JP6476302B2 - Colored layer manufacturing method, color filter, light shielding film, solid-state imaging device, and image display device - Google Patents

Description

  The present invention relates to a colored layer manufacturing method, a color filter, a light shielding film, a solid-state imaging device, and an image display device.

Conventionally, a colored layer is formed using a colored radiation-sensitive composition, and the colored layer is used as, for example, a light-shielding film and a color filter provided in a solid-state imaging device or the like.
For example, in Patent Document 1, as a method of forming a colored layer (colored pattern), “... a step of applying a colored radiation-sensitive composition on a substrate to form a colored radiation-sensitive composition layer; A method of exposing a colored radiation-sensitive composition layer in a pattern, and a step of developing the colored radiation-sensitive composition layer after exposure to form a colored pattern "[[ Claim 11]). At this time, in the development, an “alkaline development process” is performed to elute the unexposed portion into the developer and leave the exposed portion ([0236]).

JP 2012-198408 A

When forming a colored layer, it is required to suppress generation of a residue after development processing. For example, if a residue is generated when a colored layer (linear pattern) having a linear pattern is formed, rattling may be observed in the colored pattern (pattern linearity may be inferior). Moreover, a residue may adhere as a foreign substance to the colored layer, and the surface roughness of the colored layer may deteriorate.
When the present inventors formed a colored layer by a conventional method, it was found that the suppression of the generation of residues may be insufficient.

  Therefore, the present invention provides a method for producing a colored layer in which the generation of residues is suppressed, and a color filter, a light-shielding film, a solid-state imaging device, and an image display device using the colored layer obtained by the production method. With the goal.

  As a result of intensive studies to achieve the above object, the present inventors have found that by performing treatment using a developer containing an organic solvent before and after alkali development, generation of residues can be suppressed, and the present invention is Completed.

That is, the present inventors have found that the above object is achieved by the following configuration.
[1] Step a of forming a colored radiation-sensitive composition layer using a colored radiation-sensitive composition containing a coloring agent A, a polymerizable compound B, an alkali-soluble resin C, and a photopolymerization initiator D; A step b in which the colored radiation-sensitive composition layer is exposed in a pattern through a mask; and a step c in which the exposed colored radiation-sensitive composition layer is processed to form a colored layer. And the above-mentioned process c carries out either one of process c1 which processes using the developing solution containing an organic solvent, and process c2 which develops using alkaline aqueous solution, and implements the other process after that. The manufacturing method of the colored layer which is a process to do.
[2] The method for producing a colored layer according to [1], wherein the developer containing the organic solvent contains 95% by mass or more of the organic solvent.
[3] The method for producing a colored layer according to [1] or [2], wherein the colored radiation-sensitive composition further contains a resin E having a group represented by the following general formula (1).
* -X ₁ -Y (1)
In General Formula (1), X ₁ represents a single bond or a divalent linking group. Y represents an alkyl group or a silyl group. * Represents a bonding position.
[4] The method for producing a colored layer according to [3], wherein the resin E further has a group represented by the following general formula (2).
* -X ₂ -Z (2)
In general formula (2), X ₂ represents a single bond or a divalent linking group. Z represents at least one group selected from the group consisting of a (meth) acryloyl group, an allyl group, a vinyl group, an oxetanyl group, an epoxy group, and a hydroxymethylamino group. * Represents a bonding position.
[5] A color filter using a colored layer obtained by the method for producing a colored layer according to any one of [1] to [4].
[6] A light-shielding film using a colored layer obtained by the method for producing a colored layer according to any one of [1] to [4].
[7] A solid-state imaging device having a colored layer obtained by the method for producing a colored layer according to any one of [1] to [4].
[8] An image display device having a colored layer obtained by the method for producing a colored layer according to any one of [1] to [4].

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the colored layer in which generation | occurrence | production of the residue was suppressed, the color filter using the colored layer obtained by the said manufacturing method, a light shielding film, a solid-state image sensor, and an image display apparatus can be provided.

Hereinafter, the contents of the present invention will be described in detail.
In the specification of the present application, “to” is used as a meaning including numerical values described before and after the lower limit value and the upper limit value.
In addition, in the description of groups (atomic groups) in the present specification, the description that does not indicate substitution and non-substitution includes not only those having no substituent but also those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl. In this specification, “monomer” and “monomer” are synonymous. The monomer in the present invention is distinguished from an oligomer and a polymer and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.
The “radiation” in the present invention means those including visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like.

  The method for producing a colored layer of the present invention (hereinafter also simply referred to as “the production method of the present invention”) comprises a colorant A, a polymerizable compound B, an alkali-soluble resin C, and a photopolymerization initiator D. Step a for forming a colored radiation-sensitive composition layer using a radiation composition, Step b for exposing the colored radiation-sensitive composition layer in a pattern through a mask, and the exposed coloring And a step c of forming a colored layer by treating the radiation-sensitive composition layer, wherein the step c is a step c1 of treatment using a developer containing an organic solvent, and development is performed using an alkaline aqueous solution. It is the manufacturing method of a colored layer which is a process of implementing any one process among the process c2 to perform, and implementing the other process after that.

According to the production method of the present invention, the generation of a residue can be suppressed when forming a colored layer. The reason is presumed as follows.
First, a colored radiation-sensitive composition layer is formed using the colored radiation-sensitive composition layer, and then exposed to a pattern. In the exposed part of the colored radiation-sensitive composition layer, the polymerizable compound B is cured by the action of the photopolymerization initiator D. Then, by development using an aqueous alkaline solution (alkali development), the unexposed portion is eluted into the aqueous alkaline solution, and the exposed portion remains as a patterned colored layer (colored pattern).
At this time, in the unexposed portion, the alkali-soluble resin C is eluted in the alkaline aqueous solution, but a hydrophobic component other than the alkali-soluble resin C may not be eluted and may be a residue.
Therefore, in the production method of the present invention, processing using a developer containing an organic solvent (hereinafter also referred to as “organic development” for convenience) is performed before and after alkali development. Thereby, it is thought that the hydrophobic component of an unexposed part elutes in an organic solvent, and generation | occurrence | production of a residue is suppressed.

  Below, after explaining the colored radiation-sensitive composition used for the manufacturing method of the colored layer of this invention first, the manufacturing method of the colored layer of this invention is demonstrated.

[Colored radioactive composition]
The colored radiation-sensitive composition used in the production method of the present invention (hereinafter, also referred to as “the colored radiation-sensitive composition of the present invention” or “the composition of the present invention” for convenience) includes at least the colorant A, It contains a polymerizable compound B, an alkali-soluble resin C, and a photopolymerization initiator D.

[Colorant A]
The composition of the present invention contains a colorant A (hereinafter also simply referred to as “colorant”). By containing a colorant, a colored radiation-sensitive composition having a desired color can be obtained.

  The colorant contained in the composition of the present invention is not particularly limited, and one or two or more kinds selected from the group consisting of conventionally known various dyes and pigments can be mixed and used. Is appropriately selected according to the use of the composition of the present invention. For example, when the composition of the present invention is used for producing a color filter, chromatic colorants (chromatic colorants) such as R, G, and B that form color pixels of the color filter, and black matrix formation Any of the black colorants (black colorants) commonly used for the purpose can be used.

Hereinafter, the colorant that can be used in the composition of the present invention will be described in detail using a colorant suitable for color filter applications as an example.
As the chromatic pigment, various conventionally known inorganic pigments or organic pigments can be used. Further, considering that it is preferable to have a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a finer one as much as possible, and considering the handling properties, the average primary particle diameter of the pigment is 0.01 μm. ˜0.1 μm is preferable, and 0.01 μm to 0.05 m is more preferable.

  Examples of inorganic pigments include metal compounds such as metal oxides and metal complex salts. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, silver, etc. And metal oxides of the above metals. Titanium nitrides, silver tin compounds, silver compounds, and the like can also be used.

Examples of the pigment that can be preferably used in the present invention include the following. However, the present invention is not limited to these.
C. I. Pigment YELLOW 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , Etc. 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214,
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. ,
C. I. Pigment 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, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,270,272,279

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
C. I. Pigment Black 1
These organic pigments can be used alone or in various combinations in order to increase color purity.

In the composition of the present invention, when the colorant is a dye, a colored composition in a state of being uniformly dissolved in the composition can be obtained.
The dye that can be used as the colorant contained in the composition of the present invention is not particularly limited, and conventionally known dyes for color filters can be used. For example, pyrazole azo, anilinoazo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, Dyes such as phthalocyanine, benzopyran, indigo, and pyromethene can be used. Moreover, you may use the multimer of these dyes.

In addition, from the viewpoint of removing the unexposed area by alkali development, an acidic dye and / or a derivative thereof may be preferably used.
In addition, a direct dye, a basic dye, a mordant dye, an acid mordant dye, an azoic dye, a disperse dye, an oil-soluble dye, a food dye, and / or a derivative thereof can be usefully used.

Specific examples of the acid dye are shown below, but are not limited thereto. For example,
acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40-45, 62, 70, 74, 80, 83, 86 , 87, 90, 92, 103, 112, 113, 120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1; acid chroma violet K; acid Fuchsin; acid green 1, 3, 5 , 9, 16, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95;
red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91 , 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257 , 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73 76, 79, 98, 99, 111, 112, 114, 116, 184, 243; Food Yellow 3; and derivatives of these dyes.

  Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; C.I. I. Solvent orange 45; Rhodamine B, Rhodamine 110 and other acid dyes and derivatives of these dyes are also preferably used.

Among them, as the colorant, triarylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, pyrazole azo It is preferable that the colorant is selected from a series, anilinoazo, pyrazolotriazole azo, pyridone azo, and anthrapyridone pyromethene.
Further, pigments and dyes may be used in combination.

The colorant that can be used in the present invention is preferably a dye or a pigment. In particular, a pigment having an average particle size (r) of 20 nm ≦ r ≦ 300 nm, preferably 125 nm ≦ r ≦ 250 nm, particularly preferably 30 nm ≦ r ≦ 200 nm is desirable. By using a pigment having such an average particle diameter, a pixel having a high contrast ratio and a high light transmittance can be obtained. Here, the “average particle size” means the average particle size of secondary particles in which primary particles (single crystallites) of the pigment are aggregated. The average primary particle diameter is obtained by observing with an SEM (Scanning Electron Microscope) or TEM (Transmission Electron Microscope), measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating the average value. Can do.
The particle size distribution of the secondary particles of the pigment that can be used in the present invention (hereinafter, simply referred to as “particle size distribution”) is 70% by mass of secondary particles having an average particle size of ± 100 nm. As mentioned above, it is desirable that it is 80 mass% or more. In the present invention, the particle size distribution is measured using a scattering intensity distribution.

  The pigment having the above average particle size and particle size distribution is preferably a commercially available pigment mixed with other pigments optionally used (average particle size is usually over 300 nm), preferably with a dispersant and a solvent. The pigment mixture can be prepared by mixing and dispersing while pulverizing using a pulverizer such as a bead mill or a roll mill. The pigment thus obtained is usually in the form of a pigment dispersion.

