TW201710785A - Dye composition, fluorescence sensor, and production method for fluorescence sensor - Google Patents

Abstract

Provided are: a dye composition with which it is possible to obtain a fluorescence sensor of exceptional detection sensitivity; a fluorescence sensor of exceptional detection sensitivity; and a production method for a fluorescence sensor of exceptional detection sensitivity. The dye composition is used to form an emission filter of a fluorescence sensor, and includes at least one red pigment selected from Color Index Pigment Red 144 and Color Index Pigment Red 166, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent.

Description

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

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

There is a fluorescence sensor that reacts a sample such as deoxyribonucleic acid (DNA) with a reagent, and irradiates the sample with excitation light to generate a firefly generated therefrom. The light is detected and the sample is inspected. In the inspection by the fluorescent sensor, the sample is irradiated with excitation light, and the fluorescence generated by the sample is transmitted through an emission filter to transmit fluorescence of a predetermined wavelength, and the fluorescent light transmitted through the transmission filter is observed. The inspection is performed with light.

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

On the other hand, Patent Document 1 discloses a red color filter for an image display device using a composition containing Chromophthalic Red BRN (Color Index Pigment Red 144) and a photosensitive resin. . Further, Patent Document 2 describes a red color filter for an image display device using a composition containing a color index pigment red 144, polyvinyl alcohol, a surfactant, and water. [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei.

[Problems to be Solved by the Invention] The present inventors conducted intensive studies on a fluorescent sensor, and as a result, it has been found that a transmitting filter using a color index Pigment Red 254 easily generates fluorescence by excitation light, and fluorescence sensing is performed. The detection sensitivity of the device is easily lowered.

On the other hand, Patent Document 1 and Patent Document 2 do not have a description or suggestion relating to a fluorescent sensor.

Accordingly, an object of the present invention is to provide a coloring composition of a fluorescent sensor excellent in detection sensitivity, a fluorescence sensor excellent in detection sensitivity, and a method of manufacturing a fluorescent sensor. [Means for solving the problem]

The present inventors conducted intensive studies on the coloring composition for forming a transmission filter of a fluorescent sensor, and as a result, found that the color index pigment red 144 and the color index pigment red 166 are pigments which are difficult to generate fluorescence by excitation light. . Further, as a result of examining the coloring composition, it has been found that a fluorescent sensor excellent in detecting sensitivity can be obtained by using the following colored composition, thereby completing the present invention, and for the colored composition, The integrated intensity of the fluorescence in the range of 600 nm to 700 nm when the film having a thickness of 3.0 μm formed by the coloring composition is excited by light having a wavelength of 534 nm is divided by the later-described cured film containing the color index pigment red 254. The value obtained by integrating the intensity of the fluorescence in the range of 600 nm to 700 nm at the wavelength of 534 nm is 0.5 or less. The present invention provides the following. <1> A coloring composition which is a coloring composition for forming a radiation filter of a fluorescent sensor, and contains a red pigment, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent, and a coloring composition is used. The integrated intensity of the fluorescence in the range of 600 nm to 700 nm when the film having a thickness of 3.0 μm is excited by light having a wavelength of 534 nm is divided by 40% by mass of the color index pigment red 254 in the total solid content. The value of the integrated intensity of the fluorescence in the range of 600 nm to 700 nm when the cured film A having a thickness of 3.0 μm is excited by light having a wavelength of 534 nm is 0.5 or less. <2> A coloring composition which is a coloring composition for forming a radiation filter of a fluorescent sensor, and contains at least one red pigment selected from the color index pigment red 144 and the color index pigment red 166, a resin, A polymerizable compound, a photopolymerization initiator, and a solvent. <3> The coloring composition as described in <1> or <2>, wherein the red pigment has an average particle diameter of 5 nm to 500 nm. The colored composition according to any one of <1> to <3> wherein the polymerizable compound is a polymerizable monomer. <5> The colored composition according to <4>, wherein the polymerizable monomer has three or more radical polymerizable groups. <6> The colored composition according to <4> or <5> wherein the polymerizable monomer has an alkylene group. <7> The colored composition according to <6>, wherein the polymerizable monomer has a chain containing two or more alkyleneoxy groups as a repeating unit. The colored composition according to any one of <1> to <7> wherein the resin contains a graft copolymer. The colored composition according to any one of the above-mentioned items (1) to (8), wherein the resin comprises a resin containing a repeating unit represented by any one of the following formulas (1) to (4); In the formulae (1) to (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. An atom or a monovalent organic group, Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a divalent linking group, and Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a monovalent organic group, and R ³ represents An alkyl group, R ⁴ represents a hydrogen atom or a monovalent organic group, and n, m, p and q each independently represent an integer of from 1 to 500, and j and k each independently represent an integer of from 2 to 8, in the formula (3) When p is 2 to 500, a plurality of R ³ may be the same or different from each other. In the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ may be the same as each other. different. <10> A fluorescence sensor having a color filter using the coloring composition according to any one of <1> to <9>. <11> The fluorescent sensor according to <10>, wherein the fluorescent sensor is used by irradiating the sample with excitation light. <12> The fluorescent sensor according to <10> or <11>, wherein the fluorescent sensor is a DNA sensor. <13> A method of producing a fluorescent sensor, comprising the step of forming a transmission filter using the coloring composition according to any one of <1> to <9>. [Effects of the Invention]

According to the present invention, it is possible to provide a coloring composition of a fluorescent sensor excellent in detection sensitivity, a fluorescence sensor excellent in detection sensitivity, and a method of manufacturing a fluorescent sensor excellent in detection sensitivity.

In the present specification, the total solid content refers to the total mass of the components obtained by removing the solvent from the total composition of the composition. In addition, the solid component means a solid component at 25 °C. In the expression of the group (atomic group) in the present specification, the unsubstituted and unsubstituted expressions are not described as including a group having no substituent, and also a group having a substituent. For example, the term "alkyl" means not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). The term "radiation" as used herein means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (EUV light), an X-ray, an electron beam, or the like. Further, the term "light" as used in the present invention means actinic ray or radiation. In the present specification, the term "exposure" is used to describe not only the ultraviolet light, the X-ray, the EUV light, etc., which are represented by mercury lamps or excimer lasers, but also the use of particle beams such as electron beams and ion beams. Also included in the exposure. In the present specification, "(meth)acrylate" means either or both of acrylate and methacrylate, and "(meth)acrylic acid" means either or both of acrylic acid and methacrylic acid, "(A) The "alkyl propylene group" means either or both of an acryloyl group and a methacryl fluorenyl group, and "(meth)allyl" means either or both of an allyl group and a methallyl group. In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group. In the present specification, the term "step" means not only an independent step, but also a case where it is impossible to clearly distinguish from other steps, as long as the desired effect of the step can be achieved. In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene-converted values measured by Gel Permeation Chromatography (GPC). In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained, for example, by using HLC-8220 (manufactured by Tosoh Co., Ltd.) using TSKgel Super AWM-H ( Manufactured by Tosoh Co., Ltd., 6.0 mm ID (inner diameter) × 15.0 cm) as a column, using 10 mmol/L lithium bromide N-methyl pyrrolidinone (NMP) solution as the dissolution liquid. The pigment used in the present invention means an insoluble pigment compound which is not easily dissolved in a solvent. Typically, it means a dye compound which exists in a state in which the composition is dispersed in the form of particles. Here, the solvent is exemplified by any solvent, and examples thereof include a solvent exemplified in the column of the solvent described later. The pigment used in the present invention is preferably, for example, propylene glycol monomethyl ether acetate and water, and the solubility at 25 ° C is preferably 0.1 g / 100 g of solvent (Solvent) or less.

<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 requirements of the following (1) or (2). (1): contains a red pigment, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent, and a film having a thickness of 3.0 μm formed using the coloring composition is excited at a wavelength of 534 nm at a wavelength of 600 nm to 700 The integrated intensity of the fluorescence in the nm range is divided by the wavelength of 600 nm to 700 nm when the cured film A having a thickness of 3.0 μm containing 40% by mass of the color index pigment red 254 in the total solid content is excited by light having a wavelength of 534 nm. The value of the integrated intensity of the fluorescence of the range is 0.5 or less. The cured film A is preferably applied to a glass substrate such that the film thickness after curing is 3.0 μm, and the coated film is dried at 100° C., and then exposed to an exposure amount of 1000 mJ/cm ² . The cured film obtained by i-ray exposure, the composition containing 5% by mass of a color index pigment red 254 having an average particle diameter of 50 nm, 1.5% by mass of a resin represented by Formula D-1, and 0.075% by mass of Formula PZ-1 The pigment derivative represented by the formula, 0.7% by mass of the polymerizable compound represented by the formula M-1, 4.925% by mass of the resin represented by the formula B-2, and 0.3% by mass of the photopolymerization initiation represented by the formula I-1 And the remainder is propylene glycol monomethyl ether acetate. In addition, the weight average molecular weight of D-1 is 38,000, and the numerical value together with each repeating unit (main chain) shows the content (mass ratio) of each repeating unit, and the numerical value shown with the repeating site of a side chain is repeated. The number of repetitions of the part. Further, the weight average molecular weight of B-2 is 12,000, and the numerical value described together with each repeating unit (main chain) indicates the content (mass ratio) of each repeating unit. (2): at least one red pigment selected from the color index pigment red 144 and the color index pigment red 166, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent.

According to the present invention, by using the coloring composition of the above (1) or (2), an emission filter having low fluorescence for excitation light can be formed. Further, the color index pigment red 144 and the color index pigment red 166 have particularly low fluorescence for excitation light and are excellent in heat resistance, so that emission with lower fluorescence and higher heat resistance can be formed. filter. Moreover, the emission filter using the coloring composition of the present invention has low fluorescence for excitation light, and therefore, for a fluorescence sensor having a transmission filter using the coloring composition of the present invention, a transmission filter The influence caused by the fluorescence is small, and the detection sensitivity is excellent. Hereinafter, the present invention will be described in detail.

