KR20180029064A - Color composition, fluorescence sensor and method for manufacturing fluorescence sensor - Google Patents

Abstract

Provided are a coloring composition capable of obtaining a fluorescence sensor having excellent detection sensitivity, a fluorescence sensor having excellent detection sensitivity, and a method of manufacturing a fluorescence sensor having excellent detection sensitivity.
A coloring composition for forming an emission filter of a fluorescent sensor, comprising at least one red pigment selected from Color Index Pigment Red 144 and Color Index Pigment Red 166, a resin, a polymerizable compound, a photopolymerization initiator, .

Description

Color composition, fluorescence sensor and method for manufacturing fluorescence sensor

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

There is a fluorescence sensor in which a sample such as DNA (deoxyribonucleic acid) or the like is reacted with a reagent, excitation light is irradiated on the sample, and fluorescence emitted from the excitation light is detected.

In the inspection by the fluorescence sensor, the excitation light is irradiated on the sample, and the fluorescence generated from the sample is transmitted through the emission filter through the emission filter to observe the fluorescence transmitted through the emission filter.

As an emissive filter of a fluorescent sensor, for example, a filter using a red pigment is used. As the red pigment, color index pigment red 254 is conventionally used.

On the other hand, Patent Document 1 discloses that a red color filter for an image display device is manufactured by using a composition comprising chromophthalic red BRN (Color Index Pigment Red 144) and a photosensitive resin.

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

Patent Document 1: JP-A-60-129739 Patent Document 2: JP-A-10-239835

As a result of intensive investigation of the fluorescence sensor by the present inventor, it has been found that the emission filter using the color index pigment red 254 easily generates fluorescence by the excitation light, and the detection sensitivity of the fluorescence sensor is apt to be deteriorated.

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

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

The present inventors have intensively studied a coloring composition for forming an emission filter of a fluorescence sensor, and as a result, found that color index pigment red 144 and color index pigment red 166 are pigments in which fluorescence is hardly generated by excitation light . When the coloring composition was examined, the integrated intensity of fluorescence in the wavelength range of 600 to 700 nm when the film having a thickness of 3.0 탆 formed by using the coloring composition was excited with light having a wavelength of 534 nm was measured using Color Index Pigment A fluorescent sensor having an excellent detection sensitivity can be obtained by using a coloring composition having a value of 0.5 or less divided by the integrated intensity of fluorescence in a wavelength range of 600 to 700 nm when the cured film containing red 254 is excited by light having a wavelength of 534 nm And have reached the present invention. The present invention provides the following.

≪ 1 > A colored composition for forming an emulsion filter of a fluorescence sensor,

A red pigment, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent,

The integrated intensity of fluorescence in a wavelength range of 600 to 700 nm when a film having a thickness of 3.0 탆 formed by using a coloring composition was excited by light having a wavelength of 534 nm,

A value obtained by dividing the cured film A having a thickness of 3.0 占 퐉 and containing the color pigment Pigment Red 254 by 40% by mass in the total solid content divided by the integral intensity of fluorescence in a wavelength range of 600 to 700 nm when excited by light of 534 nm wavelength was 0.5 ≪ / RTI >

≪ 2 > A colored composition for forming an emulsion filter of a fluorescence sensor,

Color Index Pigment Red 144, and Color Index Pigment Red 166, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent.

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

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

<5> The coloring composition according to <4>, wherein the polymerizable monomer has three or more radically polymerizable groups.

<6> The coloring composition according to <4> or <5>, wherein the polymerizable monomer has an alkyleneoxy group.

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

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

<9> The colored composition according to any one of <1> to <8>, wherein the resin comprises a resin containing a repeating unit represented by any one of the following formulas (1) to (4)

[Chemical Formula 1]

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

X ¹ , X ² , X ³ , X ⁴ , and X ⁵ each independently represent a hydrogen atom or a monovalent organic group,

Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group,

Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a monovalent organic group,

R ³ represents an alkylene group,

R ⁴ represents a hydrogen atom or a monovalent organic group,

n, m, p, and q each independently represent an integer of 1 to 500,

j and k each independently represent an integer of 2 to 8,

In the formula (3), when p is 2 to 500, plural R ³ may be the same or different,

In the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ^{4 present} may be the same or different.

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

&Lt; 11 > The fluorescence sensor according to < 10 >, wherein the fluorescence sensor irradiates the sample with excitation light.

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

&Lt; 13 > A method for producing a fluorescent sensor having a step of forming an emissive filter using the coloring composition according to any one of < 1 > to < 9 >.

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

1 is a schematic configuration diagram of an embodiment of a fluorescence sensor of the present invention.
2 is a schematic configuration diagram of another embodiment of the fluorescence sensor of the present invention.

As used herein, the term "total solid content" refers to the total mass of components excluding the solvent from the total components of the composition. The solid content refers to the solid content at 25 占 폚.

In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes those having a substituent and having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

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

As used herein, the term " (meth) acrylate "refers to both or either of acrylate and methacrylate, and " (Meth) acryloyl "represents either or both acryloyl and methacryloyl, and" (meth) allyl "represents either or both of allyl and methallyl.

In the present specification, Me in the formula represents a methyl group, Et represents an ethyl group, Pr indicates a propyl group, Bu indicates a butyl group, and Ph indicates a phenyl group.

In the present specification, the term " process "is included in this term, not only in the independent process but also in the case where the desired action of the process is achieved even if it can not be clearly distinguished from other processes.

In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene reduced values in Gel Permeation Chromatography (GPC) measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be measured by using, for example, HLC-8220 (manufactured by TOSOH CORPORATION) as a column, TSKgel Super AWM- , 6.0 mm ID (inner diameter) x 15.0 cm) can be obtained by using 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.

The pigment used in the present invention means an insoluble dye compound which is hardly soluble in a solvent. Typically, it refers to a pigment compound present as dispersed as particles in a composition. Here, examples of the solvent include any solvent, and examples thereof include solvents exemplified in the column of the solvent to be described later. The pigment used in the present invention preferably has a solubility of 0.1 g / 100 g Solvent or less at 25 DEG C, for example, propylene glycol monomethyl ether acetate and water.

<Coloring composition>

The coloring composition of the present invention is a coloring composition for forming an emission filter of a fluorescence sensor and satisfies the following requirements (1) or (2).

(1): A film having a thickness of 3.0 m formed by using a coloring composition containing a red pigment, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent was irradiated with light having a wavelength of 534 nm, The integrated intensity of the fluorescence in the range of 1 to 700 nm was measured in a range of a wavelength of 600 to 700 nm when the cured film A having a thickness of 3.0 m and excited by light of a wavelength of 534 nm containing 40% by mass of the color index pigment red 254 in the total solid content Of the fluorescence intensity is 0.5 or less.

The cured film A was obtained by mixing 5% by mass of Color Index Pigment Red 254 having an average particle diameter of 50 nm, 1.5% by mass of a resin represented by Formula D-1, 0.075% by mass of a pigment derivative represented by Formula PZ- -1, 0.7% by mass of a polymerizable compound represented by the formula B-2, 4.925% by mass of a resin represented by the formula B-2 and 0.3% by mass of a photopolymerization initiator represented by the formula I-1, the remainder being propylene glycol monomethyl after drying in ether acetate so that the coating thickness 3.0μm after curing the composition on the glass substrate, and the coating film 100 ℃, it is preferable that the cured film obtained by exposure to i-line as the exposure amount of 1000mJ / cm ^2. In addition, the weight average molecular weight of D-1 is 38000, and the numerical values given in each repeating unit (main chain) indicate the content (mass ratio) of each repeating unit, . The weight average molecular weight of B-2 is 12,000, and the numerical values given in each repeating unit (main chain) represent the content (mass ratio) of each repeating unit.

(2)

(2): color index pigment red 144, and color index pigment red 166, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent.

According to the present invention, it is possible to form an emissive filter having low fluorescence with respect to the excitation light by using the color composition of (1) or (2).

The color index pigment red 144 and the color index pigment red 166 have particularly low fluorescence with respect to the excitation light and further have excellent heat resistance and therefore have a lower fluorescence with respect to the excitation light, This excellent emissive filter can be formed.

Since the emissive filter using the coloring composition of the present invention has low fluorescence with respect to the excitation light, the fluorescence sensor having an emissive filter using the coloring composition of the present invention is capable of suppressing the influence of fluorescence The detection sensitivity is excellent.

Hereinafter, the present invention will be described in detail.

<Coloring composition>

<< Red pigment >>

The coloring composition of the present invention contains a red pigment. The red pigment is preferably a red pigment having an azo skeleton. As the red pigment having an azo skeleton, a compound having a structure represented by the formula R-1 is preferable.

(3)

In the formula, R ¹ to R ¹⁴ each independently represent a hydrogen atom or a halogen atom. The halogen atom includes a chlorine atom, a fluorine atom and a bromine atom, and a chlorine atom is preferable.