<Miniaturization of pigment>
In the present invention, if necessary, a fine and sized organic pigment can be used. Finer pigments are prepared by preparing a high-viscosity liquid composition together with pigments, water-soluble organic solvents, and water-soluble inorganic salts, and applying a stress using a wet pulverizer and grinding. Achieved.

Examples of the water-soluble organic solvent used in the pigment refining process include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol. Examples thereof include monobutyl ether, propylene glycol, propylene glycol monomethyl ether acetate and the like.
Also, as long as it is adsorbed to the pigment when used in a small amount and is not washed away into the wastewater, other solvents having low or no water solubility such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, nitrobenzene , Aniline, pyridine, quinoline, tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, butyl acetate, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohexane, halogenated hydrocarbon, acetone, methyl ethyl ketone, methyl isobutyl A ketone, cyclohexanone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, or the like may be used.
Only one type of solvent may be used in the pigment refinement step, or two or more types may be mixed and used as necessary.

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

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

<Pigment preparation (color matching)>
These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of the above combinations are shown below. For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment, or a perylene red pigment , A mixture with an anthraquinone red pigment, a diketopyrrolopyrrole red pigment, or the like can be used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 139 or C.I. I. Mixing with Pigment Red 177 is preferred. The mass ratio of the red pigment to the other pigment is preferably 100: 5 to 100: 80. In this range, the light transmittance from 400 nm to 500 nm can be suppressed, the color purity can be improved, and a sufficient coloring power can be achieved. Particularly, the mass ratio is optimally in the range of 100: 10 to 100: 65. In addition, in the case of the combination of red pigments, it can adjust according to chromaticity.

  As the green pigment, one kind of halogenated phthalocyanine pigment may be used alone, or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment may be used. it can. For example, C.I. I. Pigment Green 7, 36, 37, 58 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 200. In the above mass ratio range, the light transmittance of 400 to 450 nm can be suppressed, the color purity can be improved, the main wavelength does not become a long wavelength, and the hue in the vicinity of the NTSC target hue according to the home position. Can be obtained. The mass ratio is particularly preferably in the range of 100: 20 to 100: 150.

As the blue pigment, a single phthalocyanine pigment or a mixture of this and a dioxazine purple pigment can be used. As a particularly preferred example, C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is mentioned.
The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 100, more preferably 100: 70 or less.

As the pigment, an inorganic pigment may be used, and examples of the inorganic pigment include metal-containing inorganic pigments composed of metal pigments, metal compounds, metal oxides, and the like, carbon black, and metal borides.
The composition of the present invention may be used not only for the formation of colored regions (pixels) of a color filter, but also for the formation of a black matrix and a light shielding film, etc. Examples of pigments having black or infrared light shielding properties used in products include carbon, titanium black, iron oxide, titanium oxide, silver tin, silver, tungsten compounds, metal borides, and metal oxides such as titanium oxide. A pigment made of a metal mixture containing the product can be used. Carbon, titanium black, tungsten compound, and metal boride are preferable from the viewpoint of excellent light shielding properties, and titanium black, tungsten compound, and metal boride are more preferable from the viewpoint of excellent sensitivity.

  Two or more of these pigments may be used in combination, or may be used in combination with the dyes described above, dyes described later, organic pigments, and the like. In order to adjust the color tone or to improve the light-shielding property in a desired wavelength region, for example, a mode in which the chromatic color pigment listed in the “pigment preparation” column is mixed with a pigment having black or infrared light-shielding property is mentioned. It is done. The pigment having black or infrared light shielding properties preferably contains a red pigment or dye and a violet pigment or dye, and it is particularly preferred that the color or pigment having infrared light shielding properties contain a red pigment.

Below, a titanium black dispersion is explained in full detail.
The titanium black dispersion is a dispersion containing titanium black as a coloring material.
By including titanium black in the composition of the present invention as a titanium black dispersion prepared in advance, the dispersibility and dispersion stability of titanium black are improved.
Hereinafter, titanium black will be described.

<Titanium Black>
Titanium black is black particles having titanium atoms. Preferred are low-order titanium oxide and titanium oxynitride. The surface of titanium black particles can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, zirconium oxide, and treatment using a water-repellent substance as disclosed in JP 2007-302836 A is also possible. is there.

  The particle size of the titanium black particles is not particularly limited, but is preferably 3 to 2000 nm, more preferably 10 to 500 nm, and still more preferably 20 to 200 nm from the viewpoint of dispersibility and colorability. .

The specific surface area of the titanium black is not particularly limited, but the water repellency after the surface treatment of the titanium black with a water repellent agent has a predetermined performance. Therefore, the value measured by the BET method is usually 5 to 150 m. ² / g approximately, and preferably from 20 to 100 m ² / g approximately.

  Examples of commercially available titanium black include, for example, Titanium Black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, Ako Kasei Co., Ltd., Tilac D manufactured by Mitsubishi Materials Corporation. However, the present invention is not limited to these.

Below, a tungsten compound and a metal boride are explained in full detail.
The composition of the present invention can use a tungsten compound and / or a metal boride.
Tungsten compounds and metal borides have high absorption with respect to infrared rays (light having a wavelength of about 800 to 1200 nm) (that is, they have high light blocking properties (shielding properties) with respect to infrared rays) and absorption with respect to visible light. It is a low infrared shielding material. For this reason, the composition of this invention can form a pattern with high light-shielding property in an infrared region, and high translucency in a visible light region by containing a tungsten compound and / or a metal boride.
In addition, the tungsten compound and the metal boride have a small absorption even for light having a shorter wavelength than that in the visible range used for exposure of a high-pressure mercury lamp, KrF, ArF, and the like used for image formation. For this reason, while combining with the polymeric compound, alkali-soluble resin, and photoinitiator which are mentioned later, while being able to obtain the outstanding pattern, a residue can be suppressed more in pattern formation.

Examples of the tungsten compound include a tungsten oxide compound, a tungsten boride compound, a tungsten sulfide compound, and the like, and a tungsten oxide compound represented by the following general formula (composition formula) (I) is preferable.
M _x W _y O _z (I)
M represents a metal, W represents tungsten, and O represents oxygen.
0.001 ≦ x / y ≦ 1.1
2.2 ≦ z / y ≦ 3.0

  As the metal of M, for example, alkali metal, alkaline earth metal, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and the like can be mentioned, and an alkali metal is preferable. 1 type or 2 types or more may be sufficient as the metal of M.

  M is preferably an alkali metal, more preferably Rb or Cs, and still more preferably Cs.

When x / y is 0.001 or more, infrared rays can be sufficiently shielded, and when it is 1.1 or less, generation of an impurity phase in the tungsten compound can be more reliably avoided. it can.
When z / y is 2.2 or more, chemical stability as a material can be further improved, and when it is 3.0 or less, infrared rays can be sufficiently shielded.

Specific examples of the tungsten oxide compound represented by the general formula (I) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _{3 and the} like. Cs _0.33 WO ₃ or Rb _0.33 WO ₃ is preferable, and Cs _0.33 WO ₃ is more preferable.

  The tungsten compound is preferably fine particles. The average particle diameter of the tungsten fine particles is preferably 800 nm or less, more preferably 400 nm or less, and further preferably 200 nm or less. When the average particle diameter is in such a range, the tungsten fine particles are less likely to block visible light by light scattering, and thus the translucency in the visible light region can be further ensured. From the viewpoint of avoiding photoacid disturbance, the average particle size is preferably as small as possible. However, for reasons such as ease of handling during production, the average particle size of the tungsten fine particles is usually 1 nm or more.

  Two or more tungsten compounds can be used.

Tungsten compounds are commercially available, but when the tungsten compound is, for example, a tungsten oxide compound, the tungsten oxide compound is obtained by a method of heat-treating the tungsten compound in an inert gas atmosphere or a reducing gas atmosphere. (See Japanese Patent No. 4096205).
The tungsten oxide compound is also available as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd.

In addition, as the metal boride, lanthanum boride (LaB ₆ ), praseodymium boride (PrB ₆ ), neodymium boride (NdB ₆ ), cerium boride (CeB ₆ ), yttrium boride (YB ₆ ), boride Titanium (TiB ₂ ), zirconium boride (ZrB ₂ ), hafnium boride (HfB ₂ ), vanadium boride (VB ₂ ), tantalum boride (TaB ₂ ), chromium boride (CrB, CrB ₂ ), boride One or more of molybdenum (MoB ₂ , Mo ₂ B ₅ , MoB), tungsten boride (W ₂ B ₅ ), and the like can be exemplified, and lanthanum boride (LaB ₆ ) is preferable.

  The metal boride is preferably fine particles. The average particle diameter of the metal boride fine particles is preferably 800 nm or less, more preferably 300 nm or less, and still more preferably 100 nm or less. When the average particle diameter is in such a range, it becomes difficult for the metal boride fine particles to block visible light by light scattering, and thus the translucency in the visible light region can be further ensured. From the viewpoint of avoiding photoacid disturbance, the average particle size is preferably as small as possible. However, for reasons such as ease of handling during production, the average particle size of the metal boride fine particles is usually 1 nm or more.

  Two or more metal borides can be used.

  The metal boride is available as a commercial product, for example, as a dispersion of metal boride fine particles such as KHF-7 manufactured by Sumitomo Metal Mining Co., Ltd.

  As content of the coloring agent contained in the composition of this invention, 20-95 mass% is preferable in the total solid of the composition of this invention, 25-90 mass% is more preferable, 30-80 mass% Is more preferable.

<Dye>
Hereinafter, the dye that the colored radiation-sensitive composition of the present invention can contain will be described in more detail.
There is no restriction | limiting in particular in dye, A well-known dye can be used for color filters conventionally. For example, dye monomers and dye multimers can be used. Specifically, pyrazole azo series, anilino azo series, triphenyl methane series, anthraquinone series, anthrapyridone series, benzylidene series, oxonol series, pyrazolo triazole azo series, pyridone azo series, cyanine series, phenothiazine series, pyrrolopyrazole azomethine series, Dyes such as xanthene, phthalocyanine, benzopyran, indigo, pyromethene, and methine can be used. Moreover, you may use the multimer of these dyes.
Moreover, when performing water or alkali image development, an acidic dye and / or its derivative may be used suitably from a viewpoint that the binder and / or dye of a light non-irradiation part are removed completely by image development.
The dye used in the present invention has a partial structure derived from a dye selected from dipyrromethene dye, azo dye, anthraquinone dye, triphenylmethane dye, xanthene dye, cyanine dye, squarylium dye, quinophthalone dye, phthalocyanine dye and subphthalocyanine dye. What has is preferable.
Furthermore, the dye used in the present invention is preferably a multimer having a partial structure and a polymerizable group, and preferably includes a structure such as a dimer, a trimer and a polymer.
In the dye used in the present invention, each of the dyes constituting the partial structure derived from the dye preferably has a dye skeleton having a maximum absorption wavelength in the range of 400 to 780 nm. This dye functions, for example, as a colorant in the colored radiation-sensitive composition of the present invention.
The “partial structure derived from a dye” means a dye multimer linking part (polymer chain or polymer chain) obtained by removing a hydrogen atom from a specific dye (hereinafter also referred to as a dye compound) that can form a dye structure described later. It represents a structure that can be linked to a dendrimer core or the like.