<Coloring Composition><<RedPigment>> The coloring composition of the present invention contains a 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 the 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, for example, be a chlorine atom, a fluorine atom or a bromine atom, and is preferably a chlorine atom. Preferably, at least two of R ¹ to R ⁵ are a halogen atom, and the balance is a hydrogen atom. More preferably, two of R ¹ to R ⁵ are a halogen atom, and the balance is a hydrogen atom. More preferably, R ¹ and R ⁴ are a halogen atom, and R ² , R ³ and R ⁵ are a hydrogen atom. Preferably, at least two of R ¹⁰ to R ¹⁴ are a halogen atom, and the balance is a hydrogen atom. More preferably, two of R ¹⁰ to R ¹⁴ are a halogen atom, and the balance is a hydrogen atom. More preferably, R ¹⁰ and R ¹³ are a halogen atom, and R ¹¹ , R ¹² and R ¹⁴ are a hydrogen atom. 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, R ⁷ is preferably a halogen atom, and the remainder 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 the group consisting of 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 that an emission filter having low fluorescence for excitation light can be formed.

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

In the present invention, the "average particle diameter" of the red pigment is an average particle diameter related to secondary particles in which primary particles of red pigment are aggregated, and is a value measured by a method such as dynamic light scattering. .

In the coloring composition of the present invention, the content of the red pigment is preferably from 10% by mass to 90% by mass based on the total solid content of the coloring composition. The lower limit is more preferably 20% by mass or more, and still more preferably 30% by mass or more. The upper limit is more preferably 80% by mass or less, and further preferably 70% by mass or less. Further, 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. Further, 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 red pigment mass contains 99% by mass or more of CI Pigment Red 144 and CI Pigment Red 166, and more preferably 99.9. More than % by mass.

The pigment shown below can also be used as the red pigment in the present invention. In the case where the red pigment does not contain any of C.I. Pigment Red 144 and C.I. Pigment Red 166, the coloring composition can be selected from one or more of the following pigments in such a manner as to satisfy the requirements of the above (1). Further, the following pigments may 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

- Refining of Pigment - In the present invention, it is preferred that the red pigment be a fine and granulated pigment. The miniaturization of the pigment is achieved by preparing a high-viscosity liquid composition together with a water-soluble organic solvent and a water-soluble inorganic salt, and applying a stress to the ground using a wet pulverizing apparatus or the like.

The water-soluble organic solvent used for the micronization step of the pigment may, for example, be methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol or diethylene glycol monomethyl. Ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether acetate, and the like. 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 having low water solubility or no water solubility, such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, or the like, may also be used. Nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, butyl acetate, hexane, heptane, octane, decane, decane, undecane, ten Dioxane, cyclohexane, methylcyclohexane, halogenated hydrocarbon, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, dimethyl hydrazine, N- Methyl pyrrolidone and the like. The solvent used for the miniaturization step of the pigment may be used alone or in combination of two or more kinds as needed.

The water-soluble inorganic salt used in the micronization step of the pigment may, for example, be sodium chloride, potassium chloride, calcium chloride, barium chloride or sodium sulfate. The amount of the water-soluble inorganic salt used in the refining step is preferably from 1 to 50 times by mass of the pigment. When the amount of the water-soluble inorganic salt used is large, there is a grinding effect, but in terms of productivity, a more preferable amount is from 1 mass to 10 mass times. Further, it is preferred to use an inorganic salt having a water content of 1% or less. The amount of the water-soluble organic solvent used in the refining step is preferably from 50 parts by mass to 300 parts by mass, more preferably from 100 parts by mass to 200 parts by mass, per 100 parts by mass of the pigment.

The operating conditions of the wet pulverizing apparatus in the step of miniaturizing the pigment are not particularly limited, and in order to effectively perform the grinding of the pulverizing medium, the operating conditions in the case where the apparatus is a kneader, the blade in the apparatus. The rotation speed is preferably from 10 rpm to 200 rpm, and the rotation of the two shafts is larger than that of the relatively large one. The operation time is preferably from 1 hour to 8 hours together with the dry pulverization time, and the internal temperature of the apparatus is preferably from 50 ° C to 150 ° C. Further, the water-soluble inorganic salt as the pulverizing medium preferably has a pulverized particle size of 5 μm to 50 μm and a narrow particle diameter distribution and is spherical.

<<Other Colored Color Colorants>> The colored composition of the present invention may also contain other colored colorants other than red pigments. Other colored colorants can be pigments or dyes. Other coloring agents may be used alone or in combination of two or more. In order to reduce the transmittance of the wavelength of 300 nm to 400 nm, other colored colorants are preferably yellow pigments. The yellow pigment is not particularly limited as long as it is commercially available. In the present invention, the colored coloring agent refers to a coloring agent other than a white coloring agent and a black coloring agent. The colored colorant is preferably a colorant having a maximum absorption wavelength in a wavelength range of 400 nm to 700 nm. In addition, the term "maximum absorption wavelength in the range of wavelengths from 400 nm to 700 nm" means a wavelength at which the maximum absorbance is exhibited in the absorption spectrum at a wavelength of from 400 nm to 700 nm. For example, it is preferable to have a wavelength showing a maximum absorbance in a wavelength range of 400 nm to 700 nm in an absorption spectrum in a wavelength range of 350 nm to 1300 nm.

The pigments may be exemplified by various pigments previously known. Further, in consideration of the fact that the high transmittance is preferable, the pigment is preferably a pigment having an average particle diameter as small as possible. If the handleability is also considered, the average particle diameter of the pigment is preferably from 0.01 μm to 0.1 μm. Preferably, it is from 0.01 μm to 0.05 μm.

The 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 11 3. CI Pigment Yellow 114, CI Pigment Yellow 115, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 118, CI Pigment Yellow 119, CI 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

For the dye, for example, Japanese Patent Laid-Open Publication No. SHO-64-90403, Japanese Patent Laid-Open Publication No. SHO-64-91102, Japanese Patent Laid-Open No. Hei No. Hei No. Hei. Japanese Patent No. 2, 592, 207, U.S. Patent No. 4,808, 510, U.S. Patent No. 5, 568, 920, U.S. Patent No. 5, 596, 950, U.S. Patent No. 5, 505, 950, Japanese Patent Laid-Open No. Hei 5- 333 207, Japanese Patent Laid-Open No. Hei 6-35183, Japanese Patent Laid-Open No. Hei 6-51115 The dye disclosed in Japanese Laid-Open Patent Publication No. Hei 6-194928 or the like. If the chemical structure is distinguished, a pyrazole azo compound, a pyrrolemethylene compound, an anilino azo compound, a triarylmethane compound, a hydrazine compound, a benzylidene compound, an oxophthalocyanine compound, or a pyrazole may be used. A triazole azo compound, a pyridone azo compound, a cyanine compound, a phenothiazine compound, a pyrrolopyrazole azomethine compound, or the like. Further, a dye polymer can also be used as the dye. The compound described in Japanese Laid-Open Patent Publication No. 2011-041097, and the Japanese Patent Publication No. 2013-041097.

When the colored composition of the present invention contains another colored coloring agent, the content of the other colored coloring agent is preferably from 1% by mass to 60% by mass based on the total solid content of the colored composition. The lower limit is more preferably 5% by mass or more, and still more preferably 10% by mass or more. The upper limit is more preferably 50% by mass or less.

<<Resin>> The coloring composition of the present invention contains a resin. The resin is formulated, for example, for the purpose of dispersing the pigment in the composition and the use of the binder. Further, a resin mainly used for dispersing a pigment is also referred to as a dispersant. Among them, such a use of the resin is an example and can be used for purposes other than such use.

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

The content of the resin is preferably from 1% by mass to 80% by mass based on 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, more preferably 60% by mass or less. The colored composition of the present invention may contain only one type of resin, or may contain two or more types. When two or more cases are contained, it is preferable that the total amount is the said range.

The colored composition of the present invention may contain a dispersant as a resin. The dispersing agent is preferably a resin having at least one selected from the group consisting of an acid group and a basic group, and more preferably a resin having an acid group. Examples of the acid group of the resin include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. The basic group which the resin has may be an amine group or the like. Further, in the present invention, a resin having no acid group or a basic group may be used as a dispersing agent.

In the case where the resin has an acid group, the acid value of the resin is preferably from 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 further 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 polymer can be preferably used as a dispersing agent for the red pigment. In the present invention, the graft copolymer refers to a resin having a graft chain. Further, the term "graft chain" means the end of a group branched from the root of the polymer main chain to the autonomous chain.

The graft copolymer is preferably a resin having a graft chain in a range of from 40 to 10,000 in terms of a hydrogen atom. Further, the number of atoms other than the hydrogen atom per one graft chain is preferably from 40 to 10,000, more preferably from 50 to 2,000, still more preferably from 60 to 500.

The main chain structure of the graft copolymer may, for example, be a (meth)acrylic resin, a polyester resin, a polyurethane resin, a polyurea resin, a polyamide resin, a polyether resin or the like. Among them, a (meth)acrylic resin is preferred. In order to improve the interaction between the grafting site and the solvent, thereby improving the dispersibility, the graft chain of the graft copolymer is preferably a graft chain having a poly(meth)acrylic acid, a polyester or a polyether, more preferably A graft chain having a polyester or a polyether.

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

A known macromonomer can be used as the macromonomer used in the production of the graft copolymer by radical polymerization, and examples thereof include a macromonomer AA-6 manufactured by East Asia Synthetic Co., Ltd. (the terminal group is a methacrylonitrile group) Polymethyl methacrylate), AS-6 (polystyrene having a terminal group of methacryl fluorenyl), AN-6S (a copolymer of styrene and acrylonitrile having a terminal group of methacryl fluorenyl), AB-6 (polybutyl acrylate of methacryl fluorenyl group), Placcel FM5 made of Daicel (share), ε-hexyl 2-hydroxyethyl methacrylate Lactone 5 molar equivalent plus finished product), FA10L (ε-caprolactone 2-hydroxyethyl acrylate 10-molar equivalent plus finished product), and the polyester giant single product described in Japanese Patent Laid-Open No. Hei 2-272009 Body and so on.

