KR102121760B1 - Coloring composition, fluorescent sensor and method for manufacturing fluorescent sensor - Google Patents

Abstract

Provided are a coloring composition capable of obtaining a fluorescent sensor excellent in detection sensitivity, a fluorescent sensor excellent in detection sensitivity, and a manufacturing method of a fluorescent sensor excellent in detection sensitivity.
As a coloring composition for forming an emission filter of a fluorescent sensor, at least one red pigment selected from color index pigment red 144 and color index pigment red 166, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent It includes.

Description

Coloring composition, fluorescent sensor and method for manufacturing fluorescent sensor

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

There is a fluorescent sensor for inspecting a sample by reacting a sample such as DNA (deoxyribonucleic acid) with a reagent and irradiating the sample with excitation light to detect fluorescence emitted therefrom.

The inspection by the fluorescence sensor is performed by irradiating the sample with excitation light, transmitting fluorescence generated from the sample through a imitation filter to transmit fluorescence of a predetermined wavelength, and observing the fluorescence transmitted through the emission filter.

As an emission filter of the fluorescent sensor, for example, a filter using a red pigment is used. As a red pigment, the 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 using a composition containing chromophthalic red BRN (color index pigment red 144) and a photosensitive resin.

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

Patent Document 1: Japanese Patent Application Publication No. 60-129739 Patent Document 2: Japanese Patent Application Publication No. Hei 10-239835

When the inventors have studied the fluorescence sensor with great care, it has been found that the emission filter using the color index pigment red 254 is likely to generate fluorescence due to excitation light and the detection sensitivity of the fluorescence sensor is likely to decrease.

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

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

As a result of careful examination of the coloring composition for forming an emission filter of a fluorescent sensor, the present inventors discovered that the color index pigment red 144 and the color index pigment red 166 are pigments that are unlikely to generate fluorescence due to excitation light . Then, as the color composition was examined, the integral intensity of fluorescence in the range of 600 to 700 nm in wavelength when excited with light at a wavelength of 534 nm of a film having a thickness of 3.0 μm formed using the color composition is a color index pigment. A fluorescent sensor having excellent detection sensitivity can also be obtained by using a colored composition having a value divided by 0.5 or less by the integral intensity of fluorescence in the range of 600 to 700 nm in wavelength when excited with light at a wavelength of 534 nm of the cured film described later containing red 254. Discovering what can be obtained, the present invention has been completed. The present invention provides the following.

<1> A coloring composition for forming an emission filter of a fluorescent sensor,

It contains a red pigment, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent,

The integral intensity of fluorescence in the wavelength range of 600 to 700 nm when excited with light at a wavelength of 534 nm of a film having a thickness of 3.0 μm formed using a coloring composition,

The value divided by the integral intensity of fluorescence in the range of 600 to 700 nm in wavelength when excited with light at a wavelength of 534 nm of the cured film A with a thickness of 3.0 μm, containing 40% by mass of the color index Pigment Red 254 in the total solid content. The following is a coloring composition.

<2> A coloring composition for forming an emission filter of a fluorescent sensor,

A coloring composition comprising at least one red pigment selected from color index pigment red 144 and color index pigment red 166, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent.

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

<4> The colored composition as described in any one of <1> to <3>, in which the polymerizable compound is a polymerizable monomer.

<5> The colored composition as described in <4>, in which the polymerizable monomer has three or more radically polymerizable groups.

<6> The colored composition as described in <4> or <5>, in which the polymerizable monomer has an alkyleneoxy group.

<7> The colored composition as described in <6>, in which the polymerizable monomer has a chain containing two or more alkyleneoxy groups as repeating units.

The coloring composition as described in any one of <1>-<7> in which <8> resin contains a graft copolymer.

The coloring composition as described in any one of <1>-<8> in which <9> resin contains the resin containing the repeating unit represented by any one of following formula (1)-(4);

[Formula 1]

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

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

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

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

R ³ represents an alkylene group,

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

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

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

In formula (3), when p is 2 to 500, a plurality of R ^{3 s} may be the same or different from each other,

In the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ may be the same or different from each other.

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

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

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

<13> A method for producing a fluorescent sensor having a step of forming an emission filter using the colored composition according to any one of <1> to <9>.

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

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

In the present specification, the total solid content refers to the total mass of components excluding the solvent from all components of the composition. Moreover, solid content means solid content in 25 degreeC.

In the description of the group (atomic group) in the present specification, the notation that does not describe substitution and unsubstitution includes those that do not have a substituent and have a substituent. For example, "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The term "radiation" in the present specification means, for example, a bright spectrum of mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In addition, in the present invention, light means actinic rays or radiation. The term "exposure" in this specification, unless specifically described, is not only exposure to far ultraviolet rays, X-rays, EUV light, etc., represented by mercury lamps, excimer lasers, etc., but also exposure to drawing by particle beams such as electron beams and ion beams. To include.

In the present specification, "(meth)acrylate" represents both or both of acrylate and methacrylate, and "(meth)acrylic" represents both of acrylic and methacryl, or either, "( "Meth)acryloyl" refers to both or both of acryloyl and methacryloyl, and "(meth)allyl" refers to both of allyl and metalyl, or either.

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

In the present specification, the term "process" is included in this term when the desired action of the process is achieved even if it is not clearly distinguishable from other processes as well as independent processes.

In this specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene conversion values in gel permeation chromatography (GPC) measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, using HLC-8220 (manufactured by Tosoh Corporation), as a column, TSKgel Super AWM-H (manufactured by Tosoh Corporation). , 6.0 mmID (inner diameter) x 15.0 cm) can be obtained by using a 10 mmol/L lithium bromide NMP (N-methylpyrrolidinone) solution as the eluent.

The pigment used in the present invention means an insoluble pigment compound that is difficult to dissolve in a solvent. Typically, it means a pigment compound that is present in a dispersed state as particles in the composition. Here, an arbitrary solvent is mentioned as a solvent, For example, the solvent illustrated in the column of the solvent mentioned later is mentioned. The pigment used in the present invention has a solubility at 25°C of 0.1 g/100 g Solvent or less, for example, for any of propylene glycol monomethyl ether acetate and water.

<Coloring composition>

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

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

In the cured film A, 5 mass% of the color index pigment red 254 having an average particle diameter of 50 nm, 1.5 mass% of the resin represented by the formula D-1, 0.075 mass% of the pigment derivative represented by the formula PZ-1, and the formula M The polymerizable compound represented by -1 contains 0.7% by mass, the resin represented by Formula B-2 contains 4.925% by mass, the photopolymerization initiator represented by Formula I-1 contains 0.3% by mass, and the remainder is propylene glycol monomethyl. It is preferable that the composition which is an ether acetate is a cured film obtained by coating a glass substrate so that the film thickness after curing is 3.0 μm, drying the coated film at 100° C., and then exposing the i-line at an exposure amount of 1000 mJ/cm ² . Moreover, the weight average molecular weight of D-1 is 38000, and the numerical value written in each repeating unit (main chain) represents content (mass ratio) of each repeating unit, and the numerical value written in the repeating part of a side chain is the number of repeating repeating parts. Indicates. Moreover, the weight average molecular weight of B-2 is 12000, and the numerical value put together in each repeating unit (main chain) represents content (mass ratio) of each repeating unit.

[Formula 2]

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

According to the present invention, by using the coloring composition of (1) or (2) above, it becomes possible to form an emission filter having low fluorescence to excitation light.

In addition, the color index pigment red 144 and the color index pigment red 166 have particularly low fluorescence with respect to excitation light, and further, have excellent heat resistance, and thus have lower fluorescence with respect to excitation light, and furthermore, heat resistance. This excellent emission filter can be formed.

In addition, since the emission filter using the coloring composition of the present invention has low fluorescence to excitation light, the fluorescence sensor having the emission filter using the coloring composition of the present invention is affected by fluorescence caused by the emission filter. This is small, and the detection sensitivity is excellent.

Hereinafter, the present invention will be described in detail.

<Coloring composition>

<<red pigment>>

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

[Formula 3]

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

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

It is preferable that at least two of R ¹⁰ to R ¹⁴ are halogen atoms and the rest are hydrogen atoms. It is more preferable that two of R ¹⁰ to R ¹⁴ are halogen atoms and the rest are hydrogen atoms. In particular, it is preferable that R ¹⁰ and R ¹³ are halogen atoms and R ¹¹ , R ¹² and R ¹⁴ are hydrogen atoms.

All of R ⁶ to R ⁹ may be hydrogen atoms, at least one of R ⁶ to R ⁹ is a halogen atom, and the rest may be hydrogen atoms. When at least one of R ⁶ to R ⁹ represents a halogen atom, R ⁷ is a halogen atom, and the rest is preferably a hydrogen atom or a halogen atom, more preferably a hydrogen atom.