(Partial structure derived from pigment)
Examples of the partial structure derived from the pigment in the dye used in the colored radiation-sensitive composition of the present invention (hereinafter also referred to as “pigment structure”) include quinone pigments (benzoquinone pigments, naphthoquinone pigments, anthraquinone pigments, anthrapyridone pigments). ), Carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes) , Cyanine dye, squarylium dye, croconium dye, etc.), quinophthalone dye, phthalocyanine dye, subphthalocyanine dye, perinone dye, indigo dye, thioindigo dye, quinoline dye, nitro dye, nitro dye Seo dyes, dipyrromethene dyes and dye structure selected from azo dyes and their metal complex dye and the like.
Among these dye structures, from the viewpoint of color separation, substrate adhesion and surface roughness, dipyrromethene dyes, azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes Particularly preferred are dye structures selected from subphthalocyanine dyes.

   In the dye used in the present invention, a hydrogen atom in the pigment structure may be substituted with a substituent selected from the following substituent group A.

(Substituent group A)
Examples of the substituent that the dye multimer may have include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, Carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group , Aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or Arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, etc. Is mentioned.
For details, for example, paragraphs 0027 to 0038 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
Hereinafter, a particularly preferable dye skeleton will be described.

(Anthraquinone dye)
As what has a partial structure derived from the anthraquinone pigment | dye (anthraquinone compound), the partial structure derived from the compound (anthraquinone compound) represented by the following general formula (AQ-1)-(AQ-3) is preferable. In the present invention, the anthraquinone compound is a general term for compounds having a dye moiety containing an anthraquinone skeleton in the molecule.

In General Formula (AQ-1), A and B each independently represent an amino group, a hydroxyl group, an alkoxy group, or a hydrogen atom. Xqa represents ORqa ₁ or NRqa ₂ Rqa _3. Rqa _{1 to} Rqa ₃ each independently represents a hydrogen atom, an alkyl group or an aryl group. Rq ₁ to Rq ₄ represents a substituent. The substituents that Rq _{1 to} Rq ₄ can take are the same as the substituents mentioned in the section of the substituent group A. Ra and Rb each independently represents a hydrogen atom, an alkyl group or an aryl group.

In general formula (AQ-2), C and D are synonymous with A and B in general formula (AQ-1). Xqb represents ORqb ₁ or NRqb ₂ Rqb _3. Rqb _{1 to} Rqb ₃ each independently represents a hydrogen atom, an alkyl group or an aryl group. Rq ₅ to Rq ₈ represents a substituent. Rq ₅ to Rq ₈ is the general formula as defined in _{(AQ-1) Rq 1 ~Rq} 4 in. Rc has the same meaning as Ra or Rb in formula (AQ-1).

In general formula (AQ-3), E and F are synonymous with A and B in general formula (AQ-1). Xqc represents ORqc ₁ or NRqc ₂ Rqc _3. Rqc ₁ ~Rqc ₃ each independently represents a hydrogen atom, an alkyl group or an aryl group. Rq ₉ to Rq ₁₂ is formula synonymous with _{(AQ-1) Rq 1 ~Rq} 4 in. Rd has the same meaning as Ra or Rb in formula (AQ-1).
As preferable ranges of the general formulas (AQ-1), (AQ-2), and (AQ-3), for example, paragraphs 0045 to 0047 of JP-A-2013-29760 can be referred to, and the contents thereof are described in this application. Incorporated in the description.

  As specific examples of the anthraquinone dye, for example, paragraphs 0049 and 0050 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

(Triphenylmethane dye)
As what has a partial structure derived from a triphenylmethane pigment | dye (triphenylmethane compound), the partial structure derived from the compound (triphenylmethane compound) represented by the following general formula (TP) is preferable. In the present invention, the triphenylmethane compound is a general term for compounds having a dye moiety containing a triphenylmethane skeleton in the molecule.

Formula (TP)

(In the formula (TP), Rtp ^{1 to} Rtp ⁴ each independently represents a hydrogen atom, an alkyl group or an aryl group. Rtp ⁵ represents a hydrogen atom, an alkyl group, an aryl group or NRtp ⁹ Rtp ¹⁰ (Rtp ⁹ And Rtp ¹⁰ represents a hydrogen atom, an alkyl group or an aryl group) Rtp ⁶ , Rtp ⁷ and Rtp ⁸ represent a substituent, a, b and c represent an integer of 0 to 4. a, If b and c is 2 or more, Rtp ^6, Rtp ⁷ and Rtp ⁸ are may be coupled to each other to form a ring .X ^- is .X representing the anion structure ^- if there is no, Rtp ¹ ~ At least one of Rtp ⁷ contains an anion.
As a preferable range of the general formula (TP), for example, paragraphs 0055 to 0062 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

(Xanthene dye)
As what has a partial structure derived from a xanthene pigment (xanthene compound), the partial structure derived from the xanthene compound represented by the following general formula (J) is preferable.

In the general formula (J), R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ each independently represents a hydrogen atom or a monovalent substituent, R ⁸⁵ each independently represents a monovalent substituent, and m is 0 Represents an integer from 5 to 5. X ⁻ represents an anion. When X ⁻ is not present, at least one of R ^{81 to} R ⁸⁵ contains an anion.
As a preferable range of the general formula (J), for example, paragraphs 0066 to 0073 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

(Cyanine dye)
As the one having a partial structure derived from a cyanine dye (cyanine compound), a partial structure derived from a compound (cyanine compound) represented by the following general formula (PM) is preferable. In the present invention, the cyanine compound is a general term for compounds having a dye moiety containing a cyanine skeleton in the molecule.

In general formula (PM), ring Z1 and ring Z2 each independently represent a heterocyclic ring which may have a substituent. l represents an integer of 0 or more and 3 or less. X ⁻ represents an anion.
As a preferable range of the general formula (PM), for example, paragraphs 0077 to 0084 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

(Squarylium dye)
As what has a partial structure derived from a squarylium pigment | dye (squarylium compound), the partial structure derived from the compound (squarylium compound) represented by the following general formula (K) is preferable. In the present invention, the squarylium compound is a general term for compounds having a dye moiety containing a squarylium skeleton in the molecule.

In general formula (K), A and B each independently represent an aryl group or a heterocyclic group. The aryl group is preferably an aryl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, and examples thereof include phenyl and naphthyl. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group, and examples include pyroyl, imidazoyl, pyrazoyl, thienyl, pyridyl, pyrimidyl, pyridazyl, triazol-1-yl, thienyl, furyl, thiadiazoyl and the like. .
As a preferable range of the general formula (K), for example, paragraphs 0088 to 0106 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

(Quinophthalone dye)
As a compound having a partial structure derived from a quinophthalone dye (quinophthalone compound), a partial structure derived from a compound (quinophthalone compound) represented by the following general formula (QP) is preferable. In the present invention, the quinophthalone compound is a general term for compounds having a dye moiety containing a quinophthalone skeleton in the molecule.

In general formula (QP), Rqp ^{1 to} Rqp ⁶ each independently represents a hydrogen atom or a substituent. When at least two of Rqp ^{1 to} Rqp ⁶ are adjacent to each other, they may be bonded to each other to form a ring, and the above-described ring may further have a substituent.
As a preferable range of the general formula (QP), for example, paragraphs 0110 to 0114 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

(Phthalocyanine dye)
As what has a partial structure derived from a phthalocyanine pigment | dye (phthalocyanine compound), what has the partial structure derived from the compound (phthalocyanine compound) represented by the following general formula (F) is preferable. In the present invention, the phthalocyanine compound is a general term for compounds having a dye moiety containing a phthalocyanine skeleton in the molecule.

In the general formula (F), M ¹ represents a metal, and Z ¹ , Z ² , Z ³ , and Z ⁴ are each independently composed of an atom selected from a hydrogen atom, a carbon atom, and a nitrogen atom. Represents a group of atoms necessary to form a 6-membered ring.
As a preferable range of the general formula (F), for example, paragraphs 0118 to 0124 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

(Subphthalocyanine compound)
As what has a partial structure derived from a subphthalocyanine pigment | dye (phthalocyanine compound), what has the partial structure derived from the compound (subphthalocyanine compound) represented by the following general formula (SP) is preferable. In the present invention, the term “subphthalocyanine compound” is a general term for compounds having a dye moiety containing a subphthalocyanine skeleton in the molecule.

In the general formula (SP), Z ^{1 to} Z ¹² each independently represent a hydrogen atom, an alkyl group, an aryl group, a hydroxy group, a mercapto group, an amino group, an alkoxy group, an aryloxy group, or a thioether group. X represents an anion.
As a preferable range of the general formula (SP), for example, paragraphs 0128 to 0133 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
As for the dipyrromethene dye and the azo dye, for example, paragraphs 0033 to 0135 of JP 2011-95732 A can be referred to, and the contents thereof are incorporated in the present specification.

  (Structure of dye used for colored radiation-sensitive composition of the present invention)

  The dye used in the colored radiation-sensitive composition of the present invention may be a dye monomer having one partial structure derived from the above-described dye in the molecule, or the partial structure derived from the above-described dye is a molecule. It may be a dye oligomer or dye multimer having two or more.

(Dye monomer)
The dye monomer preferably contains a polymerizable group.
By adopting such a configuration, the heat resistance tends to be improved. One type of polymerizable group may be included, or two or more types may be included. As the polymerizable group, a known polymerizable group that can be cross-linked by a radical, acid or heat can be used. For example, a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetane group), a methylol group, etc. In particular, a group containing an ethylenically unsaturated bond is preferable, a (meth) acryloyl group is more preferable, and (meth) acryloyl derived from glycidyl (meth) acrylate and 3,4-epoxy-cyclohexylmethyl (meth) acrylate The group is particularly preferred.

  Examples of the method for introducing a polymerizable group include a method in which a dye monomer and a polymerizable group-containing compound are copolymerized and introduced. For these methods, for example, paragraphs 0181 to 0188 in JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

  1-4 are preferable and, as for the number of the polymeric groups in 1 molecule of a pigment | dye monomer, 1-2 are more preferable.

The dye monomer may have an alkali-soluble group. Examples of the alkali-soluble group include a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
Examples of the method for introducing an alkali-soluble group into the dye monomer include a method in which an alkali-soluble group is introduced into the dye monomer in advance.
1-4 are preferable and, as for the number of alkali-soluble groups in 1 molecule of a pigment | dye monomer, 1-2 are more preferable.
Other functional groups that the dye monomer may have include development promoting groups such as lactones, acid anhydrides, amides, —COCH ₂ CO—, cyano groups, long chain and cyclic alkyl groups, aralkyl groups, Examples include an affinity control group such as an aryl group, a polyalkylene oxide group, a hydroxyl group, a maleimide group, and an amino group, which can be appropriately introduced.

  The acid value of the dye monomer is preferably 5 to 200 mgKOH / g, and more preferably 10 to 180 mgKOH / g.

(Dye oligomer)
The dye oligomer is an oligomer having two or more partial structures derived from the above-mentioned dye in the molecule, and includes any structure from a dimer to an octamer. The dye oligomer is preferably an oligomer represented by the following general formula (I).