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

In the formulae (1) to (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. An atom or a monovalent organic group, Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a divalent linking group, and Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a monovalent organic group, and R ³ represents An alkyl group, R ⁴ represents a hydrogen atom or a monovalent organic group, and n, m, p and q each independently represent an integer of from 1 to 500, and j and k each independently represent an integer of from 2 to 8, in the formula (3) When p is 2 to 500, a plurality of R ³ may be the same or different, and in the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ may be the same as each other. different.

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

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

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

In the formulae (1) to (4), Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a monovalent organic group. The structure of the monovalent organic group is not particularly limited, and specific examples thereof include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, and a heteroarylthioether. Base and amine group, etc. Among these groups, in particular, in view of improving dispersibility, the organic groups represented by Z ¹ , Z ² , Z ³ and Z ⁴ are preferably groups having a steric repulsion effect, and are preferably independently An alkyl group or an alkoxy group having 5 to 24 carbon atoms, particularly preferably a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms or an alkyl group having 5 to 24 carbon atoms. Oxygen. Further, the alkyl group contained in the alkoxy group may be any of a linear chain, a branched chain, and a cyclic group.

In the formulae (1) to (4), n, m, p and q are each independently an integer of from 1 to 500. Further, in the formulas (1) and (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 the formulae (1) and (2) are preferably an integer of 4 to 6, and most preferably 5.

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

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

The graft polymer 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), from the viewpoint of the dispersion stability and the developability.

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

The graft polymer may further contain a repeating unit having a functional group other than the graft chain and the acid group which can form an interaction 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 coordinating group, a repeating unit containing a reactive group, and the like.

Examples of the basic group include a primary amino group, a secondary amino group, a tertiary amino group, a hetero ring containing an N atom, a guanamine group, and the like. Examples of the ligand group and the reactive group include an etidinylethoxycarbonyl group, a trialkoxyalkylene group, an isocyanate group, an acid anhydride residue, and a ruthenium chloride residue. The graft polymer may contain the repeating unit having a functional group or may not contain the repeating unit having a functional group, and in the case of containing the repeating unit having a functional group, relative to the total mass of the grafted resin, It is preferably 0.1% by mass to 50% by mass, more preferably 0.1% by mass to 30% by mass.

The graft polymer is also preferably a hydrophobic repeating unit in addition to the repeating unit represented by the above formulas (1) to (4). The hydrophobic repeating unit is preferably a repeating unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, more preferably 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 a value of "calculated logP" calculated by Hansch and Leo's fragment approach (see the following documents). The fragmentation method divides the chemical structure into partial structures (fragments) according to the chemical structure of the compound, and adds the logP helper components to the fragments to estimate 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 Edited by CA Ramsden (Eds.), p. 295, Pergamon Press, 1990; C. Hansch & AJ Leo., Chemistry and Substituent Constants For Correlation Analysis in Chemistry and Biology., John Wiley &Sons.; AJ Leo., Calculation of Hydrophobic Constants for 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), which is a quantitative value indicating how the organic compound is distributed in the two-phase equilibrium of oil (usually 1-octanol) and water. The following expression is expressed. logP = log (Coil / Cwater) wherein Coil represents the molar concentration of the compound in the oil phase and Cwater represents the molar concentration of the compound in the aqueous phase. If the value of logP increases by a positive value of 0, it means that the oil solubility increases. If it is negative and the absolute value increases, it means that the water solubility increases, and it has a negative correlation with the water solubility of the organic compound, and is widely used. As a parameter for estimating the hydrophilicity of an organic compound.

The graft copolymer preferably contains one or more repeating units selected from the repeating units derived from the monomers represented by the following formulas (i) to (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 (e.g., fluorine, chlorine, bromine, etc.) or an alkane having 1 to 6 carbon atoms. Base (eg methyl, ethyl, propyl, etc.). R ¹ , R ² and R ^{3 are more} preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and most preferably a hydrogen atom or a methyl group. R ² and R ^{3 are} particularly preferably a hydrogen atom.

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

L is a single bond or a divalent linking group. The divalent linking group may be exemplified by a divalent aliphatic group (for example, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group), and a divalent group. An aromatic group (e.g., an extended aryl group, a substituted aryl group), a divalent heterocyclic group, an oxygen atom (-O-), a sulfur atom (-S-), an imido group (-NH-), substituted An imido 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 such groups, and the like. L is preferably a single bond, an alkylene group or a divalent linking group having an oxygen-extended alkyl structure. The oxygen-extended alkyl structure is more preferably an oxygen-extended ethyl structure or an oxygen-extended propyl structure. Further, L may also contain a polyoxyalkylene structure having a repeating structure comprising two or more oxygen-extended alkyl groups. The polyoxyalkylene structure is preferably a polyoxyalkylene structure or a polyoxyalkylene structure. The polyoxyalkylene structure is represented by -(OCH ₂ CH ₂ ) _n -, and n is preferably an integer of 2 or more, more preferably an integer of 2 to 10.

Z may, for example, be an aliphatic group (for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, a substituted unsaturated alkyl group), an aromatic group (for example, an aryl group, a substituted aryl group), or a heterocyclic group. , an oxygen atom (-O-), a sulfur atom (-S-), an imido group (-NH-), a 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 such groups, and the like.

The aliphatic group may also have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably from 1 to 20, more preferably from 1 to 15, and still more preferably from 1 to 10. The aliphatic group further includes a cyclic hydrocarbon group, a crosslinked cyclic hydrocarbon group, and examples of the cyclic hydrocarbon group include a dicyclohexyl group, a perhydronaphthyl group, a biphenyl group, a 4-cyclohexylphenyl group and the like. Examples of the crosslinked cyclic hydrocarbon ring include decane, borneane, norbornane, norbornane, and bicyclooctane ring (bicyclo[2.2.2]octane ring, bicyclo[3.2.1]octane ring, etc.). Equivalent bicyclic hydrocarbon ring, tricyclo[5.2.1.0 ^3,8 ]homobledane, adamantane, tricyclo[5.2.1.0 ^2,6 ]decane, tricyclo[4.3.1.1 ^2,5 ] a tricyclic hydrocarbon ring such as a monoalkyl ring, a tetracyclic ring such as tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ]dodecane, and a perhydro-1,4-methyl bridge-5,8-methylnaphthyl ring Hydrocarbon ring and the like. In addition, the cross-linked cyclic hydrocarbon ring also includes a condensed cyclic hydrocarbon ring, such as a perhydronaphthalene (decalin) ring, a perhydrohydroquinone ring, a perhydrophenanthrene ring, a perhydroacenaphthene ring, and a total A condensed ring obtained by condensing a plurality of 5- to 8-membered cycloalkane rings, such as a hydroquinone ring, a perhydroindole ring, or a perhydroindole ring. Regarding the aliphatic group, the saturated aliphatic group is superior to the unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. Here, the aliphatic group represented by Z does not have an acid group as a substituent.

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

The heterocyclic group preferably has a 5-membered or 6-membered ring as a heterocyclic ring. Other heterocyclic rings, aliphatic rings or aromatic rings may also be condensed on the heterocyclic ring. Further, the heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, a pendant oxy group (=O), a pendant thio group (=S), an imido group (=NH), a substituted imido 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. Here, 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 (e.g., fluorine, chlorine, bromine, etc.) or an alkyl group having 1 to 6 carbon atoms (e.g., methyl group). , ethyl, propyl, etc.), Z or -LZ. Here, L and Z have the same meanings 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 the representative compound represented by the formula (i) to the formula (iii) include a radically polymerizable compound selected from the group consisting of acrylates, methacrylates, and styrenes. In addition, examples of the compound represented by the formula (i) to the formula (iii) can be referred to the compounds described in Paragraph No. 0089 to Paragraph No. 0093 of JP-A-2013-249417, and the contents are incorporated herein. In the manual.

Specific examples of the graft copolymer include the following copolymers. Further, the resin described in Paragraph No. 0072 to Paragraph No. 0094 of JP-A-2012-255128 can be used.