It is preferable that at least two of R ¹ to R ⁵ are a halogen atom and the rest are hydrogen atoms. It is more preferable that two out of R ¹ to R ⁵ are a halogen atom and the rest are hydrogen atoms. Particularly, it is preferable that R ¹ and R ⁴ are halogen atoms, and R ² , R ³ and R ⁵ are hydrogen atoms.

At least two of R ¹⁰ to R ¹⁴ are preferably a halogen atom and the remainder are hydrogen atoms. It is more preferable that two out of R ¹⁰ to R ¹⁴ are a halogen atom and the rest are hydrogen atoms. In particular, it is preferable that R ¹⁰ and R ¹³ are halogen atoms, and R ¹¹ , R ¹² and R ¹⁴ are hydrogen atoms.

R ⁶ to R ⁹ may all be hydrogen atoms, at least one of R ⁶ to R ⁹ may be a halogen atom, and the remainder may be a hydrogen atom. When at least one of R ⁶ to R ⁹ represents a halogen atom, it is preferable that R ⁷ is a halogen atom and the remainder is a hydrogen atom or a halogen atom, more preferably a hydrogen atom.

In the present invention, it is preferable that the red pigment contains at least one kind selected from CI Pigment Red 144 and CI Pigment Red 166. C. I. Pigment Red 144, and C.I. Pigment Red 166 have low fluorescence with respect to the excitation light, so that an emissive filter having low fluorescence with respect to the excitation light can be formed.

In the present invention, the average particle diameter of the red pigment is preferably 5 to 1000 nm, more preferably 5 to 500 nm. The upper limit is preferably 400 nm or less, more preferably 350 nm or less, and particularly preferably 300 nm or less. According to the study by the present inventors, it has been found that by decreasing the particle diameter of the red pigment, there tends to be a low fluorescence with respect to the excitation light. When the average particle diameter of the red pigment is within the above range, it is easy to form an emissive filter having lower fluorescence with respect to the excitation light.

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

In the coloring composition of the present invention, the content of the red pigment is preferably from 10 to 90% by mass relative to the total solid content of the coloring composition. The lower limit is more preferably 20% by mass or more, and more preferably 30% by mass or more. The upper limit is more preferably 80 mass% or less, and still more preferably 70 mass% or less.

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 to 100% by mass. The lower limit is more preferably 60 mass% or more, still more preferably 70 mass% or more, and particularly preferably 80 mass% or more.

It is also preferable that the red pigment is substantially composed of only C. I. Pigment Red 144 and C. I. Pigment Red 166. When the red pigment is substantially composed only of CI Pigment Red 144 and CI Pigment Red 166, the total amount of CI Pigment Red 144 and CI Pigment Red 166 in the red pigment mass is 99 mass% or more in total , More preferably not less than 99.9% by mass.

As the red pigment, the following pigments may be used in the present invention. When the red pigment does not contain any of CI Pigment Red 144 and CI Pigment Red 166, one or more of the following pigments may be selected and used so that the coloring composition satisfies the requirement (1) . The following pigments may also be used in combination with C. I. Pigment Red 144 and / or C. I. Pigment Red 166.

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

- Minification of pigments -

In the present invention, it is preferable that the red pigment is a finely and formulated pigment. The fineness of the pigment is achieved by preparing a liquid composition having a high viscosity together with the pigment, the water-soluble organic solvent and the water-soluble inorganic salt, and performing the step of crushing by adding stress using a wet grinding apparatus or the like.

Examples of the water-soluble organic solvent to be used in the process of refining the pigment include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether acetate, and the like.

Further, as long as it is adsorbed to the pigment by a small amount and is not lost in the wastewater, other solvents having low water solubility or having no water solubility such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, The organic solvent may be selected from the group consisting of benzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, butyl acetate, hexane, heptane, octane, nonene, decane, undecane, Methyl cyclohexane, halogenated hydrocarbon, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethyl formamide, dimethyl sulfoxide, N-methylpyrrolidone and the like may be used.

The solvent to be used in the pigment refining step may be one kind or two or more kinds of them may be mixed as necessary.

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

The amount of the water-soluble inorganic salt to be used in the micronization step is preferably 1 to 50 times by mass of the pigment. The amount of the water-soluble inorganic salt to be used is effective in many cases of grinding, but a more preferable amount is 1 to 10 times in terms of productivity. It is also preferable to use inorganic salts having a water content of 1% or less.

The amount of the water-soluble organic solvent used in the micronization process is preferably 50 to 300 parts by mass, more preferably 100 to 200 parts by mass, per 100 parts by mass of the pigment.

The operating conditions of the wet grinding apparatus in the pigment refining step are not particularly limited, but in order to effectively carry out the grinding by the grinding media, the operating condition in the case where the apparatus is a kneader is that the number of rotations of the blades in the apparatus is 10 To 200 rpm is preferable, and the rotation ratio of the two axes is relatively large, the milling effect is large and it is preferable. The operating time is preferably from 1 hour to 8 hours together with the dry grinding time, and the inner temperature of the apparatus is preferably from 50 to 150 ° C. In addition, the water-soluble inorganic salt as the pulverizing medium has a particle size of 5 to 50 mu m and preferably has a sharp particle size distribution and a spherical shape.

<< Other coloring agents >>

The coloring composition of the present invention may contain a chromatic colorant other than the red pigment. The other chromatic colorants may be pigments or dyes. One kind of the other coloring agents may be used, or two or more kinds thereof may be used.

As other chromatic coloring agents, yellow pigments are preferable for the purpose of lowering the transmittance at a wavelength of 300 to 400 nm. The yellow pigment is not particularly limited as long as it is available on the market.

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

As the pigment, various conventionally known pigments can be mentioned. Considering that a high transmittance is preferable, it is preferable to use a pigment having an average particle diameter as small as possible, and considering the handling property, the average particle size of the pigment is preferably 0.01 to 0.1 mu m, more preferably 0.01 to 0.05 mu m More preferable.

As the pigment, the following may be mentioned. However, the present invention is not limited thereto.

CI pigment yellow 1, 2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35,35: 1, 36, 36, 37, 37, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 128, 129, 137, 138, 128, 129, 123, 125, 126, 127, 128, 129, 117, 118, 119, 169, 170, 171, 172, 173, 174, 175, 176, 177, 166, 167, 168, 169, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213,

CI Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 73,

C. I. Pigment Green 7, 10, 36, 37, 58, 59

C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42

15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80

As the dyes, for example, Japanese Unexamined Patent Publication No. 64-90403, Japanese Unexamined Patent Publication No. 64-91102, Japanese Unexamined Patent Publication No. 1-94301, Japanese Unexamined Patent Publication No. 6-11614, Japanese Patent No. 2592207 , U.S. Patent No. 4808501, U.S. Patent No. 5667920, U.S. Patent No. 5,05950, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, A dye disclosed in JP-A-6-194828 can be used. As a chemical structure, a pyrazole compound, a pyromethene compound, an anilino compound, a triarylmethane compound, an anthraquinone compound, a benzilidene compound, an oxolin compound, a pyrazolotriazole compound, a pyridone azo compound, A cyanine compound, a phenothiazine compound, a pyrrolopyrazolequamethane compound, and the like can be used. As the dye, a dye multimer may be used. Examples of the pigment multimer include the compounds described in JP-A-2011-213925 and JP-A-2013-041097.

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

<< Resin >>

The coloring composition of the present invention contains a resin. The resin is used, for example, for dispersing the pigment in the composition and for the binder. The resin mainly used for dispersing the pigment is also referred to as a dispersant. However, such use of the resin is merely an example, and the resin may be used for other purposes.

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

The content of the resin is preferably 1 to 80% by mass of the total 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 mass% or less, and more preferably 60 mass% or less. The coloring composition of the present invention may contain only one kind of resin or two or more kinds of resins. When two or more kinds are included, the total amount is preferably in the above range.

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

As the dispersing agent, a resin having at least one kind selected from an acid group and a basic group is preferable, and a resin having an acid group is more preferable. Examples of the acid group of the resin include a carboxy group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. Examples of the basic group of the resin include an amino group and the like. In the present invention, as the dispersing agent, a resin having neither an acid group nor a basic group may be used.

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

In the present invention, it is preferable that the resin includes a graft copolymer. In the present invention, the graft polymer can be preferably used as a dispersing agent for a red pigment. In the present invention, the graft copolymer means a resin having a graft chain. The graft chain indicates from the origin of the main chain of the polymer to the end of the group branched from the main chain.

As the graft copolymer, a resin having a graft chain in which the number of atoms excluding hydrogen atoms is in the range of 40 to 10000 is preferable. The number of atoms excluding the hydrogen atom per one graft chain is preferably 40 to 10000, more preferably 50 to 2000, and still more preferably 60 to 500.

Examples of the main chain structure of the graft copolymer include a (meth) acrylic resin, a polyester resin, a polyurethane resin, a polyurea resin, a polyamide resin, and a polyether resin. Among them, a (meth) acrylic resin is preferable.