Formula (I)
(R) _m -Q- (D) _n
(In general formula (I), Q represents a (m + n) -valent linking group, R represents a substituent, D represents the dye structure described above, m represents an integer of 0 to 6, n represents an integer of 2 to 8, and (m + n) represents an integer of 2 to 8. When m is 2 or more, a plurality of Rs may be different from each other. D may be different from each other.)

  Q in the general formula (I) represents a (m + n) -valent linking group, and is preferably a 3- to 6-valent linking group.

The (m + n) -valent linking group represented by Q is preferably a linking group represented by the following general formula (Q-1) or (Q-2).
General formula (Q-1)

(In general formula (Q-1), R ^{1 to} R ⁴ each independently represents a linking group or a substituent. However, at least two of R ^{1 to} R ⁴ are linking groups.)

The substituent represented by R ^{1 to} R ⁴ is an alkyl group having 1 to 10 carbon atoms (preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms), or 6 to 20 carbon atoms. An aryl group (preferably an aryl group having 6 to 14 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms) is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and a methyl group, an ethyl group, or a propyl group is preferable. Further preferred.

The linking group represented by R ^{1 to} R ⁴ is an alkylene group (preferably a linear or branched alkylene group, more preferably — (CH ₂ ) _n1 — (n1 is preferably an integer of 1 to 3). ), - O -, - CO -, - SO 2 - or -NRa- (where, Ra is an alkyl a group or a hydrogen atom), and combinations of two or more of these 1 to 5 carbon atoms A group is more preferable, and a group composed of a combination of two or more of an alkylene group, —O—, —CO—, and —NRa— is more preferable.
In the linking group represented by R ^{1 to} R ⁴ , the number of atoms connecting R or D and C at the center is preferably 1 to 15 respectively, and more preferably 1 to 10 respectively. For example, when the linking group is —CH ₂ —CH ₂ —C (═O) —O—CH ₂ —, the number of atoms connecting R or D and the central C is 5.

  General formula (Q-2)

(In General Formula (Q-2), A ^{1 to} A ⁴ each independently represents a carbon atom or a nitrogen atom. R ^{11 to} R ¹⁶ each independently represents a hydrogen atom, ═O, or a linking group. Represents a single bond or a double bond.)

Examples of the 6-membered ring including A ^{1 to} A ⁴ in the general formula (Q-2) include an aliphatic ring, a heterocyclic ring, and a benzene ring, and a heterocyclic ring and a benzene ring are preferable.

The linking group represented by R ¹¹ to R ^16, formula (Q-1) during the same meaning as the linking group represented by R ¹ to R ⁴ of, and preferred ranges are also the same.

  Specific examples of the (m + n) -valent linking group represented by Q are shown below. However, the present invention is not limited to these.

R in general formula (I) represents a substituent each independently, and when m is 2 or more, a plurality of R may be different from each other.
Examples of the substituent represented by R include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, and a carboxyl group. , Alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryl Oxycarbonylamino, sulfamoylamino, alkyl or arylsulfonylamino, mercapto, alkylthio, arylthio, heterocyclic thio, sulfamoyl, sulfo, alkyl or arylsulfinyl, alkyl Or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group And a silyl group.

  R may be a polymerizable group or an alkali-soluble group.

  Examples of the polymerizable group include known polymerizable groups that can be crosslinked by radicals, acids, and heat. Examples include a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetane group), a methylol group, a group containing an ethylenically unsaturated bond is preferred, a (meth) acryloyl group is more preferred, Particularly preferred are (meth) acryloyl groups derived from glycidyl (meth) acrylate and 3,4-epoxy-cyclohexylmethyl (meth) acrylate.

  Examples of the alkali-soluble group include acid groups such as a carboxyl group, a sulfo group, and a phosphoric acid group. A carboxyl group is preferred.

m represents an integer of 0 to 6, preferably an integer of 1 to 4, and more preferably an integer of 1 to 3.
n represents an integer of 2 to 8, preferably an integer of 2 to 6, and more preferably an integer of 2 to 5.
m + n represents an integer of 2-8, preferably an integer of 2-7, and more preferably an integer of 3-6.

(Dye multimer)
The dye multimer has two or more partial structures derived from the aforementioned dye in the molecule. The dye multimer is a dye multimer comprising at least one of structural units represented by the following general formula (A), general formula (B), and general formula (C), or the general formula ( A dye multimer represented by D) is preferred. According to the production method of the present invention, even when a dye multimer that is likely to retain a residue is used, the residue is reduced, the pattern linearity is excellent, the deterioration of the surface roughness can be suppressed, and the effect desired by the present invention is further improved. Remarkably obtained.

Structural unit represented by general formula (A)

In general formula (A), X ₁ represents a linking group formed by polymerization, and L ₁ represents a single bond or a divalent linking group. DyeI represents the dye structure described above.
Hereinafter, the general formula (A) will be described in detail.

In general formula (A), X ₁ represents a linking group formed by polymerization. That is, it refers to a portion that forms a structural unit corresponding to the main chain formed by the polymerization reaction. In addition, the site | part represented by two * becomes a structural unit. X ₁ is not particularly limited as long as it is a linking group formed from a known polymerizable monomer, but linking groups represented by the following (XX-1) to (X-24) are particularly preferred, (XX -1) and (XX-2) (meth) acrylic linking chains, (XX-10) to (XX-17) styrenic linking chains, (XX-18) and (XX-) 19), and more preferably selected from vinyl-based linking chains represented by (XX-24), (meth) acrylic linking chains represented by (XX-1) and (XX-2), More preferably, it is selected from styrene-based connecting chains represented by (XX-10) to (XX-17) and vinyl-based connecting chains represented by (XX-24), and (XX-1) and (XX -2) and a (meth) acrylic linking chain represented by (XX-11) Styrene connecting chains are more preferred.
In (XX-1) to (X-24), the site indicated by * is linked to L ¹ . Me represents a methyl group. R in (XX-18) and (XX-19) represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

In general formula (A), L ₁ represents a single bond or a divalent linking group. When L ₁ represents a divalent linking group, the divalent linking group may be a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (for example, a methylene group, an ethylene group, a trimethylene group, a propylene group, a butylene group). Etc.), a substituted or unsubstituted arylene group having 6 to 30 carbon atoms (for example, a phenylene group, a naphthalene group, etc.), a substituted or unsubstituted heterocyclic linking group, -CH = CH-, -O-, -S- , —C (═O) —, —CO ₂ —, —NR—, —CONR—, —O ₂ C—, —SO—, —SO ₂ — and a linking group formed by linking two or more thereof. Represents. A configuration in which L ₁ contains an anion is also preferable. L ₁ is more preferably a single bond or an alkylene group, and more preferably a single bond or — (CH ₂ ) n — (n is an integer of 1 to 5). Here, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently. An example of the case where L ₁ contains an anion will be described later.

In general formula (A), DyeI represents the dye structure described above.
The dye multimer having the structural unit represented by the general formula (A) includes (1) a method of synthesizing a monomer having a dye residue by addition polymerization, (2) an isocyanate group, an acid anhydride group or an epoxy group. It can be synthesized by a method in which a polymer having a highly reactive functional group is reacted with a dye having a functional group (hydroxyl group, primary or secondary amino group, carboxyl group, etc.) capable of reacting with the highly reactive group.
Known addition polymerizations (radical polymerization, anionic polymerization, cationic polymerization) can be applied to the addition polymerization, but among these, synthesis by radical polymerization is particularly preferable because the reaction conditions can be moderated and the dye structure is not decomposed. Known reaction conditions can be applied to the radical polymerization. That is, the dye multimer used in the present invention is preferably an addition polymer.
Among them, the dye multimer having the structural unit represented by the general formula (A) is a radical polymer obtained by radical polymerization using a dye monomer having an ethylenically unsaturated bond from the viewpoint of heat resistance. It is preferable that
For details of the general formula (A), paragraphs 0138 to 0152 of JP 2013-29760 A can be referred to, and the contents thereof are incorporated in the present specification.

Structural unit represented by general formula (B)

In general formula (B), X ₂ has the same meaning as X ₁ in general formula (A). L ₂ has the same meaning as L ¹ in formula (A). Y ₂ represents a group capable of ionic bonding or coordination bonding with DyeII. DyeII represents a dye structure. For details of the general formula (B), paragraphs 0156 to 0161 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

Structural unit represented by general formula (C)

In general formula (C), L ₃ represents a single bond or a divalent linking group. DyeIII represents a dye structure. m represents 0 or 1; For details of the general formula (C), paragraphs 0165 to 0167 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

Dye multimer represented by general formula (D)

In general formula (D), L ₄ represents an n-valent linking group. n represents an integer of 2 to 20. When n is 2 or more, the structures of DyeIV may be the same or different. DyeIV represents a dye structure. For details of the general formula (D), paragraphs 0173 to 0178 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

  Of the dye multimer having the structural unit represented by the general formula (A), the general formula (B) and / or the general formula (C), and the dye multimer represented by the general formula (D), the general formula Since the dye multimer having the structural unit represented by (A) and the general formula (C) and the dye multimer represented by the general formula (D) are linked by a covalent bond, the dye multimer contains The colored radiation-sensitive composition is preferable because it is excellent in heat resistance and has an effect of suppressing color transfer to other adjacent colored patterns when the colored radiation-sensitive composition is applied to the formation of a plurality of colored patterns. In particular, the compound represented by the general formula (A) is preferable because the molecular weight of the dye multimer is easily controlled.

  In the dye multimer, the content of the constitutional unit having a dye structure is preferably 15 to 60 mol%, when the total constitutional unit in the dye multimer is 100 mol%, and is preferably 20 to 50 mol%. Is more preferable, and it is especially preferable that it is 20-45 mol%.

<< other functional groups or other structural units >>
The dye multimer may have a functional group, a constituent unit other than the constituent unit having a dye structure, and the like.
The functional group may be contained in a constituent unit having a dye structure, or may be contained as another constituent unit containing a functional group separately from the constituent unit having a dye structure.
Examples of functional groups include polymerizable groups and alkali-soluble groups.
Details of these will be described below.

<<< polymerizable group >>
One type of polymerizable group may be included, or two or more types may be included.
As the polymerizable group, a known polymerizable group that can be crosslinked by a radical, acid, or heat can be used. For example, a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetane group), or a methylol group. In particular, a group containing an ethylenically unsaturated bond is preferable, a (meth) acryloyl group is more preferable, glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate-derived (meth) More preferred is an acryloyl group.

The structural unit having a polymerizable group is preferably represented by the following general formula (P).
General formula (P)

In general formula (P), X ¹ represents a linking group formed by polymerization, and L ¹ represents a single bond or a divalent linking group. P represents a polymerizable group.
X ¹ and L ¹ in the general formula (P), have the same meanings as X ¹ and L ₁ in formula (A), and preferred ranges are also the same.

  As a method for introducing a polymerizable group, (1) (a) a method in which a polymerizable group is introduced by modifying it with a polymerizable group-containing compound, and (2) a copolymerization of the polymerizable group-containing compound is performed. There are methods to introduce.