In the present invention, the red pigment preferably contains at least one selected from C. I. Pigment Red 144 and C. I. Pigment Red 166. Since C. I. Pigment Red 144 and C. I. Pigment Red 166 have low fluorescence for excitation light, it is possible to form an emission filter having low fluorescence for excitation light.

In the present invention, the average particle diameter of the red pigment is preferably 5 to 1000 nm, and 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 examination of the inventors, it was found that by reducing the particle size of the red pigment, there is a tendency to have low fluorescence with respect to excitation light. When the average particle diameter of the red pigment is in the above range, it is easy to form an emission filter having lower fluorescence for excitation light.

In addition, in the present invention, the "average particle diameter" of the red pigment is an average particle diameter for the secondary particles collected by the primary particles of the red pigment, and is a value measured by a method such as dynamic light scattering.

In the coloring composition of the present invention, the content of the red pigment is preferably 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 even more preferably 30% by mass or more. The upper limit is more preferably 80% by mass or less, and even more preferably 70% by 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% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more.

Moreover, it is also preferable that the red pigment consists essentially of only C. I. Pigment Red 144 and C. I. Pigment Red 166. In addition, when the red pigment is substantially composed of only CI pigment red 144 and CI pigment red 166, in the red pigment mass, CI pigment red 144 and CI pigment red 166 in total contain 99% by mass or more. It is preferable to do it, and 99.9 mass% or more is more preferable.

As the red pigment of the present invention, the pigments shown below can also be used. 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 can be selected and used so that the coloring composition satisfies the requirements of (1) described above. . In addition, the following pigments can also be used in combination with C. I. Pigment Red 144 and/or C. I. Pigment Red 166.

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

-Refinement of pigment-

In the present invention, it is preferable to use a fine and refined pigment as the red pigment. Pigment refinement is achieved by preparing a high-viscosity liquid composition together with a pigment, a water-soluble organic solvent, and a water-soluble inorganic salt, and subjecting it to a process of grinding by adding stress using a wet grinding device or the like.

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

Moreover, as long as it is adsorbed to the pigment by using a small amount and is not lost in the wastewater, the water solubility is low, or other solvents that do not have water solubility, such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, nitro Benzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, butyl acetate, hexane, heptane, octane, nonane, decaine, undecaine, dodecane, cyclohexane, Methylcyclohexane, halogenated hydrocarbons, acetone, methylethylketone, methylisobutylketone, cyclohexanone, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, etc. may be used.

As for the solvent used for the refinement process of a pigment, only 1 type may be sufficient and 2 or more types may be mixed and used as needed.

Sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate, etc. are mentioned as a water-soluble inorganic salt used for the pigment refinement process.

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

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

The operating conditions of the wet grinding device in the pigment refining process are not particularly limited, but in order to effectively proceed the grinding with the grinding media, the operating condition when the device is a kneader is 10 blades in the device. ~200rpm is preferable, and a relatively large two-axis rotation ratio has a large grinding effect. The operation time is preferably 1 hour to 8 hours in addition to the dry grinding time, and the internal temperature of the device is preferably 50 to 150°C. In addition, the water-soluble inorganic salt as the grinding media has a pulverized particle size of 5 to 50 µm, a sharp particle size distribution, and a spherical shape is preferable.

<<Other chromatic colorants>>

The coloring composition of this invention may contain other chromatic coloring agents other than a red pigment. As other chromatic colorants, a pigment may be sufficient as a dye. Other coloring agents may be used alone or in combination of two or more.

As another chromatic colorant, a yellow pigment is preferred for the purpose of lowering the transmittance at a wavelength of 300 to 400 nm. The yellow pigment is not particularly limited as long as it is commercially available.

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

As a pigment, various pigments conventionally known are mentioned. In addition, considering that it is preferable that the pigment has a high transmittance, it is preferable to use a pigment as small as possible with an average particle diameter, and when handling is also considered, the average particle diameter of the pigment is preferably 0.01 to 0.1 μm, and 0.01 to 0.05 μm. It is more preferable.

The following are mentioned as a pigment. However, the present invention is not limited to these.

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

CI Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73 lights,

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

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

C. I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66, 79, 80

As a dye, for example, Japanese Patent Application Publication No. 64-90403, Japanese Patent Application Publication No. 64-91102, Japanese Patent Application Publication No. Hei 1-94301, Japanese Patent Application Publication No. Hei 6-11614, Japanese Patent 2592207 , US Patent Publication No. 4808501, US Patent Publication No. 5667920, US Patent Publication No. 505950, Japanese Patent Publication No. Hei 5-333207, Japanese Patent Publication No. Hei 6-35183, Japanese Patent Publication No. Hei 6-51115, Japan The pigment disclosed in Unexamined Patent Publication No. Hei 6-194828 can be used. When divided into chemical structures, pyrazole azo compounds, pyrromethene compounds, anilinoazo compounds, triarylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, Cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethane compounds, and the like can be used. Moreover, a dye multimer may be used as a dye. As a dye multimer, the compound described in Unexamined-Japanese-Patent No. 2011-213925 and Unexamined-Japanese-Patent No. 2013-041097 is mentioned.

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

<<resin>>

The colored composition of the present invention contains a resin. The resin is blended, for example, for the purpose of dispersing the pigment in the composition and for the use of a binder. Also, the resin mainly used for dispersing the pigment is also called a dispersant. However, such a use of the resin is an example, and may be used for purposes other than such use.

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

It is preferable that content of resin is 1 to 80 mass% of the total solid content of a coloring composition. The lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more. The upper limit is preferably 70% by mass or less, and more preferably 60% by mass or less. The colored composition of the present invention may contain only one type of resin, or may contain two or more types. When 2 or more types are included, it is preferable that the total amount becomes said range.

The coloring composition of this invention can contain a dispersing agent as resin.

The dispersant is preferably a resin having at least one selected from an acid group and a basic group, and more preferably a resin having an acid group. Examples of the acid group of the resin include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. An amino group etc. are mentioned as a basic group which resin has. Moreover, in this invention, resin which does not have an acidic radical and a basic group can also be used as a dispersing agent.

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

In the present invention, it is preferable that the resin contains a graft copolymer. In the present invention, the graft polymer can be preferably used as a dispersant for a red pigment. In addition, in the present invention, the graft copolymer means a resin having a graft chain. In addition, the graft chain refers to the origin of the main chain of the polymer and from the main chain to the end of the branched group.

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. Moreover, 40-10000 are preferable, as for the number of atoms except the hydrogen atom per graft chain, 50-2000 are more preferable, and 60-500 are more preferable.

As a main chain structure of a graft copolymer, (meth)acrylic resin, polyester resin, polyurethane resin, polyurea resin, polyamide resin, polyether resin, etc. are mentioned. Especially, (meth)acrylic resin is preferable.

The graft chain of the graft copolymer is preferably a graft chain having poly(meth)acrylic, polyester, or polyether in order to improve the interaction between the graft site and the solvent and thereby improve dispersibility. It is more preferable that it is a graft chain having an ester or polyether.

The weight average molecular weight (Mw) of the graft copolymer is preferably 5000 to 100000, more preferably 10000 to 50000, and even more preferably 10000 to 30000. The number average molecular weight (Mn) of the graft copolymer is preferably 2500 to 50000, more preferably 5000 to 30000, and still more preferably 5000 to 15000.

As a macromonomer used when the graft copolymer is produced by radical polymerization, a known macromonomer can be used, and a macromonomer AA-6 manufactured by Toa Gosei Co., Ltd. (methyl polymethacrylate having a terminal group of a methacryloyl group) , AS-6 (polystyrene whose terminal group is a methacryloyl group), AN-6S (copolymer of styrene and acrylonitrile whose terminal group is a methacryloyl group), AB-6 (poly that the terminal group is a methacryloyl group) Butyl acrylic acid), Phellixel FM5 manufactured by Daicel Co., Ltd. (5 molar equivalents of ε-caprolactone of 2-hydroxyethyl methacrylate), FA10L (10 molar equivalents of ε-caprolactone of 2-hydroxyethyl acrylate) Accessories), and the polyester-based macromonomers described in Japanese Patent Application Laid-open No. Hei 2-272009.

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

[Formula 4]

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

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

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

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

R ³ represents an alkylene group,

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

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

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

In Formula (3), when p is 2 to 500, a plurality of R ^{3 s} may be the same or different from each other,

In the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ may be the same or different from each other.