The graft chain of the graft copolymer is preferably a graft chain having a poly (meth) acrylate, a polyester or a polyether in order to improve the interactivity of the graft region and the solvent and thereby improve the dispersibility, More preferably a graft chain having an ester or 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, and even more preferably from 10,000 to 30,000. The number average molecular weight (Mn) of the graft copolymer is preferably from 2500 to 50,000, more preferably from 5,000 to 30,000, and still more preferably from 5,000 to 15,000.

Known macromonomers can be used as the macromonomers used when the graft copolymer is produced by radical polymerization. Macromonomer AA-6 (polymethacryloylmethyl group whose terminal group is methacryloyl group) manufactured by DOKOSEI CO., LTD. , AN-6S (a copolymer of styrene and acrylonitrile having a terminal group of methacryloyl group), AB-6 (poly (meth) acrylate having a terminal group of methacryloyl group), AS-6 (polystyrene in which the terminal group is methacryloyl group) Butyl acrylate), Flaccel FM5 (manufactured by Daicel Chemical Industries, Ltd.) (5-molar equivalent of 2-hydroxyethyl methacrylate), FA10L (10 molar equivalents of? -Caprolactone of 2-hydroxyethyl acrylate And the polyester-based macromonomers described in JP-A-2-272009.

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

[Chemical Formula 4]

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

X ¹ , X ² , X ³ , X ⁴ , and X ⁵ each independently represent a hydrogen atom or a monovalent organic group,

Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group,

Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a monovalent organic group,

R ³ represents an alkylene group,

R ⁴ represents a hydrogen atom or a monovalent organic group,

n, m, p, and q each independently represent an integer of 1 to 500,

j and k each independently represent an integer of 2 to 8,

In the formula (3), when p is 2 to 500, plural R ^{3 s} may be the same or different,

In the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ^{4 present} may be the same or different.

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

In the formulas (1) to (4), X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. X ¹ , X ² , X ³ , X ⁴ , and X ⁵ are each preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and independently of each other, a hydrogen atom or a methyl group More preferably a methyl group is particularly preferable.

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

[Chemical Formula 5]

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

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

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

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

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

[Chemical Formula 6]

Formula (1A) of the, X ^1, Y ^1, Z ¹ and n is ^1, X, Y ^1, Z ¹ and n and the consent of the formula (1), are also the same preferable range.

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

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

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

Examples of the basic group include a primary amino group, a secondary amino group, a tertiary amino group, a heterocyclic ring containing an N atom, an amide group, and the like. Examples of the group having a coordinating group and a reactive group include an acetyl acetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride residue, and an acid chloride residue. The graft polymer may or may not contain a repeating unit having the above-described functional group, but if contained, it is preferably 0.1 to 50 mass%, more preferably 0.1 to 30 mass%, based on the total mass of the graft resin.

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

The ClogP value is a value calculated by the program "CLOGP" available from Daylight Chemical Information System, Inc. This program provides the value of "computed logP" calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of the compound and estimates the logP value of the compound by dividing the chemical structure into partial structures (fragments) and summing the logP contributions assigned to the fragments. The details thereof are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v 4.82 is used.

A. J. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammes, J. B. Taylor and C. A. Ramsden, Eds., P. 295, Pergamon Press, 1990; C. Hansch & A. J. Leo. Substituent Constants for Correlation Analysis &lt; RTI ID = 0.0 &gt; Chemistry & John Wiley &amp;Sons.; A. J. Leo. Calculating log Poct from structure. Chem. Rev., 93, 1281-1306,1993.

log P means a common logarithm of the partition coefficient P, and is a physical property value indicating how an organic compound is distributed in an equilibrium of a two-phase system of oil (generally, 1-octanol) and water as a quantitative value, Is expressed by the following equation.

logP = log (Coil / Cwater)

In the formula, Coil represents the molar concentration of the compound in the oil phase and Cwater represents the molar concentration of the compound in the aqueous phase.

When the value of logP is increased to 0 on the positive side, the oil solubility is increased and when the negative value is increased, the water solubility is increased. The water solubility of the organic compound is negatively correlated with that of the organic compound. And is widely used as a parameter for evaluating the hydrophilicity.

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

(7)

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

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

L is a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (e.g., an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkenylene group, a substituted alkenylene group), a divalent aromatic group (-O-), a sulfur atom (-S-), an imino group (-NH-), a substituted imino group (-NR ³¹ -, wherein R ³¹ represents a hydrogen atom or a substituted or unsubstituted arylene group), a divalent heterocyclic group, An aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-), or a combination thereof.

L is preferably a divalent linking group containing a single bond, an alkylene group or an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L may contain a polyoxyalkylene structure containing two or more repeating oxyalkylene structures. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene 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 is preferably an aliphatic group (for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, a substituted unsaturated alkyl group), an aromatic group (e.g., an aryl group or a substituted aryl group), a heterocyclic group, -S-), an imino group (-NH-), a substituted imino group (-NR ³¹ -, wherein R ³¹ is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-) .

The aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The aliphatic group further includes a cyclic hydrocarbon group and a crosslinked cyclic hydrocarbon group. Examples of the cyclic hydrocarbon groups include a bicyclohexyl group, a perhydronaphthalene group, a biphenyl group, and a 4-cyclohexylphenyl group. As the bridged cyclic hydrocarbon ring, there may be mentioned, for example, phenane, bonene, nopine, novone, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] , Etc.), tricyclic [5.2.1.0 ^2,6 ] decane, and tricyclo [4.3.1.1 ^2,5 ] undecane ring, such as homocyclododecane, homocyclododecane, Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane, and perhydro-1,4-methano-5,8-methanonaphthalene ring, and the like can be given . Examples of the bridged cyclic hydrocarbon ring include condensed cyclic hydrocarbon rings such as perhydro- naphthalene (decalin), perhydroanthracene, perhydro-phenanthrene, perhydro-acenaphthene, perhydrofluorene, perhydroindene, And a condensed ring in which a plurality of 5- to 8-membered cycloalkene rings such as a benzene ring are condensed. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group. Provided that the aliphatic group represented by Z does not have an acid group as a substituent.

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

The heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocyclic ring. The heterocycle may be condensed with another heterocycle, an aliphatic ring or an aromatic ring. The heterocyclic group may have a substituent. Examples of the substituent, a halogen atom, a hydroxyl group, an oxo group (= O), Im oxo group (= S), imino group (= NH), a substituted imino group (= NR ^32, where R ³² be an aliphatic group, An aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group. Provided that 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 represents a hydrogen atom, a halogen atom (for example, fluorine, chlorine or bromine), or an alkyl group having 1 to 6 carbon atoms For example, a methyl group, an ethyl group, a propyl group, etc.), Z, or -LZ. Wherein L and Z are the same as those in the above. As R ⁴ , R ⁵ , and R ⁶ , a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.

Examples of representative compounds represented by the formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrene, and the like. As examples of the compounds represented by formulas (i) to (iii), reference can be made to the compounds described in paragraphs 0089 to 0093 of Japanese Laid-Open Patent Publication No. 2013-249417, the contents of which are incorporated herein.

Specific examples of the graft copolymer include, for example, the following. It is also possible to use resins described in paragraphs 0072 to 0094 of Japanese Laid-Open Patent Publication No. 2012-255128.

[Chemical Formula 8]

Specific examples thereof include Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110 and 111 (copolymers containing an acid group), 130 (maleic anhydride), BYKChemie Quot; BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ", EFKA "EFKA 4047, 4050 to 4165 (polyamide), 161, 162, 163, 164, 165, 166, EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyester amide), 5765 (high molecular weight polycarboxylic acid salt), 6220 (fatty acid polyester), 6745 (Azo pigment), 6750 (azo pigment derivative), Ajinomoto Pine Techno Co., Ltd., Ajisper PB821, PB822, PB880, PB881, Kyoeisha Kagaku Corp. "Floren TG-710 (uretene oligomer) &Quot; Polyfluron No. 50E, No. 300 (acrylic copolymer) ", manufactured by Kusumoto Chemical Industry Co., Ltd., Diparron KS-860, 873SN, 874, # 2150 (Polyetherester), DA-703-50, DA-705, DA-725 ", Daido RN, N (naphthalenesulfonic acid-formaldehyde polycondensate), MS, C, SN , "Emeralgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "Acetamine (polyoxyethylene nonylphenyl ether)", 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 17000, 27000 (terminal part), " NIKKOL T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate), manufactured by Nikko Chemicals Co., Ltd., 47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 401, EFKA Polymer 40, EFKA Polymer 40, Polymer 45 Disupuse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 ", manufactured by ADEKA, Adeka Fluoronic L31, F38, L42, L44 , L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 "available from Sanyo Chemical Industries, Ltd. and" Ionet S-20 " have.