A dispersing agent (resin) can also be obtained as a commercial item, and such a specific example is "Disperbyk-101 (polyamide-amine phosphate) manufactured by BYK Chemie Co., Ltd." , Disperbyk-107 (carboxylate), Disperbyk-110, Disperbyk-111 (acid-containing copolymer), Dispa Disperbyk-130 (polyamide), Disperbyk-161, Disperbyk-162, Disperbyk-163, Despap Disperbyk-164, Disperbyk-165, Disperbyk-166, Disperbyk-170 (polymer copolymer), BYK (BYK)-P104, BYK-P105 (high molecular weight unsaturated polycarboxylic acid); Efka (EFKA) 4047 and EFKA 4050 manufactured by EFKA EFKA 4165 (polyurethane), EFKA 4330 to Efka (EFKA) 4340 (block copolymer), EFKA 4400~ EFKA 4402 (modified polyacrylate), Efka (EFKA) 5010 (polyester decylamine), Efka (EFKA) 5765 (high molecular weight polycarboxylate), Efka (EFKA) 6220 (fatty acid polyester), EFKA 6745 (phthalocyanine derivative), EFKA 6750 (azo pigment derivative); Ajinomoto Fine-techno "Ajisper PB821, Ajisper PB822, Ajisper PB880, Ajisper PB881"; Floran Chemical Co., Ltd. (Flowlen) TG-710 (urethane oligomer), "Polyflow No. 50E, Polyflow No. 300 (acrylic copolymer)"; The company's "Disparlon" KS-860, Disparlon 873SN, Disparlon 874, Disparlon #2150 (aliphatic polycarboxylic acid), Disparlon #7004 (polyether ester), Disparlon DA-703-50, Tees Disparlon DA-705, Disparlon DA-725"; Demol RN, Demol N (naphthalene sulfonic acid formaldehyde polycondensate) manufactured by Kao Corporation, Germany Demol MS, Demol C, Demol SN-B (aromatic sulfonic acid formaldehyde polycondensate), "Homogenol L-18" Carboxylic acid), "Emulgen 920, Emulgen 930, Emulgen 935, Emulgen 985 (polyoxyethylene nonylphenyl ether)", "Acitretin" (Acetamin) 86 (stearylamine acetate)"; Solsperse 5000 (phthalocyanine derivative) manufactured by Librizol Japan Co., Ltd., Solsperse 22000 (azo pigment derivative), Solsperse 13240 (polyesteramine), Solsperse 3000, Solsperse 17000, Solsperse 27000 (Polymer with functional part at the end), Solsperse 24000, Solsperse 28 000, Solsperse 32000, Solsperse 38500 (grafted polymer); Nikol T106 (polyoxyethylene sorbent) manufactured by Nikko Chemicals "Alcoholic anhydride monooleate", Nikol MYS-IEX (polyoxyethylene monostearate); "Hinoact" manufactured by Kawaken Fine Chemical Co., Ltd. ) T-8000E"; EFKA-46, EFKA Efka-47, EFKA-47EA, EFKA Polymer manufactured by Morishita Industries Co., Ltd. 100) EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450"; manufactured by Sannopco Co., Ltd. Disperse-aid 6, Disperse-aid 8, Disperse-aid 15, Disperse-aid 9100"; Adeka Pluronic L31, Eddie Pronknik (made by ADEKA) Adeka Pluronic) F38, Adeka Pluronic L42, Adeka Pluronic L44, Adeka Pluronic L61, Adeka Pluronic L64, Ai Adeka Pluronic F68, Adeka Pluronic L72, Adeka Pluronic P95, Adeka Pluronic F77, Adeka Proknik (Adeka) Pluronic) P84, Adeka Pluronic F87, Adeka Pluronic P94, Adeka Pluronic L101, Adeka Pluronic P103, Eddie Adeka Pluronic F108, Adeka Pluronic L121, Adeka Pluronic P-123"; and Sanyo Kasei Co., Ltd. "Ionet" S-20" and so on.

These resins may be used singly or in combination of two or more. In addition, the following may be used as the resin: (meth)acrylic copolymer, itaconic acid copolymer, butenoic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and in the side chain An acid group-containing resin such as an acid cellulose derivative having a carboxylic acid or a resin obtained by adding an acid anhydride to a polymer having a hydroxyl group. In addition, the N-substituted maleimide monomer copolymer described in Japanese Laid-Open Patent Publication No. Hei 10-300922, and the ether dimer copolymer described in JP-A-2004-300204 may be preferably used. Used as a resin.

Further, in the present invention, the resin may be used in a polymer having a carboxyl group in a side chain. These polymers can be used as a dispersant or as a binder. The polymer having a carboxyl group in the side chain may, for example, be a methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, a butenoic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, or a phenolic acid. An alkali-soluble phenol resin such as a varnish-type resin, or an acid cellulose derivative having a carboxyl group in a side chain, and a polymer obtained by adding an acid anhydride to a polymer having a hydroxyl group. It is especially preferred to copolymerize (meth)acrylic acid with other monomers copolymerizable therewith. Other monomers which can be copolymerized with (meth)acrylic acid include alkyl (meth)acrylate, aryl (meth)acrylate, vinyl compounds and the like. Examples of the alkyl (meth)acrylate and the aryl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. Ester, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate , (methyl) methacrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, etc., examples of the vinyl compound: styrene, α-methyl styrene, vinyl toluene, methacrylic acid Glycidyl ester, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like. Further, the other monomer may be a N-substituted maleimide monomer described in Japanese Patent Laid-Open Publication No. Hei 10-300922 (for example, N-phenylmaleimide, N-cyclohexylmaleimide). Wait). Further, these other monomers copolymerizable with (meth)acrylic acid may be used alone or in combination of two or more.

Further, in the present invention, a benzyl (meth) acrylate / (meth) acrylate copolymer, benzyl (meth) acrylate / (meth) acrylate / (meth) acrylate - 2 can be preferably used as the resin. A hydroxyethyl ester copolymer, a multicomponent copolymer comprising benzyl (meth)acrylate/(meth)acrylic acid/other monomer. Further, it is also preferred to use a copolymer of 2-hydroxyethyl (meth)acrylate, which is a 2-hydroxypropyl (meth)acrylate described in JP-A-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 macromonomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene giant Body / benzyl methacrylate / methacrylic acid copolymer.

The resin preferably further contains a polymer (a) which is a compound represented by the following formula (ED1) and/or a formula (1) of JP-A-2010-168539. The monomer component of the compound (hereinafter, these compounds are also referred to as "ether dimer") is polymerized.

In the formula (ED), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. In the formula (ED1), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited, and examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group and a positive group. a straight or branched alkyl group such as a butyl group, an isobutyl group, a tert-butyl group, a third pentyl group, a stearyl group, a lauryl group or a 2-ethylhexyl group; an aryl group such as a phenyl group; a cyclohexyl group and a third group An alicyclic group such as cyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl or 2-methyl-2-adamantyl; 1-methoxyethyl, 1- An alkyl group substituted with an alkoxy group such as an ethoxy group; an alkyl group substituted with an aryl group such as a benzyl group; and the like. Among these groups, in particular, in terms of heat resistance, a substituent of a primary or secondary carbon which is not easily removed by acid or heat such as a methyl group, an ethyl group, a cyclohexyl group or a benzyl group is preferable.

Specific examples of the ether dimer can be referred to in the specification, for example, by referring to Paragraph No. 0317 of JP-A-2013-29760. The ether dimer may be used alone or in combination of two or more.

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

In the formula (X), the alkyl group of R ₂ preferably has 2 to 3 carbon atoms. Further, 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. The benzene ring-containing alkyl group represented by R ₃ may, for example, be a benzyl group or a 2-phenyl(iso)propyl group.

The resin can be referred to the description of Paragraph No. 0558 to Paragraph No. 0571 of the Japanese Patent Application Laid-Open No. 2012-208494 (paragraph No. 0685 to Paragraph No. 0700 of the specification of the corresponding US Patent Application Publication No. 2012/0235099). Enter this manual. Further, the copolymer (B) described in Paragraph No. 0029 to Paragraph No. 0063 of JP-A-2012-32767, and the alkali-soluble resin used in the examples, and JP-A-2012-208474 can be used. The adhesive resin described in Paragraph No. 0088 to Paragraph No. 0098 and the adhesive resin used in the examples, and the adhesive resin described in Paragraph No. 0022 to Paragraph No. 0032 of JP-A-2012-137531, and Examples The adhesive resin to be used, and the adhesive resin described in Paragraph No. 0132 to Paragraph No. 0143 of JP-A-2013-024934, and the adhesive resin used in the examples, and the paragraph of JP-A-2011-242752 The binder resin described in the following paragraphs 0092 to 0098 and the binder resin used in the examples, and the paragraph number 0030 to paragraph 0072 of JP-A-2012-032770. This content is incorporated into this specification.

In the present invention, a resin having a polymerizable group can also be used as the resin. The content of the resin having a polymerizable group is preferably from 1% by mass to 80% by mass based on the total solid content of the coloring composition, and the lower limit is preferably 3% 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.

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

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

The alkyl group represented by R ¹ is preferably an alkyl group having 1 to 3 carbon atoms, 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 and an extended aryl group having 6 to 12 carbon atoms, and the groups are selected from -CO-, -OCO-, -O-, -NH- And a combination of one of -SO ₂ -. The alkylene group and the extended aryl group may have a substituent or may be unsubstituted. The substituent may, for example, be a halogen atom, an alkyl group, an aryl group, a hydroxyl group, a carboxyl group, an alkoxy group or an aryloxy group. 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, a (meth)allyl group or a (meth)acrylonyl group.

The resin having a polymerizable group preferably has a content of a repeating unit having a radical polymerizable group in a side chain of from 5 to 100% by mass based on the total of all repeating units. The lower limit is more preferably 10% by mass or more, and still more preferably 15% by mass or more. The upper limit is more preferably 95% by mass or less, and 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 a functional group such as an acid group. It may also contain no functional groups.

The acid group may, for example, be a carboxyl group, a sulfonic acid group or a phosphoric acid group. The acid group may be contained alone or in combination of two or more. The proportion of the repeating unit having an acid group is preferably from 0% by mass to 50% by mass based on all the repeating units constituting the resin. The lower limit is more preferably 1% by mass or more, and still more preferably 3% by mass or more. The upper limit is more preferably 35% by mass or less, and further preferably 30% by mass or less.

Examples of other functional groups include development promoting groups such as lactones, acid anhydrides, decylamines, and cyano groups, long-chain alkyl groups and cyclic alkyl groups, aralkyl groups, aryl groups, polyalkylene oxide groups, hydroxyl groups, and Malayanya. An amine group, an amine group or the like can be appropriately introduced. Further, a repeating unit derived from the ether dimer or a repeating unit derived from a compound represented by the formula (X) described in the resin may be contained.

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

A commercially available product of a polymerizable resin can be exemplified by Dainal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (polyacetic acid urethane oligomer containing COOH) Polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co., Ltd., Biscoat R-264, KS Resist 106 (both Osaka Organic) Chemical Industry Co., Ltd.), Cyclomer P series (such as ACA230AA), Placcel CF200 series (all manufactured by Daicel), Ebecryl 3800 (produced by UCB (Daicel UCB) Co., Ltd.), Acrycure RD-F8 (manufactured by Nippon Shokubai Co., Ltd.), etc.