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

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

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

[Formula 5]

In Formulas (1) to (4), Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a monovalent organic group. The structure of the monovalent organic group is not particularly limited, but specifically, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group And the like. Among these, as the organic groups represented by Z ¹ , Z ² , Z ³ , and Z ⁴ , it is particularly preferable to have a steric repelling effect from the viewpoint of improving dispersibility, and each independently has an alkyl group or an alkoxy group having 5 to 24 carbon atoms. It is preferable, and especially, each independently, C5-C24 branched alkyl group, C5-C24 cyclic alkyl group, or C5-C24 alkoxy group is preferable each independently. Moreover, the alkyl group contained in the alkoxy group may be either linear, branched or cyclic.

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

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

In 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, and a heteroaryl group, and 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, and a straight chain alkyl group having 1 to 20 carbon atoms is more preferable, and 1 to 20 carbon atoms. Particularly preferred is a straight chain alkyl group of 6. In the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ present in the graft copolymer may be the same or different from each other.

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

[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.

It is preferable that the said graft polymer contains the repeating unit which has an acidic radical other than the repeating unit represented by Formula (1)-(4) mentioned above. Examples of the acid group include carboxyl groups, sulfonic acid groups, phosphoric acid groups, phenolic hydroxyl groups, and the like, and carboxyl groups and phenolic hydroxyl groups are preferred. The content of the repeating unit having an acid group is preferably 5 to 95% by mass, more preferably 10 to 95% by mass relative to 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 repeating unit having the above-described functional group is not particularly limited in structure, and examples thereof include a repeating unit having a basic group, a repeating unit having a coordinating group, and a repeating unit having a reactive group.

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

It is preferable that the said graft polymer has a hydrophobic repeating unit other than the repeating unit represented by Formula (1)-(4) mentioned above. The hydrophobic repeating unit is preferably a repeating unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, and more preferably a repeating unit derived from a compound having a ClogP value of 1.2 to 8.

The ClogP value is a value calculated by the program "CLOGP" available from Daylight Chemical Information System, Inc. This program provides the value of "calculation logP" calculated by the fragment approach of Hansch, Leo (see below). The fragment approach is based on the chemical structure of the compound, and the chemical structure is divided into substructures (fragments), and the logP value of the compound is estimated by summing the logP contributions allocated to the fragment. The details are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 is used.

A. J. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. 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 Analysisin Chemistry and Biology. John Wiley &Sons.; A. J. Leo. Calculating log Poct from structure. Chem. Rev., 93, 1281-1306, 1993.

logP means a commercial logarithm of the partition coefficient P (Partition Coefficient), and is a physical property value indicating how an organic compound is distributed in a two-phase equilibrium of oil (generally 1-octanol) and water as a quantitative value, It 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 water phase.

When the value of logP increases to a positive value based on 0, the usability increases, and when the absolute value increases negatively, it means that the water solubility increases, and there is a negative correlation between the water solubility of the organic compound and the organic compound. It is widely used as a parameter for evaluating hydrophilicity.

It is preferable that the graft copolymer has at least one repeating unit selected from repeating units derived from monomers represented by the following formulas (i) to (iii) as hydrophobic repeating units.

[Formula 7]

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

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

L is a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkanylene group, and a substituted alkanylene group), and a divalent aromatic group (for example, aryl) Alkylene group, substituted arylene group), divalent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), substituted imino group (-NR ³¹ -, where R ³¹ is Aliphatic groups, aromatic groups or heterocyclic groups), carbonyl groups (-CO-), or combinations thereof.

It is preferable that L is 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. Moreover, L may contain the polyoxyalkylene structure which repeats 2 or more of 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.

As Z, an aliphatic group (for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, a substituted unsaturated alkyl group), an aromatic group (for example, an aryl group, a substituted aryl group), a heterocyclic group, an oxygen atom (-O-), a sulfur atom ( -S-), imino group (-NH-), substituted imino group (-NR ³¹ -, where R ³¹ is an aliphatic group, aromatic group or heterocyclic group), carbonyl group (-CO-), or combinations thereof, etc. Can be heard.

The aliphatic group may have a cyclic structure or a branched structure. 1-20 are preferable, as for the carbon atom number of an aliphatic group, 1-15 are more preferable, and 1-10 are more preferable. The aliphatic group further includes a ring aggregated hydrocarbon group and a cross-exchange type hydrocarbon group, and examples of the ring aggregated hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and a 4-cyclohexylphenyl group. As a temporary exchange type hydrocarbon ring, for example, pinene, bonene, nopinene, norbornene, bicyclooctane ring (bicyclo[2.2.2]octane ring, bicyclo[3.2.1]octane ring Etc.) tricyclic hydrocarbon rings such as bicyclic hydrocarbon rings, homobledine, adamantane, tricyclo[5.2.1.0 ^2,6 ]decane, tricyclo[4.3.1.1 ^2,5 ]undecane rings, etc. And a tetracyclic [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane, a 4-cyclic hydrocarbon ring such as perhydro-1,4-methano-5,8-methanonaphthalene ring. . In addition, for the temporary exchange type hydrocarbon ring, a condensed ring hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydrophenal Condensed rings in which a plurality of 5- to 8-membered cycloalkane rings such as a ren ring are condensed are also included. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Moreover, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group. However, the aliphatic group represented by Z is a substituent and does not have an acid group.

6-20 are preferable, as for carbon atom number of an aromatic group, 6-15 are more preferable, and 6-10 are more preferable. Moreover, the aromatic group may have a substituent. Examples of the substituent include halogen atoms, aliphatic groups, aromatic groups and heterocyclic groups. However, the aromatic group represented by Z does not have an acid group as a substituent.

It is preferable that a heterocyclic group has a 5-membered ring or a 6-membered ring as a heterocyclic ring. Other heterocycles, aliphatic rings, or aromatic rings may be condensed on the heterocycle. Moreover, the heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an oxo group (=O), a thioxo group (=S), an imino group (=NH), a substituted imino group (=NR ³² , where R ³² is an aliphatic group, Aromatic groups or heterocyclic groups), aliphatic groups, aromatic groups and heterocyclic groups. However, the heterocyclic group represented by Z is a substituent and does not have an acid group.

In the formula (iii), R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms ( For example, methyl group, ethyl group, propyl group, etc.), Z, or -LZ. Here, L and Z are synonymous with the thing 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 typical compounds represented by formulas (i) to (iii) include radical polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like. In addition, as examples of the compounds represented by formulas (i) to (iii), compounds described in paragraphs 0089 to 0093 of JP 2013-249417 A can be referred to, and these contents are incorporated herein.

As a specific example of the said graft copolymer, the following are mentioned, for example. Further, the resins described in paragraphs 0072 to 0094 of JP 2012-255128 A can be used.

[Formula 8]

Dispersants (resins) are also available as commercial products, and specific examples of such products include BYKChemie's "Disperbyk-101 (polyamideamine phosphate), 107 (carboxylic acid ester), 110, 111 (copolymer containing acid group), 130 (Polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)", EFKA Corporation "EFKA4047, 4050-4165 (poly Uretain type), EFKA4330~4340 (block copolymer), 4400~4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylic acid salt), 6220 (fatty acid polyester), 6745 (prop Talocyanine derivatives), 6750 (azo pigment derivatives), "Azispur PB821, PB822, PB880, PB881" manufactured by Ajinomoto Fine Techno Corporation, "Florene TG-710 (uretein oligomer)" manufactured by Kyoeisha Chemical Co., Ltd., "Polyflo No. 50E, No. 300 (acrylic copolymer)", manufactured by Kusumoto Kasei Co., Ltd. "Disparon KS-860, 873SN, 874, #2150 (aliphatic polyvalent carboxylic acid), #7004 (polyetherester) , DA-703-50, DA-705, DA-725", manufactured by Kaos Corporation "Demol RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)" , "Homogenol L-18 (polymeric polycarboxylic acid)", "Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "Acetamine 86 (Stearylamine Acetate)", Nihon Lubri Sols Co., Ltd. "Solsperth 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the terminal), 24000, 28000, 32000 , 38500 (Graft Polymer), Nikko Chemicals' "Nicole T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)", Kawaken Fine Chemicals ) "Hino Act T-8000E", Morishita Sangyo Co., Ltd. "EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450", Sannovco ( Note: "Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100", "ADEKA Pluronic L31, F38, L42, L44, L61, L64, F68, manufactured by ADEKA Corporation And L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123, and "Ionet S-20" manufactured by Sanyo Kasei Co., Ltd., and the like.

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

Moreover, as a resin, (meth)acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., acidic cellulose derivative having a carboxylic acid in the side chain, acid in a polymer having a hydroxyl group A resin having an acid group such as a resin to which anhydride is added can also be used. Moreover, the N-position substituted maleimide monomer copolymer described in JP 10-300922 A and the ether dimer copolymer described in JP 2004-300204 A can also be preferably used as a resin.