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

As the resin, it is also possible to use, as the resin, (meth) acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer and the like, acidic cellulose derivatives having a carboxylic acid in the side chain, A resin having an acid group such as a resin added with an anhydride may be used. Also, the N-substituted maleimide monomer copolymer described in JP-A-10-300922 and the ether dimer copolymer disclosed in JP-A-2004-300204 can be preferably used.

In the present invention, a resin having a carboxy group in its side chain may also be used. These polymers may be used as a dispersant or as a binder. Examples of the polymer having a carboxy group in the side chain include an alkali soluble phenol such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, Resins and the like, acidic cellulose derivatives having a carboxy group in a side chain, and acid anhydrides added to a polymer having a hydroxy group. Particularly, copolymers of (meth) acrylic acid and other monomers copolymerizable therewith are preferable. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compounds. Examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (Meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl , And cyclohexyl (meth) acrylate. Examples of the vinyl compound include styrene,? -Methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, Furfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like. Other monomers include N-substituted maleimide monomers described in JP-A No. 10-300922 (for example, N-phenylmaleimide, N-cyclohexylmaleimide, etc.). These monomers copolymerizable with (meth) acrylic acid may be used singly or in combination of two or more.

In the present invention, the resin may be at least one selected from the group consisting of benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2- ) Acrylate / (meth) acrylic acid / other monomers can be preferably used. (Meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylate copolymer as described in JP-A-7-140654, a copolymer of 2-hydroxyethyl 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 macromonomer / benzyl methacrylate / methacrylic acid copolymer, and the like can also be preferably used.

The resin may be a monomer containing a compound represented by the following formula (ED1) and / or a compound represented by the general formula (1) of Japanese Laid-Open Patent Publication No. 2010-168539 (hereinafter sometimes referred to as an "ether dimer" (A) which is obtained by polymerizing the component (a).

[Chemical Formula 9]

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

In the formula (ED1), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited, and examples thereof include methyl, ethyl, n-propyl, isopropyl, , Isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, 2-ethylhexyl and the like; An aryl group such as phenyl; Alicyclic groups such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; An alkyl group substituted by alkoxy such as 1-methoxyethyl or 1-ethoxyethyl; An alkyl group substituted with an aryl group such as benzyl; And the like. Of these, an acid such as methyl, ethyl, cyclohexyl, benzyl and the like, or a substituent of a primary or secondary carbon which is difficult to be desorbed by heat, is preferable from the viewpoint of heat resistance.

As a concrete example of the ether dimer, reference can be made, for example, to the disclosure of Japanese Patent Application Laid-Open No. 2013-29760, paragraph number 0317, which is incorporated herein by reference. The ether dimer may be one kind or two or more kinds.

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

[Chemical formula 10]

In 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 an alkyl group having 1 to 20 carbon atoms which may contain a hydrogen atom or a benzene ring . n represents an integer of 1 to 15;

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

Resin can refer to the description of Japanese Patent Laid-Open Publication No. 2012-208494, paragraphs 0558 to 0571 (corresponding US Patent Application Publication No. 2012/0235099, paragraphs 0685 to 0700), which are incorporated herein by reference do.

The copolymer (B) described in paragraphs [0029] to [0063] of JP-A No. 2012-32767 and the alkali-soluble resin used in the examples, the binder resin described in paragraphs 0088 to 0098 of JP-A No. 2012-208474 And the binder resin used in the examples, the binder resin described in paragraphs 0022 to 0032 of Japanese Laid-Open Patent Publication No. 2012-137531 and the binder resin used in the examples, and Japanese Patent Application Laid-Open No. 2013-024934, paragraphs 0132 to 0143 And binder resins used in the examples, paragraphs 0092 to 0098 of Japanese Laid-Open Patent Publication No. 2011-242752 and binder resins used in the examples, paragraphs 0030 to 0072 of JP-A No. 2012-032770 May also be used. The contents of which are incorporated herein by reference.

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

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

The resin having a polymerizable group is preferably a polymer having a radical polymerizable group in its side chain. The resin having a polymerizable group preferably contains a repeating unit having a radically polymerizable group in its side chain, and more preferably a polymer having a repeating unit represented by the formula (1).

(11)

In the formula, R ¹ represents a hydrogen atom or an alkyl group, L ¹ represents a single bond or a divalent linking group, and P ¹ represents a radical polymerizable group.

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

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

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

In the resin having a polymerizable group, the content of the repeating unit having a radically polymerizable group in the side chain is preferably 5 to 100% by mass of the total repeating units. The lower limit is more preferably 10% by mass or more, and more preferably 15% by mass or more. The upper limit is more preferably 95 mass% or less, and further preferably 90 mass% or less.

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

Examples of the acid group include a carboxy group, a sulfonic acid group and a phosphoric acid group. The acid group may be contained only in one kind or in two or more kinds.

The proportion of the repeating unit having an acid group is preferably 0 to 50 mass% of the total 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 mass% or less, and still more preferably 30 mass% or less.

Examples of other functional groups include a development promoter such as lactone, acid anhydride, amide and cyano group, long chain and cyclic alkyl group, aralkyl group, aryl group, polyalkylene oxide group, hydroxyl group, maleimide group and amino group , And can be introduced properly.

It may also contain a repeating unit derived from the above-mentioned ether dimer and a repeating unit derived from a compound represented by the formula (X) described in the above resin.

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

[Chemical Formula 12]

(Manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co., Ltd.), Viscot R-264, KS Resist 106 (All ACA 230AA), FLACCEL CF200 series (all available from DAICEL Co., Ltd.), Ebecryl 3800 (manufactured by DAICEL CO., LTD.), ARC (trade name, manufactured by BASF CORPORATION) And Liqueur RD-F8 (manufactured by Nippon Shokubai Co., Ltd.).

<< Polymerizable compound >>

The coloring composition of the present invention contains a polymerizable compound. As the polymerizable compound, a known compound that can be crosslinked by a radical can be used. For example, a compound having a radically polymerizable group such as a group having an ethylenic unsaturated bond (a radically polymerizable compound). Examples of the group having an ethylenic unsaturated bond include a vinyl group, a (meth) allyl group and a (meth) acryloyl group, and a (meth) allyl group and a (meth) acryloyl group are preferable.

In the present invention, the polymerizable compound may be, for example, a monomer, a prepolymer, that is, a chemical form such as a dimer, a trimer and an oligomer, or a mixture thereof and a multimer thereof. Monomers are preferred.

The monomer-type polymerizable compound (polymerizable monomer) preferably has a molecular weight of 100 to 3000. The upper limit is preferably 2000 or less, more preferably 1500 or less. The lower limit is preferably 150 or more, and more preferably 250 or more.

The content of the polymerizable compound is preferably 1 to 80 mass% of the total solid content of the coloring composition. The lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more. The upper limit is preferably 70 mass% or less, and more preferably 60 mass% or less.

The content of the polymerizable monomer is preferably 1 to 80% by mass of the total solid content of the coloring composition. The lower limit is preferably not less than 2% by mass, more preferably not less than 3% by mass. The upper limit is preferably 70 mass% or less, more preferably 60 mass% or less, and most preferably 50 mass% or less.

When a polymerizable monomer and a resin having a polymerizable group are used in combination, the mass ratio of the polymerizable monomer and the polymerizable group is preferably 1: 1 to 20, more preferably 1: 1 to 15, : 5 to 15 is more preferable.

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

(Polymerizable monomer)

In the present invention, the polymerizable monomer is preferably a compound having three or more radically polymerizable groups, more preferably a compound having 3 to 15 or more radically polymerizable groups, and a compound having 3 to 6 or more radically polymerizable groups Is more preferable.

Specific examples of these compounds are described in paragraphs [0095] to [0108] of JP-A No. 2009-288705, paragraphs 0227 and 027 of JP-A No. 2013-29760, paragraphs 0254 to 0257 of JP-A No. 2008-292970 Reference may be made to the disclosed compounds, the contents of which are incorporated herein by reference.

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

The number of carbon atoms of the alkyleneoxy group is preferably 2 or more, more preferably 2 to 10, still more preferably 2 to 4, and particularly preferably 2. That is, the ethyleneoxy group is particularly preferable

The alkyleneoxy 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 particularly preferably 2. b is preferably 2 to 30, more preferably 2 to 20, and even more preferably 2 to 10.

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

[Chemical Formula 13]

In the formulas (Z-4) and (Z-5), each E independently represents - ((CH ₂ ) _y CH ₂ O) - or - ((CH ₂ ) _y CH (CH ₃ ) , y each independently represents an integer of 0 to 10, and each X independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxy group.

In the formula (Z-4), the sum of the acryloyl group and the methacryloyl group is 3 or 4, m is independently an integer of 0 to 10, at least one of m represents an integer of 1 to 10 , The sum of each m is an integer of 1 to 40.

In the formula (Z-5), the sum of the acryloyl group and the methacryloyl group is 5 or 6, each n independently represents an integer of 0 to 10, at least one of n represents an integer of 1 to 10 , And the sum of each n is an integer of 1 to 60.