<<Polymerizable Compound>> The colored composition of the present invention contains a polymerizable compound. As the polymerizable compound, a known compound which can be crosslinked by a radical can be used. For example, a compound (radical polymerizable compound) having a radical polymerizable group such as a group containing an ethylenically unsaturated bond can be mentioned. The group containing an ethylenically unsaturated bond may, for example, be a vinyl group, a (meth)allyl group or a (meth)acrylonyl group, and is preferably a (meth)allyl group or a (meth)acryloyl group.

In the present invention, the polymerizable compound may be, for example, any of the following chemical forms: a monomer, a prepolymer, that is, a dimer, a trimer, and an oligomer, or a mixture thereof, and a polymer thereof. . It is preferably a monomer. The monomeric polymerizable compound (polymerizable monomer) preferably has a molecular weight of from 100 to 3,000. The upper limit is preferably 2,000 or less, and more preferably 1,500 or less. The lower limit is preferably 150 or more, and more preferably 250 or more.

The content of the polymerizable compound is preferably from 1% by mass to 80% by mass based on 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, more preferably 60% by mass or less. The content of the polymerizable monomer is preferably from 1% by mass to 80% by mass based on 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 the case where the polymerizable monomer and the resin having a polymerizable group are used in combination, the quality of both is preferably a polymerizable monomer: a resin having a polymerizable group = 1:1 to 20, more preferably 1: 1 to 15, and then preferably 1:5 to 15. The colored composition of the present invention may contain only one kind of polymerizable compound, and may contain two or more types. When two or more cases are contained, it is preferable that the total amount is the said range.

(Polymerizable monomer) In the present invention, the polymerizable monomer is preferably a compound having three or more radical polymerizable groups, and more preferably a compound having three to fifteen or more radical polymerizable groups. Further, a compound having three to six or more radical polymerizable groups is preferred. For the specific compounds, the paragraph number [0095] to the paragraph number [0108] of the Japanese Patent Laid-Open Publication No. 2009-288705, the paragraph number 0227 of Japanese Patent Laid-Open Publication No. 2013-29760, and the Japanese Patent Laid-Open No. 2008-292970 The compound described in Paragraph No. 0254 to Paragraph No. 0257 of the Japanese Patent Publication is incorporated herein by reference.

The polymerizable monomer is preferably a compound having an alkoxy group, and further preferably a compound having a chain (alkylalkoxy chain) having two or more alkyleneoxy groups as a repeating unit. The number of repeating units of the alkoxy group is preferably from 2 to 30, more preferably from 2 to 20, still more preferably from 2 to 10. The carbon number of the alkoxy group is preferably 2 or more, more preferably 2 to 10, still more preferably 2 to 4, and still more preferably 2. That is, it is especially preferred to extend the ethoxy group. 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, still more preferably 2 to 4, and still more preferably 2. b is preferably 2 to 30, more preferably 2 to 20, and still more preferably 2 to 10.

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

In the formula (Z-4) and formula (Z-5), E each independently represent _{- ((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 each independently represents an acryloyl group, a methacryl fluorenyl group, a hydrogen atom or a carboxyl group. In the formula (Z-4), the total of the acrylonitrile group and the methacryl group is three or four, and m each independently represents an integer of 0 to 10, and at least one of m represents an integer of 1 to 10, and each m The total is an integer of 1 to 40. In the formula (Z-5), the total of the acrylonitrile group and the methacryl group is five or six, and n each independently represents an integer of 0 to 10, and at least one of n represents an integer of 1 to 10, and each n The total is an integer from 1 to 60.

In the formula (Z-4), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Further, the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8. In the formula (Z-5), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Further, the total of each n is preferably an integer of from 3 to 60, more preferably an integer of from 3 to 24, still more preferably an integer of from 6 to 12. Further, -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)- in the formula (Z-4) or the formula (Z-5) is preferably an oxygen atom. The end of the side is bonded to the form of X.

The compound represented by the formula (Z-4) or the formula (Z-5) may be used alone or in combination of two or more. More preferably, in the formula (Z-5), all of the six Xs are in the form of an acrylonitrile group.

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

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

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

A commercially available product of a polymerizable compound having an alkoxy group is, for example, SR-494, which is a tetrafunctional acrylate having four ethylene oxide groups, manufactured by Sartomer Co., Ltd., Nippon Kayaku Co., Ltd. DPCA-60 as a hexafunctional acrylate having six pentyloxy groups, TPA-330 as a trifunctional acrylate having three isobutoxy groups, and the like were produced.

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

The polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. Commercially available products include M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd., for example.

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

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

The polymerizable compound is also preferably described in JP-A-48-41708, JP-A-53-37193, JP-A-2-332293, and JP-A-2-16765. The urethane amides are described in Japanese Patent Publication No. Sho 58-49860, Japanese Patent Publication No. SHO 56-17654, Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. SHO 62-39418. A urethane compound having an ethylene oxide skeleton. In addition, an amine group structure or a thioether structure is contained in the molecule as described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The addition polymerizable compound can obtain a coloring composition which is excellent in the photospeed. Commercially available products include: urethane oligomer UAS-10, urethane oligomer UAB-140 (manufactured by Shanyang Guoce Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) , DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.).

<<Photopolymerization Starter>> 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 preferred to be sensitive to light in the ultraviolet range to the visible range. In the case where a radically polymerizable compound is used as the polymerizable compound, the photopolymerization initiator is preferably a photoradical polymerization initiator. Further, the photopolymerization initiator is preferably a compound having at least one molar absorption coefficient of at least about 50 in the range of from about 300 nm to 800 nm, more preferably from 330 nm to 500 nm.

Examples of the photopolymerization initiator include a halogenated hydrocarbon derivative (for example, a triazine skeleton or a oxadiazole skeleton), a mercaptophosphine compound such as a mercaptophosphine oxide, a hexaarylbiimidazole, an anthracene derivative, or the like. An anthracene compound, an organic peroxide, a sulfur compound, a ketone compound, an aromatic onium salt, a ketoxime ether, an aminoacetophenone compound, a hydroxyacetophenone or the like. Examples of the halogenated hydrocarbon compound having a triazine skeleton include a compound described in "Bull. Chem. Soc. Japan" (42, 2924 (1969)), and a description of the British Patent No. 1,388,492. The compound described in Japanese Laid-Open Patent Publication No. SHO 53-133428, the compound described in the specification of German Patent No. 3337024, and the "J. Org. Chem." by FC Schaefer et al. A compound described in Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The compound described in the publication, the compound described in the specification of U.S. Patent No. 4,212,976, and the like.

Further, from the viewpoint of exposure sensitivity, a compound selected from the group consisting of a trihalogenated methyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, and α is preferable. An aminoketone compound, a mercaptophosphine compound, a phosphine oxide compound, a metallocene compound, an anthraquinone compound, a triallyl imidazole dimer, an anthraquinone compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, and Its derivatives, cyclopentadiene-benzene-iron complexes and salts thereof, halogenated methyl oxadiazole compounds, 3-aryl substituted coumarin compounds.

The photopolymerization initiator is a trihalogenated methyltriazine compound, an α-aminoketone compound, a mercaptophosphine compound, a phosphine oxide compound, an anthraquinone compound, a triallyl imidazole dimer, an anthracene compound, a benzophenone compound. The acetophenone compound is preferably selected from the group consisting of a trihalogenated methyltriazine compound, an α-aminoketone compound, an anthraquinone compound, a triallyl imidazole dimer, and a benzophenone compound. At least one compound. Specific examples of the photopolymerization initiator can be referred to in the specification, for example, in Paragraph No. 0265 to Paragraph No. 0268 of JP-A-2013-29760.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a mercaptophosphine compound can also be preferably used. More specifically, for example, an amino acetophenone-based initiator as described in JP-A-10-291969, and a mercaptophosphine-based initiator described in Japanese Patent No. 4,258,899 can be used. The hydroxyacetophenone-based initiator can be used: IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, Yanjiagu (IRGACURE)-127 (trade name: all manufactured by BASF). Amino acetophenone-based initiators can be used as commercially available products such as IRGACURE-907, IRGACURE-369 and IRGACURE-379EG (trade names: all are BASF) BASF) company). The amine acetophenone-based initiator may also be a compound described in JP-A-2009-191179, which has a maximum absorption wavelength and a wave source of 365 nm or 405 nm. As the mercaptophosphine-based initiator, IRGACURE-819 or DAROCUR-TPO (trade name: all manufactured by BASF) can be used as a commercial product.

The photopolymerization initiator may more preferably be a ruthenium compound. For the specific example of the ruthenium compound, the compound described in JP-A-2001-233842, the compound described in JP-A-2000-80068, and the compound described in JP-A-2006-342166 can be used. In the present invention, examples of the ruthenium compound which can be preferably used are, for example, 3-benzylideneoxyimidobutan-2-one, 3-ethyloxyiminobutan-2-one, and 3 - propionyloxyiminobutan-2-one, 2-ethoxymethoxyiminopentan-3-one, 2-ethyloxyimino-1-phenylpropan-1-one , 2-benzylideneoxyimido-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyl Oxyimido-1-phenylpropan-1-one and the like. Also available: "The British Chemical Society, JCS Perkin II" (1979) pp. 1653-1660, "British Chemical Society, JC Perkin II" (1979) pp. 156-162, "Journal of Photopolymer Science and Technology" (1995, pp. 202-232), Japanese Patent Laid-Open No. 2000-66385, A compound or the like described in each of the publications of JP-A-2000-80068, JP-A-2004-534797, and JP-A-2006-342166. Among the commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) can also be preferably used. In addition, TR-PBG-304 (made by Changzhou Power Electronic New Materials Co., Ltd.), Adeka Arkls NCI-831, and Adeka Arkls NCI-930 can also be used. (Manufactured by ADEKA).