Moreover, in this invention, the resin can also use the polymer which has a carboxyl group in a side chain. These polymers may be used as a dispersant or may be used as a binder. Examples of the polymer having a carboxyl group in the side chain include alkali-soluble phenols such as methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, and novolac resin. And resins, acidic cellulose derivatives having a carboxyl group on the side chain, and acid anhydrides added to a polymer having a hydroxy group. In particular, copolymers of (meth)acrylic acid and other monomers copolymerizable therewith are preferred. Examples of other monomers copolymerizable with (meth)acrylic acid include alkyl (meth)acrylates, aryl (meth)acrylates, and vinyl compounds. As alkyl (meth)acrylate and aryl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate , Pentyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, tolyl (meth)acrylate, naphthyl (meth)acrylate As a vinyl compound such as cyclohexyl (meth)acrylate, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydro And furfuryl methacrylate, polystyrene macromonomers, and polymethyl methacrylate macromonomers. As another monomer, an N-position substituted maleimide monomer (for example, N-phenylmaleimide, N-cyclohexylmaleimide, etc.) described in JP-A-10-300922 is exemplified. Moreover, only 1 type may be sufficient as other monomers copolymerizable with these (meth)acrylic acid, and 2 or more types may be sufficient as it.

Moreover, in this invention, resin is benzyl (meth)acrylate/(meth)acrylic acid copolymer, benzyl (meth)acrylate/(meth)acrylic acid/2-hydroxyethyl (meth)acrylate copolymer, benzyl (meth) Polyacrylate copolymers consisting of acrylate/(meth)acrylic acid/other monomers can be preferably used. In addition, 2-hydroxyethyl (meth)acrylate copolymer, 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacryl described in Japanese Patent Application Laid-open No. Hei 7-140654. Acid Copolymer, 2-hydroxy-3-phenoxypropylacrylate/polymethylmethacrylate macromonomer/benzylmethacrylate/methacrylic acid copolymer, 2-hydroxyethylmethacrylate/polystyrene macromonomer/methyl A methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, etc. can also be preferably used.

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

[Formula 9]

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

In the formula (ED1), the hydrocarbon group having 1 to 25 carbon atoms which may have substituents represented by R ¹ and R ² is not particularly limited, but is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl , Straight-chain or branched alkyl groups such as isobutyl, tert-butyl, tert-amyl, stearyl, lauryl and 2-ethylhexyl; Aryl groups such as phenyl; Alicyclic groups such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; Alkyl group substituted with alkoxy, such as 1-methoxyethyl and 1-ethoxyethyl; An alkyl group substituted with an aryl group such as benzyl; And the like. Among these, substituents of primary or secondary carbons, which are difficult to desorb by acid or heat, such as methyl, ethyl, cyclohexyl, and benzyl, are preferred from the viewpoint of heat resistance.

As a specific example of the ether dimer, the description of paragraph No. 0317 of JP 2013-29760 A can be referred to, for example, and this content is incorporated herein. As for the ether dimer, only 1 type may be sufficient and 2 or more types may be sufficient as it.

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

[Formula 10]

In the formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring. . n represents the integer of 1-15.

In the formula (X), 2 to 3 carbon atoms of the alkylene group of R ₂ are preferable. Moreover, although carbon number of the alkyl group of R<_3> is 1-20, More preferably, it is 1-10, and the alkyl group of R<_3> may contain a benzene ring. Examples of the alkyl group containing a benzene ring represented by R ₃ include a benzyl group, a 2-phenyl (iso)propyl group, and the like.

The resin can refer to the description of Japanese Patent Application Publication No. 2012-208494, paragraphs 0558 to 0571 (corresponding U.S. Patent Application Publication No. 2012/0235099, paragraphs 0685 to 0700), the contents of which are incorporated herein by reference. do.

In addition, the copolymer (B) described in paragraph Nos. 0029 to 0063 of JP 2012-32767 and alkali-soluble resins used in Examples, and the binder resin described in JP 2012-208474 of Paragraph Nos. 0088 to 0098 And the binder resin used in the Examples, the binder resin used in Examples and Binder Resins of Japanese Patent Application Publication No. 2012-137531, and the binder resins used in the examples, paragraphs 0132 to 0143 of Japanese Patent Application Publication No. 2013-024934 Binder resins used in Examples and Binder resins used in Examples, Paragraph Nos. 0092 to 0098 of Japanese Patent Application Laid-Open No. 2011-242752 and Paragraph Nos. 0030-0072 of Japanese Patent Laid-Open Nos. 2012-032770 You can also use the binder resin described in. These contents are incorporated herein.

In the present invention, a resin having a polymerizable group may be used as the resin. It is preferable that content of the resin which has a polymerizable group is 1-80 mass% of the total solid content of a 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% by mass or less, and more preferably 60% by mass or less.

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

The resin having a polymerizable group is preferably a polymer having a radical polymerizable group in the side chain. It is preferable that the resin which has a polymerizable group contains the repeating unit which has a radically polymerizable group in a side chain, and the polymer which has a repeating unit represented by Formula (1) is more preferable.

[Formula 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 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 a alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 12 carbon atoms, and a combination of these and one selected from -CO-, -OCO-, -O-, -NH- and -SO _2- And groups formed thereon. The alkylene group and arylene group may have a substituent or may be unsubstituted. Examples of the substituent include a halogen atom, an alkyl group, an aryl group, a hydroxy group, a carboxy group, an alkoxy group, and an aryloxy group. Hydroxy groups are preferred.

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

It is preferable that content of the repeating unit which has a radically polymerizable group in a side chain of the resin which has a polymerizable group is 5-100 mass% of all repeating units. The lower limit is more preferably 10% by mass or more, and even more preferably 15% by mass or more. The upper limit is more preferably 95% by mass or less, and even more preferably 90% by mass or less.

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

As an acidic radical, a carboxyl group, a sulfonic acid group, and a phosphoric acid group are illustrated. Only one type of acid group may be included, or two or more types may be included.

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

Examples of other functional groups include lactones, acid anhydrides, amides, cyano groups, and other accelerators, long-chain and cyclic alkyl groups, aralkyl groups, aryl groups, polyalkylene oxide groups, hydroxy groups, maleimide groups, and amino groups. , Can be appropriately introduced.

Moreover, you may include the repeating unit derived from the above-mentioned ether dimer, the repeating unit derived from the compound represented by Formula (X) demonstrated by the above-mentioned resin, etc.

Although specific examples of the polymerizable resin are shown, the present invention is not limited thereto.

[Formula 12]

As commercially available products of polymerizable resins, the Diana NR series (Mitsubishi Rayon Co., Ltd.), Photomer6173 (COOH-containing polyurethane acrylic oligomer.Diamond Shamrock Co., Ltd.), Biscoat R-264, KS resist 106 ( All Osaka Yuki Chemical Industry Co., Ltd., Cyclomer P series (e.g. ACA 230AA), Fracel CF200 series (all manufactured by Daicel Co., Ltd.), Ebecryl3800 (made by Daicel Yushibi Co., Ltd.), Arc And liqueur RD-F8 (manufactured by Nippon Shokubai Co., Ltd.).

<<polymerizable compound>>

The colored composition of the present invention contains a polymerizable compound. As the polymerizable compound, a known compound capable of crosslinking by a radical can be used. For example, a compound (radical polymerizable compound) having a radical polymerizable group such as a group having an ethylenically unsaturated bond is exemplified. Examples of the group having an ethylenically unsaturated bond include a vinyl group, (meth)allyl group, (meth)acryloyl group, and the like, and (meth)allyl group and (meth)acryloyl group are preferable.

In the present invention, the polymerizable compound may be any of chemical forms such as monomers, prepolymers, that is, dimers, trimers and oligomers, or mixtures thereof and multimers 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, and more preferably 1500 or less. The lower limit is preferably 150 or more, and more preferably 250 or more.

It is preferable that content of a polymeric compound is 1-80 mass% of the total solid content of a coloring composition. The lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more. The upper limit is preferably 70% by mass or less, and more preferably 60% by mass or less.

It is preferable that content of a polymerizable monomer is 1-80 mass% of the total solid content of a 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% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.

Moreover, when using a polymerizable monomer and a resin which has a polymerizable group together, the mass ratio of both is preferably a resin having a polymerizable monomer:polymerizable group = 1:1-20, more preferably 1:1-15, 1 :5 to 15 are more preferable.

The colored composition of the present invention may contain only one type of a polymerizable compound, or may contain two or more types. When 2 or more types are included, it is preferable that the total amount becomes said range.

