166. A coloring composition, which is a coloring composition for forming an emission filter of a fluorescent sensor, and contains at least one red pigment, resin, and polymerizable compound selected from color index pigment red 144 and color index pigment red 166 , A photopolymerization initiator and a solvent, and the total mass of the red pigment contains 99% by mass or more of CI Pigment Red 144 and CI Pigment Red 166. The coloring composition as described in item 1 or 2 of the patent application, wherein the average particle diameter of the red pigment is 5 nm to 500 nm. If the coloring composition described in item 1 or item 2 of the scope of patent application, Wherein the polymerizable compound is a polymerizable monomer. The coloring composition as described in item 4 of the patent application range, wherein the polymerizable monomer has three or more radical polymerizable groups. The coloring composition as described in item 4 of the patent application range, wherein the polymerizable monomer has an alkoxy group. The coloring composition as described in item 6 of the patent application range, wherein the polymerizable monomer has a chain containing two or more of the alkoxy groups as repeating units. The coloring composition as described in item 1 or 2 of the patent application, wherein the resin contains a graft copolymer. The coloring composition according to item 1 or 2 of the patent application scope, wherein the resin includes a resin containing a repeating unit represented by any one of the following formula (1) to formula (4);

In formula (1) to formula (4), W ¹ , W ² , W ³ and W ⁴ each independently represent an oxygen atom or NH, and X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent hydrogen Atom or 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 Alkyl extension, R ⁴ represents a hydrogen atom or a monovalent organic group, n, m, p and q each independently represent an integer of 1 to 500, j and k each independently represent an integer of 2 to 8, in formula (3) , When p is 2~500, multiple R ³ may be the same as or different from each other. In formula (4), when q is 2~500, multiple X ⁵ and R ⁴ may be the same as each other. different. The coloring composition as described in item 1 or 2 of the patent application scope, which is a coloring composition for forming an emission filter of a fluorescent sensor, and the fluorescent sensor is used for excitation by irradiation The sample that generates fluorescent light is irradiated with excitation light, and the light containing the fluorescent light generated by the sample is transmitted through the emission filter to detect the fluorescence sensing of the light containing the fluorescent light transmitted through the emission filter Device. A fluorescent sensor having an emission filter using the coloring composition as described in any one of patent application items 1 to 10. The fluorescent sensor according to item 11 of the patent application scope, wherein the fluorescent sensor is used to irradiate a sample with excitation light. The fluorescent sensor according to item 11 or item 12 of the patent application scope, wherein the fluorescent sensor is a deoxyribonucleic acid sensor. A method for manufacturing a fluorescent sensor, which includes the step of forming a transmission filter using the coloring composition as described in any one of claims 1 to 10 of the patent application.

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