In the formula (Z-4), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. The sum of m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and an integer of 4 to 8 is particularly preferable.

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

The - ((CH ₂ ) _y CH ₂ O) - or - ((CH ₂ ) _y CH (CH ₃ ) O) - in the formula (Z-4) or the formula (Z- The form of bonding to X is preferred.

The compounds represented by the formula (Z-4) or (Z-5) may be used singly or in combination of two or more. Particularly, in the formula (Z-5), it is preferable that all of the six X's are acryloyl groups.

The compound represented by the formula (Z-4) or (Z-5) can be produced by a process known in the art, such as pentaerythritol or dipentaerythritol, in which ethylene oxide or propylene oxide is subjected to ring- And a step of introducing a (meth) acryloyl group by reacting a terminal hydroxyl group of the ring-opening skeleton with, for example, (meth) acryloyl chloride. Each process is a well-known process, and a person skilled in the art can easily synthesize a compound represented by the formula (Z-4) or (Z-5).

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

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

[Chemical Formula 14]

Examples of commercially available products of alkyleneoxy group-containing polymerizable compounds include SR-494, a tetrafunctional acrylate having four ethyleneoxy groups, manufactured by Satomaru Co., Ltd., and 6-pentadienyloxy groups having 6 pentyleneoxy groups, manufactured by Nippon Kayaku Co., DPCA-60, which is a functional acrylate, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy groups.

In the present invention, dipentaerythritol triacrylate (KAYARAD D-330, Nippon Kayaku Kabushiki Kaisha) and dipentaerythritol tetraacrylate (KAYARAD D-320, Nippon Kayaku Co., (KAYARAD D-310 manufactured by Nippon Kayaku K.K.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) A-DPH-12E manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd.), and a structure in which these (meth) acryloyl groups are bonded through ethylene glycol and propylene glycol residues (For example, SR454, SR499 commercially available from Satorcom) can be preferably used. These oligomer types can also be used. Further, KAYARAD RP-1040, DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.), NK Ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd.)

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

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

The polymerizable compound is also a preferred embodiment of the compound having a caprolactone structure.

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

The polymerizable compound is preferably a polymerizable compound as described in JP-A-48-41708, JP-A-51-37193, JP-A-2-32293 or JP-A-2-16765 , Urethane acrylates, Japanese Patent Publication No. 58-49860, Japanese Examined Patent Publication No. 56-17654, Japanese Examined Patent Publication No. 62-39417, Japanese Examined Patent Publication No. 62-39418, ethylene Yutein compounds having an oxide-based skeleton are also suitable. Further, addition polymerizable compounds having an amino structure or sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909 and JP-A-1-105238 Whereby a coloring composition having an extremely high photosensitive speed can be obtained.

UA-7200 (manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H (manufactured by Nippon Kayaku Co., Ltd.) , UA-306T, UA-306I, AH-600, T-600 and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.).

<< Photopolymerization initiator >>

The coloring composition of the present invention preferably contains a photopolymerization initiator.

The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is preferable to have photosensitivity to light rays in the visible region from the ultraviolet ray region.

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

The photopolymerization initiator preferably contains at least one compound having a molar absorptivity of at least about 50 within a range of about 300 nm to 800 nm (more preferably, 330 nm to 500 nm).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (such as those having a triazine skeleton and an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, , Oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones. As the halogenated hydrocarbon compound having a triazine skeleton, for example, Wakabayashi et al., Bull. Chem. Soc. Compounds described in GB-A-5313428, compounds described in German Patent Publication No. 3337024, compounds described in J. Org., &Lt; RTI ID = 0.0 &gt; . Chem .; 29, 1527 (1964), compounds described in Japanese Laid-Open Patent Publication No. 62-58241, compounds described in Japanese Laid-Open Patent Publication No. 5-281728, compounds described in Japanese Laid-Open Patent Publication No. 5-34920, Compounds described in Japanese Patent Publication No. 4212976, and the like.

From the viewpoint of exposure sensitivity, a trihalomethyltriazine compound, a benzyldimethylketal compound, an? -Hydroxyketone compound, an? -Amino ketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, oxime Benzophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, 3- (3-methylphenyl) pyridine compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, Aryl-substituted coumarin compounds are preferable.

The photopolymerization initiator is a trihalomethyltriazine compound, an? -Amino ketone compound, an acylphosphine compound, a phosphine oxide compound, an oxime compound, a triallylimidazole dimer, an onium compound, a benzophenone compound, At least one compound selected from the group consisting of a trihalomethyltriazine compound, an? -Amino ketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound is preferable.

As specific examples of the photopolymerization initiator, reference may be made, for example, to paragraphs 0265 to 0268 of Japanese Laid-Open Patent Publication No. 2013-29760, the contents of which are incorporated herein by reference.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be suitably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine-based initiator disclosed in Japanese Patent Publication No. 4225898 can be used.

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959 and IRGACURE-127 (all trade names, manufactured by BASF) can be used.

As the aminoacetophenone-based initiator, commercially available IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (all trade names, manufactured by BASF) can be used. As the aminoacetophenone-based initiator, compounds described in JP-A-2009-191179 in which the maximum absorption wavelength is matched to a wave source such as 365 nm or 405 nm can be used.

As the acylphosphine-based initiator, commercially available IRGACURE-819 and DAROCUR-TPO (all trade names, all manufactured by BASF) can be used.

The photopolymerization initiator is more preferably an oxime compound.

As specific examples of the oxime compounds, compounds described in JP 2001-233842 A, compounds described in JP-A 2000-80068, and JP 2006-342166 A can be used.

Examples of oxime compounds that can be suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan- , 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino- 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like.

J. C. S. Perkin II (1979) pp. 1653-1660), J. C. S. Perkin II (1979) pp. (1995) pp. 202-232, JP-A 2000-66385, JP-A 2000-80068, JP-A 2004-534797, JP, And the compounds described in the respective publications of Patent Publication 2006-342166.

As commercial products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are suitably used. Also, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), Adeka Aches NCI-831 and Adeka Aches NCI-930 (manufactured by ADEKA) Can be used.

As oxime compounds other than the above-mentioned materials, compounds described in Japanese Patent Publication No. 2009-519904 in which oxime is linked to N of a carbazole ring, compounds described in U.S. Patent No. 7626957 in which a hetero substituent is introduced into a benzophenone moiety, Compounds disclosed in JP-A-2010-15025 and U.S. Patent Publication No. 2009-292039 wherein nitroxide groups are introduced, ketoxime compounds described in WO2009 / 131189, triazine skeletons and oxime skeletons in the same molecule A compound described in U.S. Patent Publication No. 7556910, a compound described in Japanese Patent Laid-Open Publication No. 2009-221114 which has a maximum absorption at 405 nm and a good sensitivity to a g-ray light source, a compound disclosed in Japanese Patent Application Publication No. 2014-137466 The compounds described in the above-mentioned publications may be used.

Preferably, for example, refer to Japanese Patent Application Laid-Open No. 2013-29760, paragraphs 0274 to 0275, the content of which is incorporated herein by reference.

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

[Chemical Formula 15]

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-metallic atomic group.

Examples of the monovalent nonmetal atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. These groups may have one or more substituents. The substituent described above may be substituted with another substituent.

Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

In the formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group. These groups may have one or more substituents. As the substituent, the above-mentioned substituent can be exemplified.

In the formula (OX-1), the divalent organic group represented by A is preferably an alkylene group, a cycloalkylene group or an alkane-ylene group having 1 to 12 carbon atoms. These groups may have one or more substituents. As the substituent, the above-mentioned substituent can be exemplified.

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

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

The molar extinction coefficient of the compound can be measured by a known method. For example, the measurement is preferably performed at a concentration of 0.01 g / L using an ultraviolet visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent.

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

[Chemical Formula 16]

The present invention can also use an oxime compound having a fluorine atom as a photopolymerization initiator. Specific examples of the fluorine atom-containing oxime compounds include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A No. 2014-500852, compounds described in JP-A-2013-164471 (C-3), and the like. The contents of which are incorporated herein by reference.

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

<< Pigment Derivatives >>

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

Examples of the organic pigments for constituting the pigment derivative include pigments such as diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perynone pigments, , Thioindigo pigments, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, trene pigments, metal complex pigments, and the like.

The acid group of the pigment derivative is preferably a sulfonic acid group, a carboxylic acid group or a salt thereof, more preferably a carboxylic acid group or a sulfonic acid group, and particularly preferably a sulfonic acid group. As the basic group of the pigment derivative, an amino group is preferable, and a tertiary amino group is particularly preferable.

As the pigment derivative, a quinoline-based, benzimidazoline-based, and isoindoline-based pigment derivative is preferable, and a quinoline-based or benzimidazoline-based pigment derivative is more preferable. The pigment derivative is preferably a pigment derivative having the following structure.