(Polymerizable monomer)

In the present invention, the polymerizable monomer is preferably a compound having 3 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. This is more preferred.

Specific examples of these compounds are in paragraphs [0095] to [0108] of JP 2009-288705, paragraphs 0227 of JP 2013-29760 A, and paragraphs 0254 to 0257 of JP 2008-292970 A. Reference may be made to the compounds described, which are incorporated herein by reference.

The polymerizable monomer is preferably a compound having an alkyleneoxy group, and more preferably a compound having a chain (alkyleneoxychain) containing two or more alkyleneoxy groups as repeating units. As for the alkyleneoxy chain, it is preferable that the number of repeating units of an alkyleneoxy group is 2-30, 2-20 are more preferable, and 2-10 are more preferable.

2 or more are preferable, as for carbon number of an alkyleneoxy group, 2-10 are more preferable, 2-4 are more preferable, and 2 is especially preferable. That is, the ethyleneoxy group is particularly preferred.

It is preferable that the alkyleneoxy chain is represented by "-((CH ₂ ) _a -O) _b -". In formula, 2 or more are preferable, 2-10 are more preferable, 2-4 are more preferable, and 2 is especially preferable. As for b, it is preferable that it is 2-30, 2-20 are more preferable, and 2-10 are more preferable.

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

[Formula 13]

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

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

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

In formula (Z-4), m is preferably an integer from 0 to 6, more preferably an integer from 0 to 4. Moreover, as for the sum of each m, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable.

In formula (Z-5), n is preferably an integer from 0 to 6, more preferably an integer from 0 to 4. Moreover, as for the sum of each n, the integer of 3-60 is preferable, the integer of 3-24 is more preferable, and the integer of 6-12 is especially preferable.

Moreover, -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)- in formula (Z-4) or formula (Z-5) is the terminal on the oxygen atom side The form which bonds to this X is preferable.

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

The compound represented by the formula (Z-4) or the formula (Z-5) is a conventionally known process, in which ethylene oxide or propylene oxide is bonded to a pentaerythritol or dipentaerythritol by a ring-opening addition reaction to bond the ring-opening skeleton And it can be synthesize|combined by the process of introduce|transducing a (meth)acryloyl group by making (meth)acryloyl chloride react with the terminal hydroxyl group of a ring-opening skeleton, for example. Each process is a well-known process, and a person skilled in the art can easily synthesize a compound represented by formula (Z-4) or formula (Z-5).

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

The following compounds are mentioned as a specific example of a polymerizable monomer which has an alkyleneoxy group. In addition, in M-2, the compound of the left type and the compound of the right type are mixtures of 7:3 by mass ratio.

[Formula 14]

As a commercial item of a polymerizable compound having an alkyleneoxy group, for example, SR-494, a tetrafunctional acrylate having four ethyleneoxy groups manufactured by Sartomer Corporation, and six pentyleneoxy groups manufactured by Nippon Kayaku Co., Ltd. DPCA-60 which is a functional acrylate, TPA-330 which is a trifunctional acrylate having three isobutyleneoxy groups, etc. are mentioned.

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

The polymerizable compound may have an acid group such as a carboxyl group, sulfonic acid group or phosphoric acid group. As a commercial item, M-305, M-510, M-520 etc. by Toa Kosei Co., Ltd. are mentioned, for example.

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

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

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

The polymerizable compound is as described in Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. Hei 2-32293, and Japanese Patent Publication No. Hei 2-16765. , Urea acrylates, ethylene described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, Japanese Patent Publication No. 62-39418 Uretain compounds having an oxide skeleton are also suitable. In addition, addition polymerizable compounds having an amino structure or a sulfide structure in a molecule, which are described in Japanese Patent Application Laid-open No. 63-277653, Japanese Patent Application Laid-open No. 63-260909, and Japanese Patent Application Laid-open No. Hei 1-105238 are used. Thereby, the coloring composition excellent in the photosensitive speed can be obtained.

As a commercial item, urethane oligomer UAS-10, UAB-140 (made by Sanyo Kokusaku Pulp), UA-7200 (made by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (made by Nippon Kayaku Co., Ltd.), UA-306H , UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

<< photopolymerization initiator >>

It is preferable that the coloring composition of this invention contains a photoinitiator.

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 region.

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

Further, it is preferable that the photopolymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

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

In addition, from the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oximes Compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, 3- A compound selected from the group consisting of aryl-substituted coumarin compounds is preferred.

The photopolymerization initiator is a trihalomethyltriazine compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, oxime compound, triallylimidazole dimer, onium compound, benzophenone compound, acetophenone compound, At least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, oxime compounds, triallylimidazole dimers, and benzophenone compounds is preferred.

As a specific example of a photopolymerization initiator, the description of Paragraph Nos. 0265 to 0268 of JP 2013-29760 A can be referred to, for example, and this content is incorporated herein.

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

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

As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names: all manufactured by BASF) can be used. The aminoacetophenone-based initiator can also use a compound described in Japanese Patent Application Publication No. 2009-191179 in which the maximum absorption wavelength is matched to a wave light source such as 365 nm or 405 nm.

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

As a photopolymerization initiator, an oxime compound is more preferably mentioned.

As a specific example of an oxime compound, the compound of Unexamined-Japanese-Patent No. 2001-233842, the compound of Unexamined-Japanese-Patent No. 2000-80068, and the compound of Unexamined-Japanese-Patent No. 2006-342166 can be used.

In the present invention, examples of the oxime compound that can be suitably used include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, and 3-propionyloxyiminobutan-2-one. , 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyl jade City) Iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, etc. are mentioned.

Also, J. C. S. Perkin II (1979) pp. 1653-1660), J. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995, pp. 202-232), Japanese Patent Publication No. 2000-66385, Japanese Patent Publication No. 2000-80068, Japanese Patent Publication No. 2004-534797, Japanese publication The compounds etc. described in each publication of patent publication 2006-342166 are also mentioned.

As a commercial product, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also suitably used. In addition, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), Adeka Arkles NCI-831 and Adeka Arkles NCI-930 (manufactured by ADEKA) Can be used.

In addition, as the oxime compound other than the above-described compounds, the compound described in Japanese Patent Publication No. 2009-519904, in which an oxime is connected to the N position of the carbazole ring, the compound described in U.S. Patent Publication No. 7626957, in which a hetero substituent is introduced at the benzophenone site, and the dye site The compound described in Japanese Unexamined Patent Publication No. 2010-15025 and United States Patent Publication No. 2009-292039, the ketoxime compound described in International Publication No. WO2009/131189, the triazine skeleton and the oxime skeleton are incorporated into the same molecule. Compound disclosed in U.S. Patent Publication No. 7556910, compound having a maximum absorption at 405 nm, and having good sensitivity to a g-ray light source, a compound described in Japanese Patent Application Publication No. 2009-221114, paragraph number of Japanese Patent Application Publication No. 2014-137466 The compounds described in 0076 to 0079 may be used.

Preferably, for example, reference may be made to paragraphs 0274 to 0275 of JP 2013-29760 A, the contents of which are incorporated herein by reference.

Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferable. Further, 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 (E) form and the (Z) form.

[Formula 15]

In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.

In formula (OX-1), it is preferable that it is a monovalent nonmetallic atom group as a monovalent substituent represented by R.

Examples of the monovalent nonmetal atom group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, an arylthiocarbonyl group, and the like. Moreover, these groups may have 1 or more substituents. Moreover, the above-mentioned substituent may be substituted with another substituent.

As a substituent, a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, an aryl group, etc. are mentioned.

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

In the formula (OX-1), as the divalent organic group represented by A, an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, and an alkanylene group are preferable. These groups may have one or more substituents. As a substituent, the substituent mentioned above can be illustrated.

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

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

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

Although specific examples of the oxime compound preferably used in the present invention are shown below, the present invention is not limited to these.

[Formula 16]

The present invention may use an oxime compound having a fluorine atom as a photopolymerization initiator. As specific examples of the oxime compound having a fluorine atom, the compound described in JP 2010-262028 A, the compound 24, 36-40 in JP 2014-500852 A, the compound described in JP 2013-164471 A (C-3) and the like. This content is incorporated herein.

The content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and more preferably 1 to 20% by mass relative to the total solid content of the coloring composition. Within this range, better sensitivity and pattern formability are obtained. The coloring composition may contain only one type of photopolymerization initiator, or may contain two or more types. When 2 or more types are included, it is preferable that the total amount becomes said range.

<< pigment derivative >>

It is preferable that the coloring composition of this invention 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, basic group or phthalimidemethyl group. The pigment derivative is preferably a pigment derivative having an acidic group or a basic group from the viewpoint of dispersibility and dispersion stability.