When a polymerizable group is contained in the dye monomer, the amount of the polymerizable group contained in the dye monomer is preferably 0.1 to 2.0 mmol with respect to 1 g of the dye structure, and 0.2 to 1. It is more preferable that it is 5 mmol, and it is especially preferable that it is 0.3-1.0 mmol.
Moreover, when another structural unit contains a polymeric group, 10-40 mass% is preferable with respect to 100 mass% of all structural units, for example, and 15-35 mass% is more preferable.

  Specific examples of the structural unit having a polymerizable group include the following. However, the present invention is not limited to these.

<< Alkali-soluble group >>
An example of the alkali-soluble group that the dye multimer may have is an acid group. Examples of the acid group include a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
In the present invention, the alkali-soluble group is preferably contained in the dye multimer as a structural unit having an alkali-soluble group. More specifically, in the general formula (P), a repeating unit in which P is an alkali-soluble group is preferable.

  As a method for introducing an alkali-soluble group into a dye multimer, a method in which an alkali-soluble group is introduced into a dye monomer in advance, and a monomer other than a dye monomer having an alkali-soluble group ((meth) acrylic acid, acrylic Modified product of caprolactone of acid, modified product of succinic anhydride of 2-hydroxyethyl (meth) acrylate, modified product of phthalic anhydride of 2-hydroxyethyl (meth) acrylate, 1,2-hydroxyethyl (meth) acrylate 2-cyclohexanedicarboxylic acid anhydride modified product, carboxylic acid-containing monomer such as styrene carboxylic acid, itaconic acid, maleic acid, norbornene carboxylic acid, phosphoric acid-containing monomer such as acid phosphooxyethyl methacrylate, vinyl phosphonic acid, vinyl sulfonic acid, Such as 2-acrylamido-2-methylsulfonic acid A method of copolymerizing a phosphate-containing monomer) may be mentioned, more preferably to use both methods.

The alkali-soluble group amount (acid value) of the dye multimer is preferably 15 mg KOH / g to 130 mg KOH / g, more preferably 25 mg KOH / g to 100 mg KOH / g, and more preferably 25 mg KOH / g. More preferably, it is g-80 mgKOH / g. The alkali-soluble group amount (acid value) can be measured by titration using a 0.1N sodium hydroxide aqueous solution.
Further, when the dye multimer contains a structural unit containing a dye monomer and a structural unit having an acid group, the proportion of the structural unit containing a structural unit having an acid group is the structural unit 100 containing a dye monomer. For example, 5-70 mol is preferable with respect to mol, and 10-50 mol is more preferable.

As functional groups possessed by the dye multimer, lactones, acid anhydrides, amides, —COCH ₂ CO—, development accelerator groups such as cyano groups, long chain and cyclic alkyl groups, aralkyl groups, aryl groups, polyalkylene oxide groups, hydroxyl groups Groups, maleimide groups, amino groups and other hydrophilicity adjusting groups, and the like, which can be appropriately introduced.
Examples of the introduction method include a method of introducing the dye monomer in advance and a method of copolymerizing the monomer having the functional group.

<< Structure Represented by Formulas (1) to (5) >>
In the dye multimer, the structural unit having a dye structure may include structures represented by the formulas (1) to (5).
The structure represented by the formula (1) is generically called a hindered amine system. The structure represented by the formula (2) is generically called a hindered phenol type. The structure represented by the formula (3) is generically called a benzotriazole type. The structure represented by the formula (4) is generically referred to as a hydroxybenzophenone series. The structure represented by the formula (5) is generically called a triazine type.
Of the structures represented by the formulas (1) to (5), the structure represented by the formula (1) and the structure represented by the formula (2) are preferable, and the structure represented by the formula (1) is particularly preferable. . The dye multimer used in the present invention has the dye structure and the structure represented by the formula (1) in the same molecule, so that the amine group in the structure represented by the formula (1) can interact with the substrate. Since it acts, adhesiveness can be improved more.

In formula (1), R ¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group, or an oxy radical. R ² and R ³ each independently represents an alkyl group having 1 to 18 carbon atoms. R ² and R ³ may be bonded to each other to represent an aliphatic ring having 4 to 12 carbon atoms. “*” Represents a bond between the structure represented by the formula (1) and the polymer skeleton.

In Formula (1), R ¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group, or an oxy radical, and an alkyl group having 1 to 18 carbon atoms is preferable.
The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, but is preferably linear. 1-12 are preferable, as for carbon number of a C1-C18 alkyl group, 1-8 are more preferable, 1-3 are more preferable, and 1 or 2 is especially preferable. In particular, the alkyl group having 1 to 18 carbon atoms is preferably a methyl group or an ethyl group, and more preferably a methyl group.
6-18 may be sufficient as carbon number of an aryl group, 6-12 may be sufficient, and 6-6 may be sufficient. Specific examples include a phenyl group.
When R ¹ in Formula (1) represents an alkyl group or aryl group having 1 to 18 carbon atoms, the alkyl group or aryl group having 1 to 18 carbon atoms may have a substituent or is unsubstituted. It may be. Examples of the substituent which may have include a substituent selected from the substituent group A described above.
In formula (1), R ² and R ³ each independently represent an alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. R ² and R ³ may be bonded to each other to represent an aliphatic ring having 4 to 12 carbon atoms.
In formula (1), “*” represents a bond between the structure represented by formula (1) and the polymer skeleton. The bond may be bonded to the polymer backbone directly or via a linking group, or may be bonded to the above-described dye structure directly or via a linking group. In particular, “*” in formula (1) is preferably bonded to the polymer backbone directly or via a linking group.
Hereinafter, although the specific example of the structure represented by Formula (1) is shown, it is not limited to these. In the following structure, “*” represents a bond between the structure represented by the formula (2) and the polymer skeleton.

In formula (2), R ⁴ represents the following formula (2A), an alkyl group having 1 to 18 carbon atoms or an aryl group. R ⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. “*” Represents a bond between the structure represented by the formula (2) and the polymer skeleton.
In formula (2), R ⁴ represents the above formula (2A), an alkyl group having 1 to 18 carbon atoms or an aryl group, and is preferably represented by formula (2A). Alkyl and aryl groups having 1 to 18 carbon atoms has the same meaning as the alkyl and aryl groups having 1 to 18 carbon atoms described in R ¹ in the formula (1). “*” Has the same meaning as the bond described in the formula (1).

In formula (2A), R < ⁶ > represents a C1-C18 alkyl group each independently. “*” Represents a bond between the structure represented by the formula (2A) and the structure represented by the formula (2).
In the formula (2A), R ⁶ has the same meaning as the alkyl group having 1 to 18 carbon atoms described in R ¹ in the formula (1). “*” Has the same meaning as the bond described in the formula (1).
Hereinafter, although the specific example of the structure represented by Formula (2) is shown, it is not limited to these. In the following structure, “*” represents a bond between the structure represented by the formula (2) and the polymer skeleton.

Wherein (3), R ⁷ represents an alkyl group having 1 to 18 carbon atoms; n1 represents an integer of 0 to 3. When n1 is 2 or 3, each R ⁷ may be the same or different. “*” Represents a bond between the structure represented by the formula (3) and the polymer skeleton.
In formula (3), R ⁷ has the same meaning as the alkyl group having 1 to 18 carbon atoms described in R ¹ in formula (1).
In Formula (3), n1 represents an integer of 0 to 3, an integer of 0 to 2 is preferable, and 0 or 1 is preferable.
In formula (3), “*” is synonymous with the bond described in formula (1).
Hereinafter, although the specific example of the structure represented by Formula (3) is shown, it is not limited to these. In the following structure, “*” represents a bond between the structure represented by the formula (3) and the polymer skeleton.

In formula (4), R ⁸ and R ⁹ each independently represents an alkyl group having 1 to 18 carbon atoms. n2 represents an integer of 0 to 3. n3 represents an integer of 0 to 4. When n2 is 2 or 3, each R ⁸ may be the same or different. When n3 represents an integer of 2 to 4, each R ⁹ may be the same or different. “*” Represents a bond between the structure represented by the formula (4) and the polymer skeleton.
In the formula (4), R ⁸ and R ⁹ has the same meaning as alkyl group having 1 to 18 carbon atoms described in R ¹ in the formula (1).
In formula (4), n2 represents the integer of 0-3, the integer of 0-2 is preferable and 0 or 1 is preferable.
In Formula (4), n3 represents an integer of 0 to 4, an integer of 0 to 2 is preferable, and 0 or 1 is preferable.
In formula (4), “*” has the same meaning as the bond described in formula (1).
Hereinafter, although the specific example of the structure represented by Formula (4) is shown, it is not limited to these. In the following structure, “*” represents a bond between the structure represented by the formula (4) and the polymer skeleton.

In formula (5), R ^{10 to} R ¹² each independently represents an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. n4 to n6 each independently represents an integer of 0 to 5. n7 to n9 each independently represents 0 or 1, and at least one of n7 to n9 represents 1. “*” Represents a bond between the structure represented by the formula (5) and the polymer skeleton.

If R ¹⁰ in the formula (5) represents an alkyl group having 1 to 18 carbon atoms, it has the same meaning as alkyl group having 1 to 18 carbon atoms described in R ¹ in the formula (1), 1 to 3 carbon atoms The alkyl group is preferably a methyl group. If R ¹⁰ represents an alkoxy group having 1 to 8 carbon atoms, carbon atoms in the alkoxy group is preferably 1 to 6, more preferably 1 to 5, 1 to 4 is more preferred.
N4 in Formula (5) represents an integer of 0 to 5, an integer of 1 to 4 is preferable, and 2 or 3 is preferable. When n4 represents an integer of 2 to 5, each R ¹⁰ may be the same or different.
R ¹¹ in formula (5) has the same meaning as R ¹⁰ in formula (5), and the preferred range is also the same.
N5 in Formula (5) represents an integer of 0 to 5, an integer of 1 to 3 is preferable, and 1 or 2 is preferable. When n5 represents an integer of 2 to 5, each R ¹¹ may be the same or different.
R ¹² in formula (5) has the same meaning as R ¹⁰ in formula (5), and the preferred range is also the same.
N6 in Formula (5) represents an integer of 0 to 5, an integer of 0 to 3 is preferable, and 0 or 1 is preferable. When n6 represents an integer of 2 to 5, each R ¹² may be the same or different.
N7 to n9 in the formula (5) each independently represents 0 or 1, and at least one of n7 to n9 represents 1. In particular, it is preferable that only n7 represents 1, only n8 and n9 represent 1, or only one of n7, n8 and n9 represents 1.
R < ¹⁰ > -R < ¹² > in Formula (5) may have a substituent each independently, and may be unsubstituted. Examples of the substituent which may have include a substituent selected from the substituent group A described above.
In formula (5), “*” is synonymous with the bond described in formula (1).
Hereinafter, although the specific example of the structure represented by Formula (5) is shown, it is not limited to these. In the following structure, “*” represents a bond between the structure represented by the formula (5) and the polymer skeleton.