[Chemical Formula 17]

In the formula (PZ), A represents a structure selected from the following formulas (PA-1) to (PA-3)

B represents a single bond or a linking group of (t + 1)

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 arylene group,

E represents -SO ₃ H or a salt thereof, -CO ₂ H or a salt thereof, or -N (Rpa) (Rpb)

Rpa and Rpb each independently represent an alkyl group or an aryl group, Rpa and Rpb may be connected to each other to form a ring,

t represents an integer of 1 to 5;

[Chemical Formula 18]

Rp1 represents an alkyl group or an aryl group having 1 to 5 carbon atoms,

Rp2 represents a halogen atom, an alkyl group or a hydroxy group,

Rp3 is a single _{bond, -NH-, -CONH-, -CO 2 -} , -SO 2 NH-, -O-, -S-, or -SO ₂ - represents,

s represents an integer of 0 to 4, and when s is 2 or more, plural Rp2 may be the same or different,

* Denotes the connection with B

Rp1 is preferably a methyl group or a phenyl group, more preferably a methyl group.

Rp2 is preferably a halogen atom, more preferably a chlorine atom.

In the formula (PZ), the linking group of (t + 1) represented by B includes, for example, an alkylene group, an arylene group and a heteroarylene group. Examples of the alkylene group include straight chain, branched and cyclic groups.

(t + 1) is preferably a linking group represented by the following structural formulas (PA-4) to (PA-9). * Represents the connection with A and C.

[Chemical Formula 19]

Of the formulas (PA-4) to (PA-9), a pigment derivative having a linking group represented by the structural formula (PA-5) or (PA-8) is particularly preferred because of better dispersibility.

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

In the formula (PZ), when E represents -N (Rpa) (Rpb), examples of the alkyl group and the aryl group in Rpa and Rpb include a methyl group, an ethyl group, a propyl group, an isopropyl group, A cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, A decyl group, a phenyl group, and a naphthyl group. Rpa and Rpb are preferably a straight chain or branched alkyl group, and most preferably a straight chain 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, examples of the atom or atom to form a salt include an alkali metal such as lithium atom, sodium atom, potassium atom, , Tetraalkylammonium and the like are preferable.

T is preferably 1 or 2.

Specific examples of the pigment derivative include the following.

[Chemical Formula 20]

The content of the pigment derivative is preferably from 1 to 50% by mass, more preferably from 3 to 30% by mass, based on the total mass of the pigment. 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. As the solvent, organic solvents can be mentioned. The solvent is not particularly limited so long as the solubility of each component and the coating property of the composition are satisfied, but it is preferable that the solvent is selected in consideration of coating property and safety of the composition.

Examples of the organic solvent include the following.

Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, , Methyl lactate, ethyl lactate, alkyloxyacetate (e.g., alkyloxyacetate, alkyloxyacetate, alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxy (For example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-methoxypropionate, etc.) Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid Alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionate, Ethyl propionate, ethyl 2-ethoxypropionate), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (for example, 2-methoxy- Methyl propionate, ethyl 2-ethoxy-2-methyl propionate and the like), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2- . As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like. Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like. As the aromatic hydrocarbon, for example, toluene, xylene and the like can be mentioned.

The organic solvents may be used alone or in combination of two or more.

When two or more kinds of organic solvents are used in combination, it is particularly preferable to use methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether 2-heptanone, cyclohexanone, ethylcarbitol acetate, butylcarbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate. It is a mixed solution composed of two or more kinds.

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

The content of the solvent is preferably 10 to 95% by mass with respect to the total amount of the coloring composition. The lower limit is more preferably 20% by mass or more, and more preferably 30% by mass or more. The upper limit is more preferably 90 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 curing compound during or during the production of the coloring composition.

Examples of the polymerization inhibitor include hydroquinone, para-methoxyphenol, di-tert-butyl-paracresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'- -Butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), and N-nitrosophenylhydroxyamine cerium salt. Among them, para-methoxyphenol is preferable.

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

<< Surfactant >>

The coloring composition of the present invention may contain various surfactants in order to further improve the applicability. As the surfactant, various surfactants such as a fluorine surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.

By containing the fluorosurfactant in the composition, the liquid property (particularly, the fluidity) when it is prepared as a coating liquid is further improved, and uniformity of coating thickness and liquidity can be further improved.

That is, in the case of forming a film by using a coating liquid to which a composition containing a fluorine-containing surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is lowered and the wettability to the surface to be coated is improved, . This makes it possible to more appropriately form a film having a uniform thickness with a small thickness deviation.

The fluorine content in the fluorine surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. The fluorine-containing surfactant having a fluorine content within this range is effective from the viewpoint of the uniformity of the thickness of the coating film and the lyophobic property, and the solubility in the composition is also good.

Examples of the fluorine-based surfactant include Megapak F171, Dong F172, Dong F173, Dong F176, Dong F177, Dong F141, Dong F142, Dong F143, Dong F144, Dong R30, Dong F437, Dong F475, Dong F479, Dong F482 (Manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, Copper SC-422 (manufactured by DIC Corporation), Fluorad FC430, Copper FC431, Copper FC171 (Manufactured by Asahi Glass Co., Ltd.), PF636 (manufactured by Asahi Glass Co., Ltd.), SC-103, SC-104, SC-105, SC- , PF656, PF6320, PF6520 and PF7002 (manufactured by OMNOVA). As the fluorine-based surfactant, a block polymer may be used. Specific examples thereof include the compounds described in Japanese Laid-Open Patent Publication No. 2011-89090.

The fluorine-containing surfactant is preferably a fluorine-containing surfactant having two or more (preferably five or more) repeating units derived from a (meth) acrylate compound having a fluorine atom and an alkyleneoxy group (preferably an ethyleneoxy group and a propyleneoxy group) ) Acrylate compounds, and the following compounds are also exemplified as the fluorinated surfactants used in the present invention.

[Chemical Formula 21]

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000. A fluorine-containing polymer having an ethylenic unsaturated group in its side chain may also be used as a fluorine-containing surfactant. Specific examples thereof include compounds described in Japanese Laid-Open Patent Publication Nos. 2010-164965, 0050 to 0090 and 0289 to 0295, for example, Megapark RS-101, RS-102 and RS-718K manufactured by DIC.

The fluorine-based surfactant may also be the following compounds.

[Chemical Formula 22]

Specific examples of the nonionic surfactant include glycerol, trimethylol propane, trimethylol ethane and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate and the like), polyoxyethylene Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol di-laurate, polyethylene glycol di Lactic acid esters such as stearate and consumptive fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904 and 150R1 manufactured by BASF) Ltd.) and the like. NCW-101, NCW-1001 and NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. may also be used.

Specific examples of the cationic surfactants include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Meth) acrylic acid-based (co) polymer Polyflu No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusoh Co., Ltd.).

Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusoh Corp.), and Santett BL (manufactured by Sanyo Chemical Industries, Ltd.).

Examples of silicone based surfactants include TORAY silicone DC3PA, TORAY silicone SH7PA, TORAY silicone DC11PA, TORAY silicone SH21PA, TORAY silicone SH28PA, TORAY silicone SH29PA, TORAY silicone SH30PA, TORAY silicone SH8400 (manufactured by Toray Dow Corning Co., ), TSF-4440, TSF-4300, TSF-4445, TSF-4460 and TSF-4452 (manufactured by Momentive Performance Materials Co., Ltd.), KP-341, KF6001 and KF6002 (all manufactured by Shin-Etsu Silicones Co., BYK307, BYK323, BYK330 (manufactured by BICKEMI Co., Ltd.), and the like.

Only one surfactant may be used, or two or more surfactants may be combined.

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

<< Other ingredients >>

The coloring composition of the present invention can be suitably used in combination with a coloring composition such as a thermal polymerization initiator such as an azo compound or a peroxide compound, a thermopolymerization component, an ultraviolet absorber such as alkoxybenzophenone, a plasticizer such as dioctyl phthalate, An external filler, an antioxidant, an anti-aggregation agent, and the like.

The content of the second group element (calcium, magnesium, etc.) in the coloring composition is preferably 50 ppm or less, more preferably 0.01 to 10 ppm in terms of suppressing the generation of defects, . The total amount of the inorganic metal salt in the coloring composition is preferably 100 ppm or less, more preferably 0.5 to 50 ppm.

&Lt; Preparation method of colored composition >

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

When the coloring composition is prepared, each component may be blended at one time, or each component may be dissolved and dispersed in a solvent and then blended in succession. The order of addition and the working conditions at the time of compounding are not particularly limited. For example, the composition may be prepared by dissolving and dispersing the entire components in a solvent at the same time. If necessary, the components may be appropriately prepared as two or more solutions and dispersions, and they may be mixed at the time of use .

It is also preferable to prepare a pigment dispersion by dispersing the red pigment together with other components such as a resin, an organic solvent and a pigment derivative, if necessary, and mixing the obtained pigment dispersion with other components of the coloring composition .