As an organic pigment for constituting a pigment derivative, diketopyrrolopyrrole pigment, azo pigment, phthalocyanine pigment, anthraquinone pigment, quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment , Thioindigo-based pigments, isoindoline-based pigments, isoindoline-based pigments, quinophthalone-based pigments, tren-based pigments, and metal complex-based pigments.

Moreover, as an acidic group which a pigment derivative has, a sulfonic acid group, a carboxylic acid group, and its salt are preferable, a carboxylic acid group and a sulfonic acid group are more preferable, and a sulfonic acid group is especially preferable. As the basic group of the pigment derivative, an amino group is preferable, and a tertiary amino group is particularly preferable.

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

[Formula 17]

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

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

C represents a single bond, -NH-, -CONH-, -CO ₂ -, -SO ₂ NH-, -O-, -S-, or -SO ₂ -,

D represents a single bond, an alkylene group, or an arylene group,

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

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

t represents the integer of 1-5;

[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 represents a single bond, -NH-, -CONH-, -CO ₂ -, -SO ₂ NH-, -O-, -S-, or -SO ₂ -,

s represents an integer of 0 to 4, and when s is 2 or more, a plurality of Rp2s may be the same or different from each other,

* Indicates a connection with B.

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

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

In the formula (PZ), examples of the (t+1) valent linking group represented by B include an alkylene group, an arylene group, and a heteroarylene group. Examples of the alkylene group include straight chain, branch, and cyclic.

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

[Formula 19]

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

In the formula (PZ), examples of the alkylene group and the arylene group represented by D are methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, dexylene group, cyclopropylene group, and cyclobutylene group. And cyclopentylene groups, cyclohexylene groups, cyclooxylylene groups, cyclodecylene groups, phenylene groups, and naphthylene groups. Among these, as D, a straight-chain alkylene group is preferable, and a C1-C5 straight-chain alkylene group is more preferable.

In the formula (PZ), when E represents -N(Rpa)(Rpb), examples of the alkyl group and aryl group in Rpa and Rpb include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec -Butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, octyl group, decyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclo And a decyl group, a phenyl group, and a naphthyl group. As Rpa and Rpb, a straight-chain or branched alkyl group is particularly preferable, and a straight-chain or branched alkyl group having 1 to 5 carbon atoms is most preferable.

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

The t is preferably 1 or 2.

The following are mentioned as a specific example of a pigment derivative.

[Formula 20]

As for content of a pigment derivative, 1-50 mass% is preferable with respect to the whole mass of a pigment, and 3-30 mass% is more preferable. As for the pigment derivative, only 1 type may be used and 2 or more types may be used together.

<< solvent >>

The colored composition of the present invention may contain a solvent. An organic solvent is mentioned as a solvent. The solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition, but is preferably selected in consideration of the coatability and safety of the composition.

As an example of an organic solvent, the following are mentioned, for example.

As the esters, for example, ethyl acetate, acetic acid-n-butyl, isobutyl acetate, cyclohexyl acetate, amyl acetate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and butyrate butyrate , Methyl lactate, ethyl lactate, alkyl alkyloxyacetate (e.g., alkyloxyacetic acid methyl, alkyloxyacetic acid ethyl, alkyloxyacetic acid butyl (e.g. methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid butyl, ethoxy Methyl acetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionic acid alkyl esters (for example, 3-alkyloxypropionic acid methyl, 3-alkyloxypropionic acid ethyl, etc. (for example, 3-methoxypropionic acid methyl, 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), 2-alkyloxypropionic acid alkyl esters (for example, methyl 2-alkyloxypropionic acid, ethyl 2-alkyloxypropionic acid, 2- Propyl alkyloxypropionic acid and the like (for example, methyl 2-methoxypropionic acid, ethyl 2-methoxypropionic acid, propyl 2-methoxypropionic acid, methyl 2-ethoxypropionic acid, ethyl 2-ethoxypropionic acid), 2-alkyloxy Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate , Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like. As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, And propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like. As ketones, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, etc. are mentioned, for example. Examples of aromatic hydrocarbons include toluene, xylene, and the like.

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

When using two or more organic solvents in combination, particularly preferably, the methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether , Selected from butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate It is a mixed solution composed of two or more.

In the present invention, the organic solvent preferably has a peroxide content of 0.8 mmol/L or less, and more preferably does not substantially contain peroxide.

It is preferable that content of a solvent is 10-95 mass% with respect to the total amount of a coloring composition. The lower limit is more preferably 20% by mass or more, and even more preferably 30% by mass or more. The upper limit is more preferably 90% by mass or less.

<< polymerization inhibitors >>

The colored composition of the present invention may contain a polymerization inhibitor to prevent unnecessary thermal polymerization of the curable compound during production or during storage of the colored composition.

Examples of the polymerization inhibitor include hydroquinone, paramethoxyphenol, di-tert-butyl-paracresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert -Butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine first cerium salt and the like. Especially, paramethoxyphenol is preferable.

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

<<surfactant>>

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

By incorporating a fluorine-based surfactant in the composition, the liquid properties (especially, fluidity) when prepared as a coating liquid are further improved, and the uniformity and liquid-liquidity of the coating thickness can be further improved.

That is, in the case of forming a film using a coating solution to which a composition containing a fluorine-based surfactant is applied, the interfacial tension between the surface to be coated and the coating solution decreases, so that the wettability to the surface to be coated is improved, and the coating property to the surface to be coated is applied. This is improved. For this reason, it is possible to more appropriately form a film having a uniform thickness with a small thickness variation.

The fluorine content in the fluorine-based 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-based surfactant having a fluorine content in this range is effective in terms of uniformity of the thickness of the coating film and liquid-repellency, and solubility in the composition is also good.

Examples of the fluorine-based surfactant include Megapak F171, Copper F172, Copper F173, Copper F176, Copper F177, Copper F141, Copper F142, Copper F143, Copper F144, Copper R30, Copper F437, Copper F475, Copper F479, Copper F482 , Copper F554, Copper F780, RS-72-K (above, manufactured by DIC Corporation), Fluorad FC430, Copper FC431, Copper FC171 (above, Sumitomo 3M Co., Ltd.), Surfon S-382, Copper SC -101, Copper SC-103, Copper SC-104, Copper SC-105, Copper SC1068, Copper SC-381, Copper SC-383, Copper S393, Copper KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636 , PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA) and the like. A block polymer may also be used as the fluorine-based surfactant, and specific examples thereof include compounds described in JP 2011-89090 A.

The fluorine-based surfactant (meth) having a repeating unit derived from a (meth)acrylate compound having a fluorine atom and two or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups). ) A fluorinated polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.

[Formula 21]

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example 14,000. Moreover, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as a fluorine-based surfactant. Specific examples include the compounds described in Japanese Patent Application Laid-open No. 2010-164965 0050 to 0090 and 0289 to 0295, such as Megapak RS-101, RS-102, RS-718K manufactured by DIC.

In addition, the following compounds may be used as the fluorine-based surfactant.

[Formula 22]

Specifically as a nonionic surfactant, glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene Lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol di Stearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1 from BASF), Solspers 20000 (Nihon Lubri Sol Co., Ltd. product) etc. are mentioned. Moreover, it is also possible to use NCW-101, NCW-1001, and NCW-1002 manufactured by Wako Junyaku High School.

Specifically as a cationic surfactant, a phthalocyanine derivative (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), an organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), ( (Meth)acrylic acid (co)polymer polyflow No. 75, No. 90, No. 95 (made by Kyoeisha Chemical Co., Ltd.), W001 (made by Yusho Corporation), and the like.

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

Examples of the silicone surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (above, manufactured by Toray Dow Corning Co., Ltd.) ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials), KP-341, KF6001, KF6002 (above, Shin-Etsu Silicone Co., Ltd.) No.), BYK307, BYK323, BYK330 (above, manufactured by Big Chemical), and the like.

As surfactant, only 1 type may be used and 2 or more types may be combined.

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

<< other ingredients >>

The coloring composition of the present invention includes a thermal polymerization initiator such as an azo-based compound or a peroxide-based compound, a thermal polymerization component, an ultraviolet absorber such as alkoxybenzophenone, a plasticizer such as dioctylphthalate, and a developability improving agent such as a low molecular weight organic carboxylic acid. In addition, various additives such as fillers, antioxidants, and anti-agglomerates may be contained.

Depending on the raw material to be used, a metal element may be included in the composition, but from the viewpoint of suppressing the occurrence of defects, the content of the group 2 element (calcium, magnesium, etc.) in the colored composition is preferably 50 ppm or less, and controlled to 0.01 to 10 ppm It is desirable to do. Moreover, it is preferable that the total amount of the inorganic metal salt in a coloring composition is 100 ppm or less, and it is more preferable to control at 0.5-50 ppm.