<<<<<< Structural Unit having at least one of the structures represented by Formulas (1) to (5) >>>>
The structural unit having at least one of the structures represented by the formulas (1) to (5) is preferably represented by the following formula (E).

Formula (E)

In general formula (E), X ³ has the same meaning as X ¹ in general formula (A). L ⁴ has the same meaning as L ¹ in formula (A). Z ¹ represents a structure represented by the above-described formulas (1) to (5).
Hereinafter, although the specific example of the structural unit which has at least 1 of the structure represented by Formula (1)-(5) is shown, this invention is not limited to these.

In the dye multimer, when the total constitutional unit in the dye multimer is 100% by mass, the content of the constitutional unit having at least one of the structures represented by the formulas (1) to (5) is 0.5 to It is preferably 20% by mass, more preferably 1 to 10% by mass, and particularly preferably 1 to 5% by mass.
The content of the structural unit having at least one of the structures represented by the formulas (1) to (5) with respect to 1 mol of the structural unit including the dye structure is preferably 0.5 to 25 mol%. 10 mol% is more preferable and 1-5 mol% is further more preferable.

《Counter anion》
When the dye structure used in the present invention has a cation structure, the counter anion may be in the same constituent unit of the dye multimer or outside the same constituent unit. The counter anion is in the same structural unit means that the cation and the anion are bonded via a covalent bond in the structural unit having a dye structure. On the other hand, “outside the same structural unit” means a case other than the above. For example, the case where the cation and the anion are not bonded via a covalent bond and exist as separate compounds, and the case where the cation and the anion are contained as independent structural units of the dye multimer, etc.
The anion in the present invention is preferably a non-nucleophilic anion. The non-nucleophilic anion may be an organic anion or an inorganic anion, and an organic anion is preferred. Examples of the counter anion used in the present invention include known non-nucleophilic anions described in paragraph No. 0075 of JP-A-2007-310315, the contents of which are incorporated herein. Here, the non-nucleophilic property means a property that does not nucleophilic attack the dye by heating.

When the counter anion is in the same structural unit The first embodiment of the anion in the present invention is when the counter anion is in the same structural unit. Specifically, in the structural unit having a dye structure, the cation And an anion are bonded via a covalent bond.
The anion moiety in this case is at least selected from —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , a structure represented by the following general formula (A1), and a structure represented by the following general formula (A2). 1 type is preferable and at least 1 sort (s) selected from the structure represented by the following general formula (A1) and the structure represented by the following general formula (A2) is more preferable.
Moreover, the anion part may contain the carboxylic acid anion, the sulfonic acid anion, the anion represented by general formula (A1-1-2), or the anion represented by general formula (A1-1-3).

General formula (A1)

(In general formula (A1), R ¹ and R ² each independently represent —SO ₂ — or —CO—.)
In formula (A1), at least one of R ¹ and R ² -SO ₂ - preferably represents an, both R ¹ and R ² are -SO ₂ - and more preferably represents.

The general formula (A1) is more preferably represented by the following general formula (A1-1).
Formula (A1-1)

(In General Formula (A1-1), R ¹ and R ² each independently represent —SO ₂ — or —CO—, and X ¹ and X ² each independently represent an alkylene group or an arylene group. )
In formula (A1-1), R ¹ and R ² of the general formula (A1) in the same meaning as R ¹ and R ^2, and preferred ranges are also the same.
When X < ¹ > represents an alkylene group, 1-8 are preferable and, as for carbon number of an alkylene group, 1-6 are more preferable. When X < ¹ > represents an arylene group, 6-18 are preferable, as for carbon number of an arylene group, 6-12 are more preferable, and 6 is more preferable. When X ¹ has a substituent, it is preferably substituted with a fluorine atom.
X ² represents an alkyl group or an aryl group, and an alkyl group is preferable. 1-8 are preferable, as for carbon number of an alkyl group, 1-6 are more preferable, 1-3 are more preferable, and 1 is especially preferable. When X ² has a substituent, it is preferably substituted with a fluorine atom.

General formula (A2)

(In the general formula (A2), R ³ represents —SO ₂ — or —CO—. R ⁴ and R ⁵ each independently represents —SO ₂ —, —CO— or —CN).
Preferably representing the at least two R ³ to R ⁵ is -SO ₂ - - In formula (A2), at least one of R ³ to R ⁵ -SO ₂ more preferably represents.

Particularly in the present embodiment, when the skeleton of the dye multimer is represented by the structural unit represented by the general formula (A), a part of L ₁ is represented by the general formula (A1). The case where it contains is mentioned as a preferable example. Specific examples in this case include (a-xt-1), (a-xt-5), and (a-xt-6) among examples of structural units having a dye structure to be described later.
In the present embodiment, the case where the skeleton of the dye multimer includes the structural unit represented by the general formula (B) is also given as an example. Specific examples in this case include (B-dp-1), (B-mp-1), (B-xt-1), (B-xt-) among examples of structural units having a dye structure described later. 2) is exemplified.

In the case where the counter anion is a different molecule The second embodiment of the anion in the present invention is a case where the counter anion is outside the same structural unit, and the cation and the anion do not bind via a covalent bond and exist as separate molecules. This is the case.
Examples of the anion in this case include a fluorine anion, a chlorine anion, a bromine anion, an iodine anion, a cyanide ion, a perchlorate anion, and a non-nucleophilic anion, and a non-nucleophilic anion is preferable.
The non-nucleophilic counter anion may be an organic anion or an inorganic anion, and an organic anion is preferred. Examples of the counter anion used in the present invention include known non-nucleophilic anions described in paragraph No. 0075 of JP-A-2007-310315, the contents of which are incorporated herein.
Preferably, bis (sulfonyl) imide anion, tris (sulfonyl) methyl anion, tetraarylborate anion, B ⁻ (CN) _n1 (OR ^a ) _4-n1 (R ^a is ^a C 1-10 alkyl group or carbon number Represents an aryl group of 6 to 10, n1 represents 1 to 4) and PF _n2 R ^P _(6-n2) ⁻ (R ^P represents a fluorinated alkyl group having 1 to 10 carbon atoms, and n2 represents 1 to 6 And is more preferably selected from a bis (sulfonyl) imide anion, a tris (sulfonyl) methyl anion and a tetraarylborate anion, and more preferably a bis (sulfonyl) imide anion. By using such a non-nucleophilic counter anion, the effects of the present invention tend to be exhibited more effectively.

  As the bis (sulfonyl) imide anion which is a non-nucleophilic counter anion, a structure represented by the following general formula (AN-1) is preferable.

(In Formula (AN-1), X ¹ and X ² each independently represent a fluorine atom or a C 1-10 alkyl group having a fluorine atom. X ¹ and X ² are bonded to each other to form a ring. It may be formed.)

X ¹ and X ² each independently represents a fluorine atom or an alkyl group having 1 to 10 carbon atoms having a fluorine atom, preferably a fluorine atom or an alkyl group having 1 to 10 carbon atoms having a fluorine atom. 10 to 10 perfluoroalkyl groups, more preferably 1 to 4 carbon perfluoroalkyl groups, and particularly preferably a trifluoromethyl group.

  As the tris (sulfonyl) methyl anion which is a non-nucleophilic counter anion, a structure represented by the following general formula (AN-2) is preferable.

(In formula (AN-2), X ³ , X ⁴ and X ⁵ each independently represents a fluorine atom or an alkyl group having 1 to 10 carbon atoms.)

X ³ , X ⁴ and X ⁵ are each independently the same as X ¹ and X ² , and the preferred range is also the same.

  The tetraarylborate anion which is a non-nucleophilic counter anion is preferably a compound represented by the following general formula ((AN-5)).

(In Formula (AN-5), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represents an aryl group.)

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and further an aryl group having 6 to 10 carbon atoms preferable.
The aryl group represented by Ar ¹ , Ar ² , Ar ³ and Ar ⁴ may have a substituent. In the case of having a substituent, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a carbonyl group, a carbonyloxy group, a carbamoyl group, a sulfo group, a sulfonamide group, a nitro group and the like can be mentioned, and a halogen atom and an alkyl group are preferable, A fluorine atom and an alkyl group are more preferable, and a fluorine atom and a perfluoroalkyl group having 1 to 4 carbon atoms are more preferable.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently more preferably a phenyl group having a halogen atom and / or an alkyl group having a halogen atom, and a phenyl group having a fluorine atom and / or an alkyl group having fluorine. Is more preferable.

The non-nucleophilic counter anion also represents —B (CN) _n1 (OR ^a ) _4-n1 (R ^a represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and n1 represents It is preferably an integer of 1 to 4. R ^a as the alkyl group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. R ^a as the aryl group having 6 to 10 carbon atoms is preferably a phenyl group or a naphthyl group.
n1 is preferably 1 to 3, and more preferably 1 or 2.

The non-nucleophilic counter anion is further —PF ₆ R ^P _(6-n2) ⁻ (R ^P represents a fluorinated alkyl group having 1 to 10 carbon atoms, and n2 represents an integer of 1 to 6). It is preferable that R ^P is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably a C 1 to 3 perfluoroalkyl group.
n2 is preferably an integer of 1 to 4, and more preferably 1 or 2.

The mass per molecule of the non-nucleophilic counter anion used in the present invention is preferably from 100 to 1,000, more preferably from 200 to 500.
The dye multimer of the present invention may contain only one type of non-nucleophilic counter anion, or may contain two or more types.

  Specific examples of the non-nucleophilic counter anion used in the present invention are shown below, but the present invention is not limited thereto.

  In the second embodiment, the anion may be a multimer. Examples of the multimer in this case include a multimer containing a structural unit containing an anion and not containing a structural unit derived from a dye structure containing a cation. Here, the structural unit containing an anion can mention the structural unit containing the anion described in 3rd embodiment mentioned later as a preferable example. Furthermore, the multimer containing an anion may have a structural unit other than the structural unit containing an anion. As such a structural unit, another repeating unit that may be contained in the dye multimer used in the present invention to be described later is exemplified as a preferred example.

Case where Cation and Anion are Included in Separate Constituent Units of Dye Multimer As a third embodiment of the present invention, a case where a cation and an anion are contained in independent constituent units of the dye multimer is mentioned.
In the case of this embodiment, the anion may be present in the side chain of the dye multimer, may be present in the main chain, or has a counter anion in both the main chain and the side chain. Also good. Preferably, it is a side chain.
Preferable examples of the structural unit containing an anion include the structural unit represented by the general formula (C1) and the structural unit represented by the general formula (D1).

Formula (C1)

(In general formula (C1), X ¹ represents the main chain of the structural unit. L ¹ represents a single bond or a divalent linking group. Anion represents a counter anion.)

In general formula (C1), X ¹ represents the main chain of the structural unit, and usually represents a linking group formed by a polymerization reaction. For example, (meth) acrylic, styrene, vinyl, and the like are preferable, More preferred are (meth) acrylic and styrene, and (meth) acrylic is more preferred. In addition, the site | part represented by two * becomes a structural unit.