In the production of the colored composition, it is preferable to filter with a filter for the purpose of eliminating foreign matters or reducing defects. The filter is not particularly limited as long as it is conventionally used for filtration and the like. For example, fluororesin such as polytetrafluoroethylene (PTFE), polyamide resin such as nylon (e.g., nylon-6, nylon-6,6), polyolefin resin such as polyethylene, polypropylene (PP) High-density, ultra-high molecular weight polyolefin resin), and the like. Of these materials, polypropylene (including high-density polypropylene) and nylon are preferred.

The pore diameter of the filter is preferably about 0.01 to 7.0 mu m, preferably about 0.01 to 3.0 mu m, and more preferably about 0.05 to 0.5 mu m. By setting this range, it is possible to inhibit the preparation of a uniform and smooth composition in a subsequent step, and it is possible to reliably remove minute foreign matter. Examples of the filter material include polypropylene fiber, nylon fiber, and glass fiber. Specific examples thereof include SBP type series (SBP008, etc.), TPR type series TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) filter cartridges can be used.

When using a filter, other filters may be combined. At this time, the filtering by the first filter may be performed once, or may be performed twice or more.

It is also possible to combine the first filters having different pore diameters within the above-mentioned range. The hole diameter here can refer to the nominal value of the filter manufacturer. Examples of commercially available filters include those available from Nippon Oil Corporation (DFA4201NXEY and the like), Advantech Toyobo Co., Ltd., Nippon Integrity Corporation (formerly Nippon Mica Roller Co., Ltd.) You can choose from various filters.

The second filter may be formed of the same material as the first filter described above.

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

&Lt; Physical Properties of Coloring Composition >

The coloring composition of the present invention is characterized in that the integral intensity of fluorescence in the wavelength range of 600 to 700 nm when the film having a thickness of 3.0 탆 is excited by light having a wavelength of 534 nm formed using the coloring composition of the present invention is set to the above- Of the cured film A divided by the integral intensity of fluorescence in the wavelength range of 600 to 700 nm when the cured film A is excited by light having a wavelength of 534 nm is preferably 0.5 or less, more preferably 0.3 or less, still more preferably 0.2 or less, 0.1 or less is particularly preferable.

<Emission filter>

The emulsion filter of the present invention is made using the above-described coloring composition of the present invention. The emissive filter of the present invention is preferably used as an emissive filter of a fluorescent sensor.

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

The film thickness of the emissive filter of the present invention is preferably 10000 to 50000 nm, more preferably 10000 to 35000 nm.

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

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

<Fluorescent Sensor>

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

The fluorescence sensor of the present invention is not particularly limited as long as it has an emissive filter using the coloring composition of the present invention.

As the fluorescence sensor, a sample may be irradiated with excitation light. The sample is not particularly limited, and fluorescence may be generated by irradiating excitation light. For example, proteins, nucleic acids (DNA (deoxyribonucleic acid), RNA (ribonucleic acid), etc.), cells, microorganisms and the like.

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

One embodiment of the fluorescence sensor of the present invention will be described with reference to Fig. Further, the fluorescent sensor of the present invention is not limited to the following embodiments.

The fluorescence sensor shown in Fig. 1 is a drop type fluorescence sensor. The fluorescence 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, an emission filter 6, And an eyepiece portion (7). The emissive filter 6 is composed of the coloring composition of the present invention. Arrows in the figure indicate the traveling direction of light (excitation light, fluorescence, etc.).

In the fluorescence sensor shown in Fig. 1, the light irradiated from the light source 1 is limited to the light of the excitation wavelength by the excitation filter 2, and becomes the 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 LED (ultraviolet LED), an excimer laser generator, or the like.

The excitation filter 2 can be appropriately selected depending on the type of the excitation light to be aimed at. For example, when light having a wavelength of 534 nm is used as excitation light, it is preferable to use a filter that transmits light having a wavelength of 534 nm and shields light having other wavelengths.

The excitation light is reflected by the beam splitter 3, passes through the objective lens 4, and is irradiated onto the sample 100 on the sample holder 5. When excitation light is irradiated onto the sample 100, fluorescence generated from the sample and excitation light scattered by the sample pass through the objective lens 4 and are guided to the beam splitter 3. Of the light guided to the beam splitter 3, light including a fluorescent component is guided to the emission filter 6 straightly through the beam splitter 3. In the emissive filter 6, only the wavelength of the desired fluorescence is transmitted through the beam straight ahead of the beam splitter 3, and the wavelength of the desired fluorescence is guided to the eyepiece 7. Fluorescence guided to the eyepiece can be observed with a naked eye or a camera.

In the fluorescence sensor of the present invention, since the emissive filter 6 has low fluorescence with respect to the excitation light, it is possible to suppress the influence of the fluorescence caused by the emissive filter, and the detection sensitivity is excellent.

Another embodiment of the fluorescence sensor of the present invention will be described with reference to Fig.

The fluorescence sensor shown in Fig. 2 is a transmission type fluorescence sensor. 2 includes a light source 11, an excitation filter 12, a mirror 13, a sample holder 14, an objective lens 15, an emission filter 16, (17). The emissive filter 16 is composed of the coloring 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 excited light by the excitation filter 12, and becomes the excitation light. The excitation light is reflected by the mirror 13 and irradiated to the sample 101 on the sample holder 14. [ When the excitation light is irradiated on the sample 101, the fluorescence generated from the specimen and the excitation light scattered by the specimen pass through the objective lens 15 and are guided to the emission filter 16. In the emissive filter 16, only the wavelength of the desired fluorescence is transmitted, and the wavelength of the desired fluorescence is guided to the eyepiece section 17. [ Fluorescence guided to the eyepiece can be observed with a naked eye or a camera.

&Lt; Method of manufacturing fluorescent sensor &

The method for producing a fluorescent sensor of the present invention has a step of forming an emissive filter using the coloring composition of the present invention.

Specifically, the coloring composition of the present invention can be used to prepare a coloring composition layer on a support, and to cure the coloring composition layer. Further, a step of forming a pattern may be further performed. Hereinafter, each process will be described.

First, a coloring composition layer is formed on a support using the coloring composition of the present invention. The support is not particularly limited. Glass, a silicon wafer, and a polymer resin (epoxy resin, etc.). As the application method of the composition onto the support, various methods such as slit coating, ink jetting, spin coating, casting, roll coating, screen printing and the like can be used.

The colored composition layer formed on the support may be pre-baked. When prebaking is performed, the prebake temperature is preferably 150 占 폚 or lower, more preferably 120 占 폚 or lower, and even more preferably 110 占 폚 or lower. For example, the lower limit may be 50 ° C or higher, and may be 80 ° C or higher. The prebake time is preferably 10 seconds to 300 seconds, more preferably 40 seconds to 250 seconds, and even more preferably 80 seconds to 220 seconds. Drying can be performed by a hot plate, an oven, or the like.

Next, the colored composition layer formed on the support is cured by curing. The curing treatment is preferably an exposure treatment.

As the radiation (light) usable at the time of exposure, ultraviolet rays such as g-line and i-line are preferably used (particularly preferably i-line). Irradiation dose (exposure dose) of, for example 0.03 ~ 2.5J / cm ² are preferred, 0.05 ~ 1.0J / cm ² is more preferred, 0.08 ~ 0.5J / cm ² is most preferred.

The oxygen concentration at the time of exposure can be appropriately selected. In addition to being performed under the atmosphere, for example, in a low oxygen atmosphere (for example, 15 vol%, 5 vol%, substantially anoxic) in which the oxygen concentration is 19 vol% or less Or may be exposed in a high oxygen atmosphere (for example, 22 vol%, 30 vol%, or 50 vol%) in which the oxygen concentration exceeds 21 vol%. Further exposure illumination may be possible to appropriately set and selected from the range of ^{usually, 1000W / m 2 ~ 100000W /} m 2 ( for example, ^{5000W / m 2, 15000W / m} 2, 35000W / m 2). Oxygen concentration and exposure illuminance may be combined as appropriate, and the conditions, for example, roughness on the oxygen concentration of 10 volume% 10000W / m ^2, 20000W roughness in oxygen concentration 35 vol% / m ² and the like.

After performing the exposure process, a further heat treatment (post-baking) may be performed. The post-baking is post-development heat treatment to make the film completely cured. When the post-baking is carried out, the post-baking temperature is preferably 100 to 240 ° C, for example. From the viewpoint of film hardening, 200 to 230 캜 is more preferable. The post-baking can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot-air circulation type drier), or a high-frequency heater so as to achieve the above conditions.

In this way, an emissive filter can be manufactured. The fluorescence sensor can be manufactured by introducing the emulsion filter thus obtained into a fluorescence sensor.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it is beyond the ordinary knowledge. Unless otherwise stated, "part" and "%" are based on mass. In the following, one inch is 2.54 cm.