<Preparation method of coloring composition>

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

When preparing a coloring composition, you may mix|blend each component collectively, and you may mix|blend sequentially after dissolving and dispersing each component in a solvent. In addition, the order of injection and the working conditions when compounding are not particularly limited. For example, the composition may be prepared by dissolving and dispersing all the components in a solvent at the same time, and if necessary, make each component into two or more solutions/dispersions as appropriate, and mix them at the time of use (when applied) to form a composition. You may prepare.

Moreover, it is preferable to disperse|distribute a red pigment with other components, such as resin, an organic solvent, a pigment derivative, etc. as needed, to prepare a pigment dispersion liquid, and to mix and obtain the obtained pigment dispersion liquid with other components of a coloring composition. .

In the production of the colored composition, it is preferable to filter with a filter for the purpose of removing foreign substances or reducing defects. The filter is not particularly limited as long as it has been conventionally used for filtration applications and the like. For example, fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) ( And filters using materials such as high density and ultra high molecular weight polyolefin resins). Among 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 μm, preferably about 0.01 to 3.0 μm, more preferably about 0.05 to 0.5 μm. By setting it as this range, it becomes possible to suppress preparation of a uniform and smooth composition in a post process, and to remove fine foreign matters reliably. Moreover, it is also preferable to use a fiber-shaped filter medium, and examples of the filter medium include polypropylene fiber, nylon fiber, glass fiber, etc., specifically, SBP type series (SBP008, etc.) manufactured by Rocky Techno, TPR type series ( TPR002, TPR005, etc.), SHPX type series (SHPX003, etc.) filter cartridges can be used.

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

Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The hole diameter here can refer to the nominal value of a filter manufacturing company. Commercially available filters include, for example, Nippon Paul Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd. (formerly Nippon Microlois Co., Ltd.) or Kabuki Co., Ltd. Kits micro filters, etc. You can choose from various filters.

As the second filter, one formed of the same material or the like as the first filter described above can be used.

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

<Physical properties of coloring composition>

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

<Emission filter>

The emission filter of the present invention is obtained by using the coloring composition of the present invention described above. It is preferable to use the emission filter of this invention as an emission filter of a fluorescent sensor.

In the emission filter of the present invention, the integrated intensity of fluorescence in the wavelength range of 600 to 700 nm when excited with light at a wavelength of 534 nm is preferably 0.5 to 0.0001, and more preferably 0.3 to 0.001.

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

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

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

<Fluorescence sensor>

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

The fluorescent sensor of the present invention is not particularly limited as long as it is a configuration having an emission filter using the colored composition of the present invention.

As a fluorescent sensor, what irradiates excitation light with a sample and uses it is mentioned. As a sample, there is no restriction|limiting in particular, The thing etc. which generate|occur|produce fluorescence by irradiating excitation light are mentioned. Examples include proteins, nucleic acids (DNA (deoxyribonucleic acid), RNA (ribonucleic acid), etc.), cells, and microorganisms.

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

An embodiment of the fluorescent sensor of the present invention will be described with reference to FIG. 1. In addition, the fluorescent sensor of this invention is not limited to the following embodiment.

The fluorescent sensor shown in Fig. 1 is a drop-type fluorescent sensor. The fluorescent sensor shown in FIG. 1 includes a light source 1, an excitation filter 2, a beam splitter 3, an objective lens 4, a sample holder 5, an emission filter 6, It has an eyepiece 7. The emission filter 6 is composed of the colored composition of the present invention. The arrow in the figure indicates the direction of travel of light (excitation light, fluorescence, etc.).

In the fluorescent sensor shown in FIG. 1, light irradiated from the light source 1 is restricted to light of an excitation wavelength by the excitation filter 2 and becomes excitation light.

The light source 1 is not particularly limited. For example, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, a xenon lamp, an ultraviolet light emitting diode (ultraviolet LED), an excimer laser generator, and the like can be used.

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

The excitation light is reflected by the beam splitter 3, passes through the objective lens 4, and is irradiated to the sample 100 on the sample holder 5. When the sample 100 is irradiated with excitation light, fluorescence generated from the sample and excitation light scattered by the sample pass through the objective lens 4 and are guided to the beam splitter 3. Of the light directed to the beam splitter 3, light containing a fluorescent component is directed to the emission filter 6 by going straight through the beam splitter 3. In the emission filter 6, only the wavelength of the target fluorescence is transmitted out of the light passing through the beam splitter 3, and the target wavelength of the fluorescence is guided to the eyepiece 7. The fluorescence induced by the eyepiece can be observed by visual observation, camera, or the like.

In the fluorescent sensor of the present invention, since the emission filter 6 has low fluorescence with respect to excitation light, the influence of fluorescence caused by the emission filter can be suppressed, and detection sensitivity is excellent.

Another embodiment of the fluorescent sensor of the present invention will be described with reference to FIG. 2.

The fluorescent sensor shown in Fig. 2 is a transmission type fluorescent sensor. The fluorescent sensor shown in FIG. 2 includes a light source 11, an excitation filter 12, a mirror 13, a sample holder 14, an objective lens 15, an emission filter 16, and an eyepiece (17). The emission filter 16 is composed of the colored composition of the present invention.

In the fluorescent sensor shown in FIG. 2, light irradiated from the light source 11 is restricted to light of an excitation wavelength by the excitation filter 12 and becomes excitation light. The excitation light is reflected by the mirror 13 and irradiated to the sample 101 on the sample holder 14. When the sample 101 is irradiated with excitation light, fluorescence generated from the sample and excitation light scattered by the sample pass through the objective lens 15 and are guided to the emission filter 16. In the emission filter 16, only the target wavelength of fluorescence is transmitted, and the target wavelength of fluorescence is guided to the eyepiece 17. The fluorescence induced by the eyepiece can be observed by visual observation, camera, or the like.

<Manufacturing method of fluorescent sensor>

The manufacturing method of the fluorescent sensor of this invention has the process of forming an emission filter using the coloring composition of this invention.

Specifically, using the coloring composition of this invention, it can manufacture through the process of forming a coloring composition layer on a support body, and the process of hardening a coloring composition layer. Moreover, you may further perform the process of forming a pattern. Hereinafter, each process is demonstrated.

First, using the colored composition of the present invention, a colored composition layer is formed on a support. The support is not particularly limited. And transparent substrates such as glass, silicon wafers, and polymer resins (epoxy resins, etc.). As a method of applying the composition onto the support, various methods such as slit application, inkjet method, rotational application, flexible application, roll application, and screen printing can be used.

The coloring composition layer formed on the support may be prebaked. When pre-baking, the pre-baking temperature is preferably 150°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower. The lower limit may be, for example, 50°C or higher, or 80°C or higher. The prebaking 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 with a hot plate, an oven, or the like.

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

As the radiation (light) that can be used during exposure, ultraviolet rays such as g-rays and i-rays are preferably used (particularly preferably i-rays). 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, and in addition to being performed under the atmosphere, for example, in a low oxygen atmosphere having an oxygen concentration of 19 vol% or less (eg, 15 vol%, 5 vol%, substantially oxygen-free) It may be exposed, or may be exposed in a high oxygen atmosphere (for example, 22% by volume, 30% by volume, 50% by volume) in which the oxygen concentration exceeds 21% by volume. In addition, the exposure illuminance can be appropriately set, and can be usually selected from a range of 1000W/m ² to 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 the exposure treatment, heat treatment (post-baking) may also be performed. Post-baking is a post-development heat treatment for making the film hard to be complete. When performing post-baking, the post-baking temperature is preferably 100 to 240°C, for example. From the viewpoint of film curing, 200 to 230°C is more preferable. The post-baking can be performed continuously or in a batch manner by using heating means such as a hot plate, a convection oven (hot air circulation dryer), and a high-frequency heater to achieve the above-described conditions.

In this way, an emission filter can be produced. The fluorescence sensor can be manufactured by introducing the imitation filter thus obtained into the 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 goes beyond the spirit. In addition, unless otherwise specified, "parts" and "%" are based on mass. Moreover, in the following, 1 inch is 2.54 cm.

(Measurement method of average particle size of pigment)

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

(Used raw materials)

The components used as 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, the numerical value assigned to each repeating unit (main chain) represents the content (mass ratio) of each repeating unit. The numerical value assigned to the repeating site of the side chain is the repeating number of repeating sites. Indicates)

[Formula 23]

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

[Formula 24]

D-3: The following structure (weight average molecular weight 24000, the numerical value assigned to each repeating unit (main chain) represents the content (mass ratio) of each repeating unit. The numerical value assigned to the repeating site of the side chain is the repeating number of repeating sites. Indicates)

[Formula 25]

(Resin 2)

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

[Formula 26]

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

[Formula 27]

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

[Formula 28]

· Pigment derivatives

PZ-1: Structure

[Formula 29]

·Polymerizable compound

M-1 to M-3: the following structure. In addition, in M-2, the compound of the left type and the compound of the right type are mixtures of 7:3 by mass ratio. N of M-3 is 1-3, and the sum of four n is 12 or less.