When L ¹ represents a divalent linking group, an alkylene group having 1 to 30 carbon atoms (methylene group, ethylene group, trimethylene group, propylene group, butylene group, etc.), an arylene group having 6 to 30 carbon atoms (phenylene group, Naphthalene group, etc.), heterocyclic linking group, -CH = CH-, -O-, -S-, -C (= O)-, -CO-, -NR-, -CONR-, -OC-, -SO —, —SO ₂ — and a linking group obtained by combining two or more thereof are preferred. Here, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.
In particular, L ¹ is a single bond or an alkylene group having 1 to 10 carbon atoms (preferably — (CH ₂ ) n — (n is an integer of 5 to 10), an arylene group having 6 to 12 carbon atoms (preferably phenylene group, naphthalene group) _{is, - NH -, - CO 2} -, - O- and -SO ₂ - is a divalent linking group formed by combining two or more preferred.

Specific examples of X ^1, examples of X ¹ in formula (A) are exemplified as preferable examples.

General formula (D1)

(In general formula (D1), L ² and L ³ each independently represent a single bond or a divalent linking group. Anion represents the counter anion.)

In General Formula (D1), when L ² and L ³ represent a divalent linking group, an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, a heterocyclic linking group, —CH═CH— , —O—, —S—, —C (═O) —, —CO ₂ —, —NR—, —CONR—, —O ₂ C—, —SO—, —SO ₂ — and combinations of two or more thereof The linking group is preferred. Here, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.
L ² is preferably an arylene group having 6 to 12 carbon atoms (particularly a phenylene group). The arylene group having 6 to 30 carbon atoms is preferably substituted with a fluorine atom.
L ³ is preferably a group composed of a combination of an arylene group having 6 to 12 carbon atoms (particularly a phenylene group) and —O—, and at least one arylene group having 6 to 12 carbon atoms is substituted with a fluorine atom. It is preferable.

  As a counter anion, the anion part described when the said counter anion exists in the same structural unit is illustrated as a preferable anion.

  Although the specific example of the structural unit containing the anion in this embodiment is shown below, this invention is not limited to these.

  The following specific examples show a state where the anion structure is not dissociated, but it goes without saying that the state where the anion structure is dissociated is also within the scope of the present invention.

(Specific examples of dyes)
Although the specific example of dye is shown below, this invention is not limited to this. In the following specific examples, X ⁻ represents an anion. In addition, any hydrogen atom in the dye structure shown below is bonded to the polymer skeleton.
Specific examples of the triphenylmethane compound include the following.

  Specific examples of the xanthene compound include the following.

Examples of structural units having a dye structure used in the present invention are shown below. X ⁻ represents a counter anion. Moreover, although a part of X is shown in a state where the anion structure is not dissociated, it goes without saying that the dissociated state is also included in the present invention.

  Examples of the structural unit having a dye structure include structural units derived from any of the following exemplary compounds M-17 to M-37, M-39, M-40, and M-43.

(Dye characteristics)
The dye used in the present invention preferably has a maximum absorption wavelength of 400 to 650 nm, and more preferably 450 to 600 nm.

The weight average molecular weight of the dye used in the present invention is preferably 2000 or more, more preferably 3000 or more, still more preferably 4000 or more, and particularly preferably 5000 or more. In particular, when the weight average molecular weight of the dye is 5000 or more, the solubility of the colored radiation-sensitive composition of the present invention in a developer is improved. The upper limit of the weight average molecular weight of the dye is not particularly limited, but is preferably 30000 or less, more preferably 20000 or less, further preferably 15000 or less, and particularly preferably 10,000 or less. preferable.
In this specification, the weight average molecular weight and the number average molecular weight are values measured in terms of styrene by the GPC method.
When the dye is a pigment multimer, the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) [(Mw) / (Mn)] is preferably 1.0 to 3.0, It is more preferable that it is 1.6-2.5, and it is especially preferable that it is 1.6-2.0.

  The glass transition temperature (Tg) of the dye used in the present invention is preferably 50 ° C. or higher, and more preferably 100 ° C. or higher. Further, the 5% weight loss temperature by thermogravimetric analysis (TGA measurement) is preferably 120 ° C. or higher, more preferably 150 ° C. or higher, and further preferably 200 ° C. or higher. By being in this region, when the colored radiation-sensitive composition of the present invention is applied to the production of a color filter or the like, it becomes possible to reduce the concentration change caused by the heating process.

Further, the extinction coefficient per unit weight (hereinafter referred to as ε ^′ ; ε ^′ = ε / average molecular weight, unit: L / g · cm) of the dye used in the present invention is preferably 30 or more, and 60 or more. More preferably, it is more preferably 100 or more. By being in this range, when producing a color filter using the colored radiation-sensitive composition of the present invention, a color filter having good color reproducibility can be produced.

The molar extinction coefficient of the dye is preferably as high as possible from the viewpoint of coloring power.
The maximum absorption wavelength and molar extinction coefficient are measured with a spectrophotometer carry5 (manufactured by Varian).

The dye used in the present invention is preferably a compound that dissolves in the following organic solvent. Examples of the organic solvent include esters (eg, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate), ethers (eg, methyl cellosolve acetate, ethyl cellosolve acetate). , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), ketones (methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.), aromatic hydrocarbons (for example, toluene, xylene, etc.), and these solvents It is preferable that 1 mass% or more and 50 mass% or less melt | dissolve with respect to it, More preferably, it is 5-40 mass%, More preferably, it is preferable that it is 10-30 mass%. By being in this region, when the colored radiation-sensitive composition of the present invention is applied to the production of a color filter or the like, it is easy to obtain a suitable coated surface shape, or the concentration decreases due to elution after coating with other colors. It becomes easy to reduce.
In the colored radiation-sensitive composition of the present invention, the dye may be used alone or in combination of two or more.

When using the dye mentioned above, 10-70 mass% is preferable with respect to the total solid of a coloring radiation sensitive composition, and, as for content of the dye in the coloring radiation sensitive composition of this invention, 10-50 % By mass is more preferable, and 15 to 30% by mass is particularly preferable.
Moreover, it is preferable that the density | concentration of the coloring agent containing the dye with respect to the total solid of colored radiation-sensitive composition is 50 mass% or more, and it is more preferable that it is 60 mass% or more.

[Polymerizable compound B]
The polymerizable compound B (hereinafter also simply referred to as “polymerizable compound”) may be any compound that is polymerized by the photopolymerization initiator D described later, and a known polymerizable compound can be used.
Among these, from the viewpoint of polymerizability, an addition polymerizable compound having at least one ethylenically unsaturated double bond can also be used, and at least one terminal ethylenically unsaturated bond, preferably 2 or more, 10 It is preferable to use a compound having no more than one.

Among these, a polymerizable compound having three or more ethylenically unsaturated double bonds (hereinafter sometimes referred to as “polyfunctional monomer”) is preferable as the polymerizable compound from the viewpoint of better adhesion of the colored layer. . Such compounds are widely known in the industrial field, and can be used without particular limitation in the present invention. The polyfunctional monomer in this invention may be used individually by 1 type, and may use 2 or more types together. The polyfunctional monomer used in the present invention is preferably a (meth) acrylate monomer.
As these specific compounds, the compounds described in paragraphs [0095] to [0108] of JP-A-2009-288705 can be suitably used.

  In addition to the above, radically polymerizable monomers represented by the following general formulas (MO-1) to (MO-6) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In the formula, n is 0 to 14 respectively, and m is 1 to 8 respectively. A plurality of R, T and Z present in one molecule may be the same or different. When T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R. At least three of R are polymerizable groups.
n is preferably 0 to 5, and more preferably 1 to 3.
m is preferably 1 to 5, and more preferably 1 to 3.
R is

Is preferred,

Is more preferable.
Specific examples of the radical polymerizable monomer represented by the above general formulas (MO-1) to (MO-6) are described in paragraphs [0248] to [0251] of JP-A No. 2007-26979. A compound can be preferably used.

Among them, as polyfunctional monomers, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku) Co., Ltd.), dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; Nippon Kayaku) And a structure in which these (meth) acryloyl groups are interposed via ethylene glycol and propylene glycol residues. These oligomer types can also be used.
For example, RP-1040 (made by Nippon Kayaku Co., Ltd.) etc. are mentioned.

  As a polyfunctional monomer, you may have acid groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Therefore, if the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is. The acid group may be introduced by reacting the group with a non-aromatic carboxylic acid anhydride. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronix series M-305, M-510, and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g.

  The content of the polymerizable compound (particularly the polyfunctional monomer) is preferably 3% by mass or more, more preferably 5% by mass or more, and further preferably 7% by mass or more in the total solid content of the composition of the present invention. Although there is no restriction | limiting in particular in an upper limit, 50 mass% or less is preferable and 40 mass% or less is more preferable.

  A polymeric compound may be used individually by 1 type, and may be used in combination of 2 or more type. As a preferable example of the combination, it is preferable to combine two kinds of monomers having different polymerizable groups, and combining a monomer having a polymerizable group of 4 or less and a monomer having 5 or more functions can be developed and adhesive. From the viewpoint of

  In the composition of the present invention, the mass ratio (C / B) of the alkali-soluble resin C described later to the polymerizable compound B is preferably 0.3 or more and 2.5 or less, more preferably 0.4 or more and 2.3 or less. Preferably, it is 0.5 or more and 2.0 or less. By being in this range, the residual color at the time of development can be suppressed, and it is excellent in suppressing pattern defects.

[Alkali-soluble resin C]
The alkali-soluble resin C (hereinafter, also simply referred to as “alkali-soluble resin”) is a linear organic high molecular polymer having a molecule (preferably an acrylic copolymer or a styrene copolymer as a main chain). The molecule can be suitably selected from alkali-soluble resins having at least one group that promotes alkali solubility in the molecule. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acryl / acrylamide copolymer resins are preferable. From the viewpoint of development control, acrylic resins and acrylamide resins are preferable. Resins and acrylic / acrylamide copolymer resins are preferred.

  Examples of the group that promotes alkali solubility (hereinafter, also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. What can be developed is preferable, and (meth) acrylic acid is particularly preferable. These acid groups may be used alone or in combination of two or more.

Examples of monomers that can impart an acid group after polymerization include, for example, monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, monomers having an epoxy group such as glycidyl (meth) acrylate, and 2-isocyanatoethyl (meth). And monomers having an isocyanate group such as acrylate. These monomers for introducing an acid group may be only one type or two or more types. In order to introduce an acid group into an alkali-soluble resin, for example, a monomer having an acid group and / or a monomer capable of imparting an acid group after polymerization (hereinafter sometimes referred to as “monomer for introducing an acid group”) .) May be polymerized as a monomer component.
In addition, when introducing an acid group using a monomer capable of imparting an acid group after polymerization as a monomer component, for example, a treatment for imparting an acid group as described later is required after the polymerization.

  For production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

  As the linear organic polymer used as the alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferable, such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, and a crotonic acid copolymer. , Maleic acid copolymers, partially esterified maleic acid copolymers, alkali-soluble phenolic resins such as novolak resins, etc., acid cellulose derivatives having a carboxylic acid in the side chain, and acid anhydrides added to polymers having a hydroxyl group. Can be mentioned. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Examples of vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene Macromonomer, polymethylmethacrylate macromonomer, as N-position-substituted maleimide monomer described in JP-A-10-300922, may be mentioned N- phenylmaleimide, an N- cyclohexyl maleimide and the like. In addition, only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acids, and 2 or more types may be sufficient as it.