In addition, a compound described in Japanese Patent Laid-Open Publication No. 2009-519904, which is attached to the N-position of the carbazole ring, and a hetero substituent introduced to the benzophenone moiety may be used. The compound described in the U.S. Patent No. 7,626,957, the Japanese Patent Publication No. 2010-15025, the nitro group, and the compound disclosed in U.S. Patent Publication No. 2009-292039, the International Publication No. WO 2009/131189 The ketone oxime compound described in Japanese Patent No. 7556910, which contains a triazine skeleton and an anthracene skeleton in the same molecule, has a maximum absorption at 405 nm and has a good sensitivity to a g-ray source. The compound described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. For example, it is preferable to refer to paragraph No. 0274 to Paragraph No. 0275 of Japanese Patent Laid-Open No. 2013-29760, the contents of which are incorporated herein. Specifically, the ruthenium compound is preferably a compound represented by the following formula (OX-1). Further, the ruthenium compound in which the N-O bond of ruthenium is (E), the ruthenium compound of the (Z) form, or a mixture of the (E) form and the (Z) form may be used.

In the 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-metal atomic group. The monovalent non-metal atomic group may, for example, be an alkyl group, an aryl group, a decyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group or an arylthiocarbonyl group. In addition, the groups may have more than one substituent. Further, the substituents described above may be further substituted with other substituents. The substituent may, for example, be a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, a decyloxy group, a decyl group, an alkyl group or an aryl group. In the formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group. These groups may also have more than one substituent. The substituents described above can be exemplified as the substituents described above. In the formula (OX-1), the divalent organic group represented by A is preferably an alkylene group having a carbon number of 1 to 12, a cycloalkyl group or an alkynylene group. These groups may also have more than one substituent. The substituents described above can be exemplified as the substituents described above.

The ruthenium compound preferably has a maximum absorption wavelength in a wavelength range of 350 nm to 500 nm, more preferably has an absorption wavelength in a wavelength range of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 405 nm. By. With respect to the cerium compound, the molar absorption coefficient at 365 nm or 405 nm is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, still more preferably from 5,000 to 200,000, from the viewpoint of sensitivity. The molar absorption coefficient of the compound can be determined by a known method. For example, it is preferred to use an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Co., Ltd.) using an ethyl acetate solvent at a concentration of 0.01 g/L. Determination.

Specific examples of the ruthenium compound which 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 a ruthenium compound having a fluorine atom as a photopolymerization initiator. Specific examples of the ruthenium compound having a fluorine atom include the compound described in JP-A-2010-262028, and the compound 24 and the compound 36 to the compound 40 described in JP-A-2014-500852. The compound (C-3) and the like described in Japanese Laid-Open Patent Publication No. 2013-164471. This content is incorporated into the present specification.

The content of the photopolymerization initiator is preferably from 0.1% by mass to 50% by mass, more preferably from 0.5% by mass to 30% by mass, even more preferably from 1% by mass to 20% by mass, based on the total solid content of the coloring composition. Within this range, better sensitivity and pattern formation can be obtained. The coloring composition may contain only one kind of photopolymerization initiator, and may contain two or more types. When two or more cases are contained, it is preferable that the total amount is the said range.

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

Examples of the organic pigment constituting the pigment derivative include a diketopyrrolopyrrole pigment, an azo pigment, a phthalocyanine pigment, an anthraquinone pigment, a quinacridone pigment, a dioxazine pigment, and a violet pigment. Perinone pigment, anthraquinone pigment, thioindigo pigment, isoporphyrin pigment, isoindolinone pigment, quinophthalone pigment, threne pigment, metal complex Pigments, etc. Further, the acid group of the pigment derivative is preferably a sulfonic acid group, a carboxylic acid group or a salt thereof, and further preferably a carboxylic acid group and a sulfonic acid group, and particularly preferably a sulfonic acid group. The basic group which the pigment derivative has is preferably an amine group, and more preferably a tertiary amine group.

The pigment derivative is preferably a quinoline-based, benzimidazolone-based or isoporphyrin-based pigment derivative, and further preferably a quinoline-based or benzimidazolone-based pigment derivative. Further, the pigment derivative is preferably a pigment derivative having the following structure.

In the formula (PZ), A represents a structure selected from the following formula (PA-1) to formula (PA-3), B represents a single bond or a (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, an alkylene group or an extended aryl group, and E represents -SO ₃ H or a salt thereof -CO ₂ H or a salt thereof, or -N(Rpa)(Rpb), Rpa and Rpb each independently represent an alkyl group or an aryl group, and Rpa and Rpb may be bonded to each other to form a ring, and t represents an integer of 1 to 5 ;

Rp ₁ represents an alkyl group or an aryl group having 1 to 5 carbon atoms, Rp ₂ represents a halogen atom, an alkyl group or a hydroxyl group, and 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 or different, and * represents a connection portion with B.

Rp _{1 is} preferably a methyl group or a phenyl group, more preferably a methyl group. 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 may, for example, be an alkylene group, an extended aryl group or a heteroaryl group. The alkyl group may be a straight chain, a branch or a ring. The (t+1)-valent linking group is 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 formula (PA-4) to the formula (PA-9), the linking group represented by the structural formula (PA-5) or the structural formula (PA-8) is particularly excellent in dispersibility as a pigment derivative of B. Preferably.

In the formula (PZ), the alkylene group and the extended aryl group represented by D may, for example, be a methylene group, an exoethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a hydrazine group, or a hydrazine ring. A propyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexylene group, a cyclooctyl group, a fluorenyl group, a phenyl group, a naphthyl group, and the like. Among these groups, D is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 5 carbon atoms.

In the formula (PZ), when E represents -N(Rpa)(Rpb), examples of the alkyl group and the aryl group of Rpa and Rpb include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Second butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, octyl, decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclopentane Base, phenyl, naphthyl and the like. Rpa and Rpb are particularly preferably a linear or branched alkyl group, and most preferably a linear or branched alkyl group 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 atom or atomic group forming the salt is preferably an alkali metal such as a lithium atom, a sodium atom or a potassium atom, ammonium or tetra. Alkyl ammonium and the like. The t is preferably 1 or 2.

Specific examples of the pigment derivative include the following compounds.

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

<<Solvent>> The coloring composition of the present invention may contain a solvent. The solvent can be exemplified by an organic solvent. The solvent is not particularly limited as long as it satisfies the solubility of each component or the coating property of the composition, and is preferably selected in consideration of coatability and safety of the composition.

Examples of the organic solvent include the following solvents. Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl acetate, isoamyl acetate, isobutyl acetate, butyl propionate, and isopropyl butyrate. Ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl alkoxyacetate (eg methyl alkoxyacetate, ethyl alkoxylate, butyl alkoxy acetate (eg A Methyl oxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-alkoxypropionate (for example) Methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Ester, ethyl 3-ethoxypropionate, etc.), 2-alkoxypropionic acid alkyl esters (eg methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, 2- Propyl alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, Ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropanoate and 2-alkoxy-2- Ethyl propyl propionate (eg methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, acetone Acid propyl ester, ethyl acetate methyl acetate, ethyl acetate ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like. Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, and diethylene glycol. 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, and the like. Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone. Examples of the aromatic hydrocarbons include toluene and xylene.

The organic solvent may be used alone or in combination of two or more. In the case where two or more organic solvents are used in combination, it is particularly preferred to contain methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate selected from the group consisting of Ester, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbene 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 of 0.8 mmol/L or less, more preferably substantially no peroxide.

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

<<Polymerization inhibitor>> The coloring composition of the present invention may contain a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the curable compound during or during storage of the colored composition. The polymerization inhibitor may, for example, be 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 sulfonium salts and the like. Among them, p-methoxyphenol is preferred. The content of the polymerization inhibitor is preferably from 0.01% by mass to 5% by mass based on the total solid content of the colored composition.

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

By containing the fluorine-based surfactant in the composition, the liquid properties (especially fluidity) at the time of preparing the coating liquid are further improved, and the uniformity of the coating thickness or the liquid-saving property can be further improved. In other words, when the film formation is carried out using a coating liquid to which a composition containing a fluorine-based surfactant is applied, the interfacial tension between the applied surface and the coating liquid is lowered, and the wettability of the surface to be coated is improved. The coating property to the coated surface is improved. Therefore, it is possible to more preferably form a film having a uniform thickness with a small thickness unevenness.

The fluorine content in the fluorine-based surfactant is preferably from 3% by mass to 40% by mass, more preferably from 5% by mass to 30% by mass, even more preferably from 7% by mass to 25% by mass. The fluorine-containing surfactant is effective in the uniformity of the thickness of the coating film or the liquid-saving property in the fluorine-based surfactant in this range, and the solubility in the composition is also good.

Examples of the fluorine-based surfactant include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, and Megafac F141. , Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac RS-72-K (above produced by Di Aisheng (DIC)), Flaorad ) FC430, Fluorad FC431, Fluorad FC171 (above Sumitomo 3M (share)), Surflon S-382, Surflon SC-101, sand Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Shafulong (Surflon) SC-383, Surflon S393, Sha Fulong (Su Rflon) KH-40 (above is manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA). As the fluorine-based surfactant, a block polymer can also be used. Specific examples thereof include a compound described in JP-A-2011-89090. The fluorine-based surfactant may preferably be a fluorine-containing polymer compound containing a repeating unit derived from a (meth) acrylate compound having a fluorine atom, and having two or more derived materials. The repeating unit of a (meth) acrylate compound which is preferably an alkoxy group (preferably an ethoxy group, a propenyloxy group), and the following compounds may also be used as the fluorine system used in the present invention. The surfactant is exemplified. The weight average molecular weight of the compound is preferably from 3,000 to 50,000, for example, 14,000. Further, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain may also be used as the fluorine-based surfactant. Specific examples include compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of Japanese Patent Laid-Open Publication No. 2010-164965, for example, Megafac RS-101 manufactured by DIC Corporation, Meijiafa (Megafac) RS-102, Megafac RS-718K, etc. Further, as the fluorine-based surfactant, the following compounds can also be used.

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

Specific examples of the cationic surfactant include a phthalocyanine derivative (trade name: EFKA-745, manufactured by Morishita Industries Co., Ltd.), an organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (methyl) Acrylic (co)polymer Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (Yu Shang (share) manufacturing) and so on.