[Formula 30]

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

·Photopolymerization initiator

I-1 to I-2: the following structure

[Formula 31]

·Surfactants

W-1: Mixture (Mw=14000, 10% PGMEA solution)

[Formula 32]

W-2: Structure

[Formula 33]

(Preparation of coloring composition)

It evaluated using the coloring composition of the components shown in Table 1.

(Composition ratio)

Pigment: 5% by mass

Resin (Resin 1): 1.5% by mass

Pigment derivative: 0.075% by mass

Polymerization initiator: 0.3 mass%

Polymerizable compound: 0.7% by mass

Resin (Resin 2): 4.925 mass%

Surfactant: 0.001% by mass

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

In the coloring composition, a pigment dispersion liquid was prepared by mixing pigment and resin 1 and a pigment derivative, and the remaining components were blended into the pigment dispersion liquid to prepare a coloring composition having the above composition.

[Table 1]

(Fluorescence intensity measurement)

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

Next, pre-baking was performed at 100°C for 2 minutes, followed by exposure under conditions of 1000 mJ/cm ² , and post-baking at 220°C for 5 minutes to prepare a cured film.

About the obtained cured film, the integral intensity of fluorescence in the range of wavelength 600-700nm was measured on the condition of excitation wavelength 534nm, excitation slit 5nm, fluorescence slit 5nm, and photomultiplier tube voltage 950V using F4500 by Hitachi Hi-Tech. . In addition, in the measurement of fluorescence intensity, a measurement was performed using a band pass filter of 530 nm on the light source side to suppress stray light and a sharp cut filter on the detection side to suppress scattered light. Using the integral value of 600-700 nm of the obtained fluorescence spectrum, the value divided by the result of the colored composition of Comparative Example 1 was calculated as the fluorescence intensity ratio.

(Evaluation of dispersion stability)

Each coloring composition was stored in a constant temperature bath at 50°C, and the spectroscopy was measured one week later. Spectra of 400 to 800 nm before and after storage were measured, and the maximum wavelength before and after storage was determined under the following conditions.

5: Spectral fluctuation is 1% or less before and after storage

4: Spectral fluctuation exceeds 1% before and after storage 3% or less

3: Spectral fluctuation exceeds 3% before and after storage 5% or less

2: Spectral fluctuation exceeds 5% before and after storage 10% or less

1: Spectral fluctuation exceeds 10% before and after storage

(Evaluation of light resistance)

The substrate where the fluorescence intensity was measured was irradiated with an xenon lamp at an illuminance of 1.0×10 ⁵ lux for 50 hours to measure light resistance. The spectral of 400-800 nm before and after the treatment was measured, and the maximum wavelength before and after the treatment was determined under the following conditions.

5: Spectral fluctuation is 1% or less before and after treatment

4: Spectral fluctuation exceeds 1% before and after treatment 3% or less

3: Spectral fluctuation exceeds 3% before and after treatment 5% or less

2: Spectral fluctuation exceeds 5% before and after treatment 10% or less

1: Spectral fluctuation exceeds 10% before and after treatment

(Resolution evaluation)

A photomask having a pattern was exposed by exposure on a substrate for measuring fluorescence intensity. Thereafter, development was performed in a 2.5 mass% aqueous solution of TMAH (tetramethylammonium hydroxide). The limit size of the pattern shape which can be produced after development was judged on condition of the following.

5: The limit resolution is 1.4 μm or less

4: limit resolution exceeds 1.4 μm, 1.7 μm or less

3: limit resolution exceeds 1.7 μm, 2 μm or less

2: The limit resolution exceeds 2 μm and 3 μm or less

1: No plasticity

(Residual defect evaluation)

The number of defects of the solid film was measured on a substrate having a measured fluorescence intensity using ComPlus, manufactured by Applied Materials. The measurement results were judged under the following conditions. A foreign material judged to be derived from a material having a thickness of 1 μm or more was judged as a defect of the solid film.

5: 100 defects or less per 8-inch wafer

4: The number of defects per 8-inch wafer is more than 100 and less than 300

3: More than 300 defects per 8 inch wafer

2: The 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, in the Examples, the fluorescence intensity ratio was small. Moreover, the fluorescent sensor using the cured film of the Example as an emission filter had excellent detection sensitivity.

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

Further, the cured films of Examples 1 to 38 and Comparative Examples 1 to 5 were introduced as an emission filter of a fluorescent sensor, and samples were irradiated with excitation light having a wavelength of 534 nm to perform fluorescence detection, and Examples 1 to 38 were compared. Detection sensitivity was superior to Examples 1-5.

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

Claims (21)

delete Fluorescence sensor for irradiating excitation light to a sample generating fluorescence by irradiating excitation light, and transmitting light containing fluorescence generated from the sample through an emission filter to detect light containing fluorescence transmitted through the emission filter Of, as the coloring composition for forming the emission filter,
At least one red pigment selected from color index pigment red 144, and color index pigment red 166, a resin, a polymerizable compound, a photopolymerization initiator, and a solvent,
The coloring composition whose total content of the color index pigment red 144 and the color index pigment red 166 is 99 mass% or more in the total mass of the said red pigment. The method according to claim 2,
The colored composition having an average particle diameter of the red pigment is 5 to 500 nm. The method according to claim 2,
A coloring composition in which the polymerizable compound is a polymerizable monomer. The method according to claim 4,
The coloring composition in which the said polymerizable monomer has three or more radically polymerizable groups. The method according to claim 4,
The coloring composition in which the said polymerizable monomer has an alkyleneoxy group. The method according to claim 6,
A coloring composition in which the polymerizable monomer has a chain containing two or more alkyleneoxy groups as repeating units. The method according to claim 2,
The coloring composition, wherein the resin comprises a graft copolymer. The method according to claim 2,
A coloring composition wherein the resin contains a resin containing a repeating unit represented by any one of the following formulas (1) to (4);
[Formula 1]

In Formulas (1) to (4), W ¹ , W ² , W ³ , and W ⁴ each independently represent an oxygen atom or NH,
X ¹ , X ² , X ³ , X ⁴ , and X ⁵ each independently represent a hydrogen atom or a monovalent organic group,
Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group,
Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a monovalent organic group,
R ³ represents an alkylene group,
R ⁴ represents a hydrogen atom or a monovalent organic group,
n, m, p, and q each independently represent an integer from 1 to 500,
j and k each independently represent an integer of 2 to 8,
In formula (3), when p is 2 to 500, a plurality of R ^{3 s} may be the same or different from each other,
In the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ may be the same or different from each other. Fluorescence sensor having an emission filter using the coloring composition according to claim 2. delete The method according to claim 10,
The fluorescence sensor, wherein the fluorescence sensor is a DNA sensor. A method for manufacturing a fluorescent sensor having a step of forming an emission filter using the colored composition according to claim 2. The method according to claim 2,
The coloring composition in which the said resin contains the resin which has a polymerizable group in a side chain. The method according to claim 2,
A coloring composition further comprising a fluorine-based surfactant. The method according to claim 2,
The coloring composition whose said photoinitiator is an oxime compound. The method according to claim 2,
The resin comprises a resin comprising a repeating unit represented by any one of the following formulas (1) to (4) and a resin comprising a repeating unit represented by the following formula (11).

[In Formulas (1) to (4), W ¹ , W ² , W ³ , and W ⁴ each independently represent an oxygen atom or NH,
X ¹ , X ² , X ³ , X ⁴ , and X ⁵ each independently represent a hydrogen atom or a monovalent organic group,
Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group,
Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a monovalent organic group,
R ³ represents an alkylene group,
R ⁴ represents a hydrogen atom or a monovalent organic group,
n, m, p, and q each independently represent an integer of 1 to 500,
j and k each independently represent an integer of 2 to 8,
In formula (3), when p is 2 to 500, a plurality of R ^{3 s} may be the same or different from each other,
In the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ may be the same or different from each other.]
[Formula 11]

[In Formula 11, 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 group having an ethylenically unsaturated bond.] The method according to claim 2,
A coloring composition having an average particle diameter of the red pigment of 5 to 50 nm. The method according to claim 2,
Content of the said red pigment is 30-90 mass% with respect to the total solid content of a coloring composition, The coloring composition. delete delete

Images