(Method of measuring average particle diameter of pigment)

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

(Raw materials used)

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

· Red pigment

PR144: C. I. Pigment Red 144

PR166: C. I. Pigment Red 166

PR254: C.I. Pigment Red 254

·Suzy

(Resin 1)

D-1: The following structure (weight average molecular weight: 38000, numerical value given in each repeating unit (main chain) represents the content (mass ratio) of each repeating unit. Lt; / RTI &gt;

(23)

D-2: The following structure (weight average molecular weight: 20000, numerical value given in each repeating unit (main chain) represents content (mass ratio) of each repeating unit. Lt; / RTI &gt;

&Lt; EMI ID =

D-3: The following structure (weight average molecular weight: 24000, numerical value given in each repeating unit (main chain) represents the content (mass ratio) of each repeating unit. Lt; / RTI &gt;

(25)

(Resin 2)

B-1: The following structure (weight average molecular weight: 11000, numerical value given in each repeating unit (main chain) represents the content (mass ratio) of each repeating unit)

(26)

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

(27)

B-3: The following structure (weight average molecular weight: 40000, numerical value given in each repeating unit (main chain) represents the content (mass ratio) of each repeating unit)

(28)

· Pigment derivatives

PZ-1: Structure

[Chemical Formula 29]

· Polymerizable compound

M-1 to M-3: The following structure. M-2 is a mixture of the left-handed compound and the right-handed compound in a mass ratio of 7: 3. N of M-3 is 1 to 3, and the sum of 4 n is 12 or less.

(30)

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

· Photopolymerization initiator

I-1 to I-2: The following structures

(31)

·Surfactants

W-1: The following mixture (Mw = 14000, 10% PGMEA solution)

(32)

W-2: Structure

(33)

(Preparation of coloring composition)

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

(Composition ratio)

Pigment: 5 mass%

Resin (resin 1): 1.5 mass%

Pigment derivative: 0.075 mass%

Polymerization initiator: 0.3 mass%

Polymerizable compound: 0.7 mass%

Resin (resin 2): 4.925 mass%

Surfactant: 0.001 mass%

Solvent (propylene glycol monomethyl ether acetate (PGMEA)): balance

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

[Table 1]

(Fluorescence intensity measurement)

Each coloring composition was applied onto a glass substrate to form a coloring composition layer. The film thickness was adjusted so that the transmittance of the cured film at a wavelength of 500 nm was 5%.

Next, there were prepared after carrying out pre-bake for 2 minutes at 100 ℃, subjected to exposure under the condition of 1000mJ / cm ^2, post-baking is performed for 5 minutes at 220 ℃, cured film.

With respect to the obtained cured film, the integrated intensity of fluorescence in a wavelength range of 600 to 700 nm was measured under the conditions of an excitation wavelength of 534 nm, an excitation slit of 5 nm, a fluorescent slit of 5 nm, and a photomultiplier tube voltage of 950 V using F4500 manufactured by Hitachi High- . Further, in the measurement of fluorescence intensity, a band-pass filter of 530 nm was provided on the light source side and a sharp cut filter was used on the detection side to suppress stray light for suppressing stray light. Using the integrated value of the obtained fluorescence spectrum of 600 to 700 nm, the value obtained by dividing the result of the coloring composition of Comparative Example 1 was calculated as the fluorescence intensity ratio.

(Evaluation of dispersion stability)

Each coloring composition was stored in a thermostatic chamber at 50 DEG C and spectroscopy was measured after one week. The spectra of 400 to 800 nm before and after storage were measured, and it was judged that the spectral fluctuation before and after storage was not more than the maximum wavelength.

5: 1% or less before and after storage

4: Spectroscopic fluctuations exceed 1% before and after storage 3% or less

3: The spectral fluctuation is more than 3% and less than 5% before and after storage

2: Spectral fluctuations exceed 5% before and after storage 10% or less

1: Spectral fluctuations exceed 10% before and after storage

(Evaluation of light resistance)

The substrate on which the fluorescence intensity was measured was irradiated with a xenon lamp at an illuminance of 1.0 x 10 ⁵ lux for 50 hours to measure the light resistance. The spectra of 400 to 800 nm before and after the treatment were measured, and it was judged that the spectral fluctuation before and after the treatment was the maximum wavelength or less.

5: 1% or less before and after treatment

4: Spectroscopic fluctuation exceeding 1% to 3% before and after treatment

3: Spectroscopic fluctuation exceeding 3% and not more than 5% before and after treatment

2: Spectroscopic fluctuation exceeding 5% and before 10% before and after treatment

1: Spectral fluctuations exceed 10% before and after treatment

(Evaluation of Resolution)

On the substrate for measuring the fluorescence intensity, a photomask having a pattern was placed upon exposure to perform exposure. Thereafter, development processing was performed in an aqueous solution of 2.5 mass% TMAH (tetramethylammonium hydroxide). The limit size of a pattern shape that can be manufactured after development was determined as the following conditions.

5: Limit resolution is 1.4μm or less

4: The limiting resolution exceeds 1.4 탆 and 1.7 탆 or less

3: The limiting resolution is more than 1.7 탆 and less than 2 탆

2: The limiting resolution is more than 2 탆 and less than 3 탆

1: No recrystallization

(Residual defect evaluation)

The number of defects of the solid film was measured with a ComPlus manufactured by Applied Materials, the substrate having the fluorescence intensity measured. The measurement results were judged as the following conditions. Foreign matter judged to be originated from a material having a thickness of 1 m or more was judged to be a defect of the solid film.

5: No more than 100 defects per 8-inch wafer

4: More than 100 defects per 8-inch wafer and less than 300

3: More than 300 defects per 8-inch wafer less than 500

2: Number of defects per 8-inch wafer is more than 500 and less than 1000

1: More than 1000 defects per 8-inch wafer

[Table 2]

As shown in the above table, the fluorescent intensity ratio of the examples was small. The fluorescence sensor using the cured film of the Example as an emission filter was excellent in detection sensitivity.

On the other hand, the fluorescence sensor using the cured film of the comparative example as an emissive filter was inferior in detection sensitivity.

The cured films of Examples 1 to 38 and Comparative Examples 1 to 5 were introduced as an emission filter of a fluorescence sensor and fluorescence was detected by irradiating excitation light having a wavelength of 534 nm to the sample. In Examples 1 to 38, Detection sensitivity was superior to Examples 1 to 5.

1 light source
2 excitation filter
3 beam splitter
4 objective lens
5 Sample holder
6 Emission filter
7 Eyepiece
11 light source
12 excitation filter
13 Mirror
14 Sample holder
15 objective lens
16 Emission Filters
17 eyepiece

Claims (13)

As a coloring composition for forming an emulsion filter of a fluorescent sensor,
A red pigment, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent,
The integrated intensity of fluorescence in a wavelength range of 600 to 700 nm when the film of 3.0 μm thick formed using the above colored composition was excited by light having a wavelength of 534 nm,
A value obtained by dividing the cured film A having a thickness of 3.0 占 퐉 and containing the color pigment Pigment Red 254 by 40% by mass in the total solid content divided by the integral intensity of fluorescence in a wavelength range of 600 to 700 nm when excited by light of 534 nm wavelength was 0.5 &Lt; / RTI &gt; As a coloring composition for forming an emulsion filter of a fluorescent sensor,
Color Index Pigment Red 144, and Color Index Pigment Red 166, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent. The method according to claim 1 or 2,
Wherein the red pigment has an average particle diameter of 5 to 500 nm. The method according to any one of claims 1 to 3,
Wherein the polymerizable compound is a polymerizable monomer. The method of claim 4,
Wherein the polymerizable monomer has three or more radically polymerizable groups. The method according to claim 4 or 5,
Wherein the polymerizable monomer has an alkyleneoxy group. The method of claim 6,
Wherein the polymerizable monomer has a chain containing two or more alkyleneoxy groups as repeating units. The method according to any one of claims 1 to 7,
Wherein the resin comprises a graft copolymer. The method according to any one of claims 1 to 8,
Wherein the resin comprises a resin comprising a repeating unit represented by any one of the following formulas (1) to (4);
[Chemical Formula 1]

In the formulas (1) to (4), W ¹ , W ² , W ³ and W ⁴ each independently represent an oxygen atom or NH,
X ¹ , X ² , X ³ , X ⁴ , and X ⁵ each independently represent a hydrogen atom or a monovalent organic group,
Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group,
Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a monovalent organic group,
R ³ represents an alkylene group,
R ⁴ represents a hydrogen atom or a monovalent organic group,
n, m, p, and q each independently represent an integer of 1 to 500,
j and k each independently represent an integer of 2 to 8,
In the formula (3), when p is 2 to 500, plural R ³ may be the same or different,
In the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ^{4 present} may be the same or different. A fluorescent sensor having an emission filter using the coloring composition according to any one of claims 1 to 9. The method of claim 10,
Wherein the fluorescence sensor irradiates the sample with excitation light. The method according to claim 10 or 11,
Wherein the fluorescence sensor is a DNA sensor. A method of manufacturing a fluorescent sensor having a step of forming an emissive filter using the coloring composition according to any one of claims 1 to 9.

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