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

Examples of the fluorenone-based surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (above Toray-Dow) Corning), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above is Momentive Performance Materials), KP341, KF6001, KF6002 (above) It is manufactured by Shintosu Silicon Co., Ltd., BYK 307, BYK 323, BYK 330 (above, BYK Chemie).

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

<<Other components>> The colored composition of the present invention may contain a thermal polymerization initiator such as an azo compound or a peroxide compound, a thermal polymerization component, an ultraviolet absorber such as an alkoxybenzophenone, or the like. Various additives such as a plasticizer such as dioctyl phthalate, a developability improver such as a low molecular weight organic carboxylic acid, another filler, an antioxidant, and an anti-agglomeration agent.

In the case where the metal element is contained in the composition due to the raw material to be used, the content of the second group element (calcium, magnesium, etc.) in the coloring composition is preferably 50 ppm from the viewpoint of suppressing the occurrence of defects. Hereinafter, it is preferably controlled within 0.01 ppm to 10 ppm. Further, the total amount of the inorganic metal salt in the colored composition is preferably 100 ppm or less, more preferably 0.5 ppm to 50 ppm.

<Method for Preparing Colored Composition> The colored composition of the present invention can be prepared by mixing the above-described components. In the preparation of the colored composition, the components may be blended together, or the components may be dissolved and dispersed in a solvent and then sequentially formulated. In addition, the order of input or the working conditions at the time of preparation are not particularly limited. For example, all the components may be simultaneously dissolved and dispersed in a solvent to prepare a composition, and if necessary, each component may be appropriately prepared into two or more kinds of solutions and dispersions, and these may be used at the time of application (at the time of coating). The solution and the dispersion are mixed to prepare a composition.

Further, it is preferred to prepare a pigment dispersion liquid by dispersing the red pigment together with other components such as a resin, an organic solvent, and a pigment derivative, and mixing the obtained pigment dispersion liquid with other components of the coloring composition.

In the production of the colored composition, it is preferred to filter by a filter in order to remove foreign matter, reduce defects, and the like. The filter is not particularly limited as long as it is used in a filter or the like. For example, a filter using the following materials: a fluororesin such as polytetrafluoroethylene (PTFE), a polyamine resin such as nylon (for example, nylon-6, nylon-6, 6), polyethylene or polypropylene (Polypropylene) can be used. , PP) and other polyolefin resins (including high density, ultra high molecular weight polyolefin resin) and the like. Among these raw materials, polypropylene (including high density polypropylene) and nylon are preferred. The pore diameter of the filter is suitably from about 0.01 μm to about 7.0 μm, preferably from about 0.01 μm to about 3.0 μm, and more preferably from about 0.05 μm to about 0.5 μm. By setting it as this range, the micro foreign material which obstructs the preparation of the uniform and smooth composition in the subsequent steps can be reliably removed. In addition, a fibrous filter medium is preferably used, and examples of the filter material include polypropylene fiber, nylon fiber, and glass fiber. Specifically, an SBP type series (SBP008 or the like) manufactured by Roki Techno Co., Ltd., and a TPR type can be used. Series (TPR002, TPR005, etc.), SHPX series (SHPX003, etc.) filter cartridge.

Different filters can also be combined when using filters. At this time, the filtration by the first filter may be performed only once, or may be performed twice or more. Further, the first filters having different pore diameters may be combined in the above range. The aperture here can be referred to the nominal value of the filter manufacturer. Commercially available filters are available, for example, from Pall Corporation of Japan (DFA4201NXEY, etc.), Advantec Toyo Co., Ltd., and Entegris Japan Co., Ltd. of Japan (original Among the various filters offered by Japan Microris Co., Ltd. or Kitz Micro Filter Co., Ltd., etc. As the second filter, a filter formed of the same material as the first filter or the like can be used. For example, the filtration by the first filter may be carried out only with a dispersion, and after mixing other components, the second filtration may be performed.

<Physical Properties of Colored Composition> The colored composition of the present invention is preferably a wavelength range of 600 nm to 700 nm when a film having a thickness of 3.0 μm formed using the coloring composition of the present invention is excited by light having a wavelength of 534 nm. The integrated intensity of the fluorescence is 0.5 or less, more preferably 0.5 or less, in addition to the integrated intensity of the fluorescence in the range of 600 nm to 700 nm when the cured film A having a thickness of 3.0 μm is excited by light having a wavelength of 534 nm. It is 0.3 or less, more preferably 0.2 or less, and particularly preferably 0.1 or less.

<Emission Filter> The transmission filter of the present invention is formed using the coloring composition of the present invention described above. The transmit filter of the present invention is preferably used as a transmit filter for a fluorescent sensor.

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

<Fluorescent 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 configuration in which an emission filter using the coloring composition of the present invention is used. The fluorescent sensor can be exemplified by irradiating the sample with excitation light. The sample is not particularly limited, and examples thereof include a sample which generates fluorescence by irradiation with excitation light. For example, a protein, a nucleic acid (DNA (deoxyribonucleic acid), ribonucleic acid (RNA), etc.), a cell, a microorganism, etc. are mentioned. 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 with reference to 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. The fluorescent sensor shown in FIG. 1 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 attachment portion 7. The transmit filter 6 comprises the colored composition of the present invention. The arrows in the figure indicate the traveling direction of light (excitation light, fluorescent light, etc.).

In the fluorescence sensor shown in FIG. 1, the light irradiated from the light source 1 is limited to light of an excitation wavelength by the excitation filter 2, and becomes excitation light. The light source 1 is not particularly limited. For example, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, a xenon lamp, an ultraviolet light emitting diode (ultraviolet LED), an excimer laser generating device, or the like can be used. The excitation filter 2 can be appropriately selected depending on the kind of the target excitation light. For example, when light having a wavelength of 534 nm is used as the excitation light, it is preferable to use a filter that transmits light having a wavelength of 534 nm and shields light of other wavelengths. The excitation light is reflected by the spectroscope 3, and is irradiated onto the sample 100 on the sample holder 5 through the objective lens 4. When the sample 100 is irradiated with the 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, light containing a fluorescent component is directly introduced into the transmission filter 6 in the beam splitter 3. In the transmission filter 6, only the wavelength of the target fluorescent light is transmitted through the straight light entering the dichroic mirror 3, and the wavelength of the target fluorescent light is introduced into the contact portion 7. The fluorescent light introduced into the eye portion can be observed by visual observation or a camera or the like. Since the fluorescence sensor of the present invention has low fluorescence for the excitation light, the effect of the fluorescence caused by the emission filter can be suppressed, and the detection sensitivity is excellent.

Another embodiment of the fluorescent sensor of the present invention will be described with reference to Fig. 2 . The fluorescent sensor shown in Fig. 2 is a transmissive fluorescent sensor. The fluorescent sensor shown in FIG. 2 has a light source 11, an excitation filter 12, a mirror 13, a sample holder 14, an objective lens 15, a transmission filter 16, and an eye portion 17. The transmit filter 16 comprises the colored composition of the present invention. In the fluorescence sensor shown in FIG. 2, the light irradiated from the light source 11 is limited to the excitation wavelength light by the excitation filter 12, thereby becoming excitation light. The excitation light is reflected by the mirror 13 and irradiated to 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 contact portion 17. The fluorescent light introduced into the eye portion can be observed by visual observation or a camera or the like.

<Manufacturing Method of Fluorescent Sensor> The method of manufacturing the fluorescent sensor of the present invention includes the step of forming a transmitting filter using the colored composition of the present invention. Specifically, it can also be produced by the step of forming a colored composition layer on the support using the colored composition of the present invention and the step of curing the colored composition layer. Further, the step of forming a pattern may be further performed. Hereinafter, each step will be described.

First, a colored composition layer is formed on a support using the colored composition of the present invention. The support is not particularly limited. A transparent substrate such as glass, tantalum wafer, or polymer resin (epoxy resin) may be mentioned. Various methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, and screen printing can be used for the application of the composition on the support.

The colored composition layer formed on the support may also be prebaked. In the case of prebaking, the prebaking temperature is preferably 150 ° C or less, more preferably 120 ° C or less, and still more preferably 110 ° C or less. The lower limit can be, for example, 50 ° C or higher, or 80 ° C or higher. The prebaking time is preferably from 10 seconds to 300 seconds, more preferably from 40 seconds to 250 seconds, and further preferably from 80 seconds to 220 seconds. Drying can be carried out using a hot plate, an oven or the like.

Then, the colored composition layer formed on the support is hardened and hardened. The hardening treatment is preferably an exposure treatment. Radiation (light) which can be used for exposure can preferably use ultraviolet rays such as g-rays and i-rays (i-rays can be preferably used). The irradiation amount (exposure amount) is, for example, preferably 0.03 J/cm ² to 2.5 J/cm ² , more preferably 0.05 J/cm ² to 1.0 J/cm ² , most preferably 0.08 J/cm ² to 0.5 J/cm. ² . The oxygen concentration at the time of exposure can be appropriately selected, and may be carried out in a low oxygen atmosphere (for example, 15% by volume, 5% by volume, or substantially oxygen-free) having an oxygen concentration of 19% by volume or less, in addition to being carried out in the atmosphere. Exposure may also be carried out in a high oxygen environment (e.g., 22% by volume, 30% by volume, 50% by volume) in which the oxygen concentration exceeds 21% by volume. Further, the exposure illuminance can be appropriately set, and can be usually selected from the range of 1000 W/m ² to 100000 W/m ² (for example, 5000 W/m ² , 15000 W/m ² , and 35000 W/m ² ). The oxygen concentration and the exposure illuminance may be appropriately combined, and may be, for example, an oxygen concentration of 10% by volume, an illuminance of 10,000 W/m ² , an oxygen concentration of 35 vol%, and an illuminance of 20,000 W/m ² .

After the exposure treatment, heat treatment (post-baking) may be further performed. Post-baking is a heat treatment after development for completely hardening the film. In the case of post-baking, the post-baking temperature is, for example, preferably from 100 ° C to 240 ° C. From the viewpoint of film hardening, it is more preferably from 200 ° C to 230 ° C. The post-baking can be carried out in a continuous or batch manner using a heating means such as a hot plate or a convection oven (hot air circulation dryer) or a high-frequency heating machine to form the film after development.

In the manner described, a transmit filter can be fabricated. A fluorescent sensor can be fabricated by incorporating the transmit filter obtained in the manner described above into a fluorescent sensor.

EXAMPLES Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited to the following examples as long as the scope of the invention is not exceeded. In addition, unless otherwise indicated, "part" and "%" are the quality standards. In addition, hereinafter, 1吋 is 2.54 cm.

(Method for Measuring Average Particle Diameter of Pigment) The average particle diameter of the pigment was measured by a dynamic light scattering method. Specifically, it was measured using a DLS-8000 series (manufactured by Otsuka Electronics Co., Ltd.).

(Use of raw materials) The components used in the coloring compositions of the examples and the comparative examples were the following components. - Red pigment PR144: CI Pigment Red 144 PR166: CI Pigment Red 166 PR254: CI Pigment Red 254 - Resin (Resin 1) D-1: The following structure (weight average molecular weight 38,000, together with each repeating unit (main chain) The numerical values indicated indicate the content (mass ratio) of each repeating unit. The numerical value described together with the overlapping portion of the side chain indicates the number of repeating portions. D-2: the following structure (weight average molecular weight: 20,000, and the numerical value shown by each repeating unit (main chain) shows the content (mass ratio) of each repeating unit. The numerical value shown with the repeating site of a side chain is repeated. Repeat number of parts) D-3: the following structure (weight average molecular weight 24000, the numerical value shown with each repeating unit (main chain) shows the content (mass ratio) of each repeating unit. The numerical value shown with the repeating site of a side chain is repeated. Repeat number of parts) (Resin 2) B-1: The following structure (weight average molecular weight: 11,000, and the numerical value together with each repeating unit (main chain) shows the content (mass ratio) of each repeating unit) B-2: the following structure (weight average molecular weight 12000, the numerical value together with each repeating unit (main chain) shows the content (mass ratio) of each repeating unit) B-3: the following structure (weight average molecular weight: 40000, and the numerical value together with each repeating unit (main chain) shows the content (mass ratio) of each repeating unit) ·Pigment derivative PZ-1: the following structure Polymerizable Compounds M-1 to M-3: The following structures. Further, M-2 is a mixture of a compound of the left form and a compound of the right formula in a mass ratio of 7:3. n of M-3 is 1 to 3, and the total of four n is 12 or less. M-4: NK Ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) · Photopolymerization initiator I-1 to I-2: the following structure · Surfactant W-1: the following mixture (Mw=14000, 10% PGMEA solution) W-2: The following structure

(Preparation of Colored Composition) Evaluation was carried out using the coloring composition of the components shown in Table 1. (composition ratio) Pigment: 5 mass% Resin (resin 1): 1.5% by mass Pigment derivative: 0.075 mass% Polymerization initiator: 0.3 mass% Polymerizable compound: 0.7 mass% Resin (resin 2): 4.925 mass% interface Active agent: 0.001% by mass Solvent Glycol Monomethyl Ether Acetate (PGMEA): Remaining part

In the colored composition, a pigment, a resin 1 and a pigment derivative are mixed to prepare a pigment dispersion, and the remaining components are blended in the pigment dispersion to produce a colored composition of the composition.

[Table 1]

(Measurement of Fluorescence Intensity) Each colored composition was applied onto a glass substrate to form a colored composition layer. The film thickness was adjusted such that the transmittance of the cured film at a wavelength of 500 nm was 5%. Then, after prebaking at 100 ° C for 2 minutes, exposure was carried out under conditions of 1000 mJ/cm ² , and baking was carried out 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 at 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. Next, the integrated intensity of the fluorescence in the range of 600 nm to 700 nm was measured. Further, in order to suppress the disordered light, a 530 nm band pass filter was used for the light source side, and a sharp wave filter was used for the detection side to suppress the scattered light. Using the integrated value of the obtained fluorescence spectrum from 600 nm to 700 nm, the value obtained by dividing 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 at which the spectral fluctuation before and after storage was maximized was determined under the following conditions. 5: The spectral fluctuation is 1% or less before and after storage. 4: The spectral fluctuation exceeds 1% before and after storage and is 3% or less. 3: The spectral fluctuation exceeds 3% before and after storage and is 5% or less. 2: The spectral fluctuation exceeds 5 before and after storage. % and less than 10% 1: Spectral change exceeds 10% before and after storage

(Evaluation of Light Resistance) The substrate having the measured fluorescence intensity was irradiated with an illuminance of 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 at which the spectral fluctuation before and after the treatment was the largest was judged according to the following conditions. 5: The spectral fluctuation is 1% or less before and after the treatment. 4: The spectral fluctuation exceeds 1% before and after the treatment and is 3% or less. 3: The spectral fluctuation exceeds 3% before and after the treatment and is 5% or less. 2: The spectral variation exceeds 5 before and after the treatment. % and less than 10% 1: Spectral change exceeds 10% before and after treatment

(Analytical Evaluation) On a substrate on which the fluorescence intensity was measured, a mask having a pattern was placed on the substrate during exposure to perform exposure. Thereafter, development treatment was carried out with a 2.5% by mass aqueous solution of TMAH (tetramethylammonium hydroxide). The limit size of the pattern shape that can be produced after development is judged according to the following conditions. 5: The limit resolution is 1.4 μm or less 4: The limit resolution exceeds 1.4 μm and is 1.7 μm or less 3: The limit resolution exceeds 1.7 μm and is 2 μm or less 2: The limit resolution exceeds 2 μm and is 3 μm or less 1: No lithiation

(Residue Defect Evaluation) For the substrate on which the fluorescence intensity was measured, the number of defects of the entire film was measured using ComPlus (Applied Material). The measurement results were judged according to the following conditions. The waste which is judged to be derived from the material of 1 μm or more is judged to be a defect of the integral film. 5:8吋The number of defects around the wafer is less than 100. 4:8吋The number of defects around the wafer exceeds 100 and is less than 300. The number of defects around the 3:8吋 wafer exceeds 300 and is less than 500. 2:8吋The number of defects around the wafer exceeds 500 and is less than 1000. 1:8吋 The number of defects around the wafer exceeds 1000

[Table 2]

As shown in the table, the fluorescence intensity ratio of the examples was small. In addition, the fluorescence sensitivity of the fluorescent sensor using the cured film of the embodiment as the emission filter is excellent. On the other hand, the detection sensitivity of the fluorescent sensor using the cured film of the comparative example as the emission filter was poor. Further, the cured films of Examples 1 to 38 and Comparative Examples 1 to 5 were incorporated as an emission filter of a fluorescence sensor, and the sample was irradiated with excitation light having a wavelength of 534 nm to perform fluorescence. As a result of the detection, Examples 1 to 38 were more excellent in detection sensitivity than Comparative Examples 1 to 5.

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‧‧‧Contacts
13‧‧‧Mirror
100, 101‧‧‧ samples

Fig. 1 is a schematic block diagram showing an embodiment of a fluorescent sensor of the present invention. Fig. 2 is a schematic block diagram showing another embodiment of the fluorescent sensor of the present invention.

1‧‧‧Light source

2‧‧‧Excitation filter

3‧‧‧beam splitter

4‧‧‧ objective lens

5‧‧‧sample holder

6‧‧‧Transmission filter

7‧‧‧Contacts

100‧‧‧sample

Claims (13)

A coloring composition which is a coloring composition for forming a radiation 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 is used. The integrated intensity of the fluorescence in the range of 600 nm to 700 nm when the film having a thickness of 3.0 μm is excited by light having a wavelength of 534 nm is divided by the thickness of the color index pigment red 254 containing 40% by mass of the total solid content. The value of the integrated intensity of the fluorescence in the range of 600 nm to 700 nm when the cured film A of 3.0 μm is excited by light having a wavelength of 534 nm is 0.5 or less. A coloring composition which is a coloring composition for forming a radiation filter of a fluorescent sensor, and contains at least one red pigment selected from the color index pigment red 144 and the color index pigment red 166, a resin, a polymerizable compound , photopolymerization initiator and solvent. The colored composition according to Item 1 or 2, wherein the red pigment has an average particle diameter of 5 nm to 500 nm. The coloring composition according to Item 1 or 2, wherein the polymerizable compound is a polymerizable monomer. The colored composition according to Item 4, wherein the polymerizable monomer has three or more radical polymerizable groups. The colored composition according to claim 4, wherein the polymerizable monomer has an alkoxy group. The coloring composition according to claim 6, wherein the polymerizable monomer has a chain containing two or more alkyleneoxy groups as a repeating unit. The coloring composition of claim 1 or 2, wherein the resin contains a graft copolymer. The coloring composition according to the first or second aspect of the invention, wherein the resin comprises a resin containing a repeating unit represented by any one of the following formulas (1) to (4); In the formulae (1) to (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. An atom or a monovalent organic group, Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a divalent linking group, and Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a monovalent organic group, and R ³ represents An alkyl group, R ⁴ represents a hydrogen atom or a monovalent organic group, and n, m, p and q each independently represent an integer of from 1 to 500, and j and k each independently represent an integer of from 2 to 8, in the formula (3) When p is 2 to 500, a plurality of R ³ may be the same or different from each other. In the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ may be the same as each other. different. A fluorescent sensor having a transmission filter using the coloring composition according to any one of claims 1 to 9. The fluorescent sensor according to claim 10, wherein the fluorescent sensor is used by irradiating the sample with excitation light. The fluorescent sensor of claim 10, wherein the fluorescent sensor is a deoxyribonucleic acid sensor. A method of producing a fluorescent sensor, comprising the step of forming a transmission filter using the coloring composition according to any one of claims 1 to 9.