  As the alkali-soluble resin, a compound represented by the following general formula (ED) and / or a compound represented by the following general formula (ED2) (hereinafter, these compounds may be referred to as “ether dimers”) are essential. It is also preferable to include a polymer (a) obtained by polymerizing the monomer component.

In General 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.
General formula (ED2)

  In General Formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the general formula (ED2), the description of JP 2010-168539 A can be referred to.

Thereby, the composition of this invention can form the cured coating film which was very excellent also in heat resistance and transparency. In the general formula (ED) showing the ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited. Linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; Alicyclic groups such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; substituted by alkoxy such as 1-methoxyethyl, 1-ethoxyethyl Alkyl groups substituted by aryl groups such as benzyl; and the like It is. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance.

  Specific examples of the ether dimer include, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, (N-propyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) ) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tert-butyl) -2, 2 ′-[oxybis (methylene)] bis-2-propenoate, di (tert-amyl) -2,2 ′-[oxybis (methylene)] bis-2-prope , Di (stearyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2- Ethylhexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-ethoxy) Ethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 ′-[oxybis (methylene) )] Bis-2-propenoate, dicyclohexyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tert-butyl) Cyclohexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tricyclo Decanyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 ′ -[Oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate and the like. Among these, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2′- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be only one kind or two or more kinds. The structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.

  Moreover, in order to improve the crosslinking efficiency of the composition in the present invention, an alkali-soluble resin having a polymerizable group may be used. By having a polymerizable group, the heat resistance and light resistance tend to be further improved. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful. Examples of the polymer containing the above-mentioned polymerizable group include: NR series (manufactured by Mitsubishi Rayon), Photomer 6173 (manufactured by COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co. Ltd.), Biscote R-264, KS resist. 106 (all manufactured by Osaka Organic Chemical Industry), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries), Ebecryl 3800 (manufactured by Daicel UCB), and the like. As the alkali-soluble resin containing these polymerizable groups, an isocyanate resin and an OH group are reacted in advance to leave one unreacted isocyanate group, and a compound containing a (meth) acryloyl group and an acrylic resin containing a carboxyl group. Unsaturation obtained by reaction of urethane-modified polymerizable double bond-containing acrylic resin obtained by reaction with acryl, acrylic resin containing carboxyl group and compound having both epoxy group and polymerizable double bond in the molecule Group-containing acrylic resin, acid pendant epoxy acrylate resin, polymerizable double bond-containing acrylic resin obtained by reacting OH group-containing acrylic resin and dibasic acid anhydride having polymerizable double bond, OH group A resin obtained by reacting an acrylic resin containing an isocyanate with a compound having a polymerizable group, By subjecting a resin having an ester group having a leaving group such as a halogen atom or a sulfonate group at the α-position or β-position as described in JP-A-229207 and JP-A-2003-335814 to a basic chain The resulting resin is preferred.

Moreover, alkali-soluble resin may contain the structural unit derived from the ethylenically unsaturated monomer shown by following formula (X).
Formula (X)

(In Formula (X), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 2 to 10 carbon atoms, and R ³ represents a hydrogen atom or a benzene ring that may contain a benzene ring. Represents an alkyl group of 20. n represents an integer of 1 to 15.)
In the formula (X), the number of carbon atoms of the alkylene group R ² is preferably 2-3. Although the carbon number of the alkyl group of R ³ is 1 to 20, more preferably 1 to 10, alkyl group of R ³ may include a benzene ring. Examples of the alkyl group containing a benzene ring represented by R ³ include a benzyl group and a 2-phenyl (iso) propyl group.

  As alkali-soluble resins, in particular, benzyl (meth) acrylate / (meth) acrylic acid copolymer and / or multi-component copolymer consisting of benzyl (meth) acrylate / (meth) acrylic acid / other monomers Is preferred. In addition, benzyl (meth) acrylate / (meth) acrylic acid / (meth) acrylic acid-2-hydroxyethyl copolymer copolymerized with 2-hydroxyethyl methacrylate, 2 described in JP-A-7-140654 -Hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl Methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, etc. Are particularly preferred examples include a copolymer of benzyl methacrylate / methacrylic acid.

As the alkali-soluble resin, paragraphs 0558 to 0571 of JP2012-208494A (corresponding to [0685] to [0700] of the corresponding US Patent Application Publication No. 2012/0235099) can be referred to, and the contents thereof can be referred to. Are incorporated herein.
Furthermore, the copolymer (B) described in paragraph Nos. 0029 to 0063 described in JP 2012-32767 A and the alkali-soluble resin used in Examples, paragraph Nos. 0088 to 2020 of JP 2012-208474 A The binder resin described in 0098 and the binder resin used in the examples, the binder resin described in paragraphs 0022 to 0032 of JP2012-137531A, and the binder resin used in the examples, No. 024934, paragraph numbers 0132 to 0143 and binder resins used in Examples, JP-A No. 2011-242752 paragraph numbers 0092 to 0098 and binder resins used in Examples, Open 2012 It preferred to use a binder resin described in 032770 JP paragraphs 0030-0072. These contents are incorporated herein. More specifically, the following resins are preferable.

The acid value of the alkali-soluble resin is preferably 30 mgKOH / g to 200 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, and particularly preferably 70 mgKOH / g to 120 mgKOH / g.
Further, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and particularly preferably 7,000 to 20,000.

The content of the alkali-soluble resin is preferably 0.1 to 15% by mass, more preferably 0.1 to 12% by mass, and still more preferably 1 to 10% by mass with respect to the total solid content of the composition of the present invention. .
The composition of the present invention may contain only one kind of alkali-soluble resin, or may contain two or more kinds. When two or more types are included, the total amount is preferably within the above range.

[Photopolymerization initiator D]
The composition of the present invention contains a photopolymerization initiator D (hereinafter also simply referred to as “photopolymerization initiator”).
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be an activator that generates some action with a photoexcited sensitizer and generates an active radical, or may be an initiator that initiates cationic polymerization according to the type of monomer.
In addition, the photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives. Oxime compounds such as organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones. Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.

  From the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, oniums Compounds selected from the group consisting of compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.

  More preferred are trihalomethyltriazine compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, oxime compound, triallylimidazole dimer, onium compound, benzophenone compound, acetophenone compound, trihalomethyltriazine compound, α-aminoketone Particularly preferred is at least one compound selected from the group consisting of compounds, oxime compounds, triallylimidazole dimer, and benzophenone compounds.

In particular, when the colored composition of the present invention is used for the production of a color filter of a solid-state imaging device, it is necessary to form a fine pattern with a sharp shape. It is important that it be developed. From such a viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator. In particular, when a fine pattern is formed in a solid-state imaging device, stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and the amount of photopolymerization initiator added must be kept low. Therefore, in view of these points, it is particularly preferable to use an oxime compound as a photopolymerization initiator for forming a fine pattern such as a solid-state imaging device. Further, the use of an oxime compound can improve the color transfer.
As specific examples of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine initiator described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long-wave light source such as 365 nm or 405 nm can also be used.
As the acylphosphine-based initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) and the like can be used.

More preferred examples of the photopolymerization initiator include oxime compounds. In particular, an oxime initiator is preferable because it has high sensitivity, high polymerization efficiency, can be cured regardless of the color material concentration, and can be easily designed with a high color material concentration.
Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
Examples of the oxime compound that can be suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyimibutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane 2-one and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
In addition, J.H. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. Examples thereof include compounds described in 202-232, JP-A 2000-66385, JP-A 2000-80068, JP-T 2004-534797, JP-A 2006-342166.
IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used as commercially available products. Further, TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arkles NCI-831 and Adeka Arkles NCI-930 (made by ADEKA) can also be used.

Further, as oxime compounds other than those described above, compounds described in JP-A-2009-519904, in which an oxime is linked to the carbazole N position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, Compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292209, in which a nitro group is introduced into the dye moiety, a ketoxime compound described in International Patent Publication No. 2009-131189, a triazine skeleton and an oxime skeleton in the same molecule A compound described in U.S. Pat. No. 7,556,910, a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source, and the like may be used.
Preferably, for example, paragraphs 0274 to 0275 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The N—O bond of the oxime may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .

In General 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 General Formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
In General Formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
In general formula (OX-1), as a bivalent organic group represented by A, a C1-C12 alkylene group, a cycloalkylene group, and an alkynylene group are preferable. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.

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

  In the present invention, a compound represented by the following general formula (1) or (2) can also be used as a photopolymerization initiator.

In Formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or When an arylalkyl group having 7 to 30 carbon atoms is represented and R ¹ and R ² are phenyl groups, the phenyl groups may be bonded to each other to form a fluorene group, and R ³ and R ⁴ are each independently Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X is a direct bond or carbonyl group Indicates a group.

In the formula ^(2), R ^1, R 2, ^{R 3} and ^{R 4} have the same meanings as ^{R 1,} R 2, ^{R 3} and ^{R 4} in Formula (1), ^{R 5 is} -R 6, -OR ⁶ , -SR ⁶ , -COR ⁶ , -CONR ⁶ R ⁶ , -NR ⁶ COR ⁶ , -OCOR ⁶ , -COOR ⁶ , -SCOR ⁶ , -OCSR ⁶ , -COSR ⁶ , -CSOR ⁶ , -CN, halogen Represents an atom or a hydroxyl group, and R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, X represents a direct bond or a carbonyl group, and a represents an integer of 0 to 4.

In the above formulas (1) and (2), R ¹ and R ² are preferably each independently a methyl group, ethyl group, n-propyl group, i-propyl, cyclohexyl group or phenyl group. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ⁵ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. X is preferably a direct bond.
Specific examples of the compounds represented by formula (1) and formula (2) include, for example, compounds described in paragraph numbers 0076 to 0079 of JP-A No. 2014-137466. This content is incorporated herein.

  It is also possible to use an oxime initiator having a fluorine atom. Specific examples of such an initiator include compounds described in JP 2010-262028 A, compounds 24, 36-40 described in paragraph No. 0345 of JP 2014-500852 A, JP The compound (C-3) described in the paragraph number 0101 of 2013-164471 gazette is mentioned.

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

The oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has an absorption wavelength in the wavelength region of 360 nm to 480 nm, and particularly preferably has high absorbance at 365 nm and 405 nm.
The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
A known method can be used for the molar extinction coefficient of the compound. For example, in a UV-visible spectrophotometer (Cary-5 spctrophotometer manufactured by Varian), an ethyl acetate solvent is used at a concentration of 0.01 g / L. It is preferable to measure.
You may use the photoinitiator used for this invention in combination of 2 or more type as needed.

As for content of a photoinitiator, 0.1-50 mass% is preferable in the total solid of the composition of this invention, More preferably, it is 0.5-30 mass%, More preferably, it is 1-20 mass. %. Within this range, better sensitivity and pattern formability can be obtained.
The composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

[Resin E]
The composition of the present invention preferably further contains a resin E having a group represented by the following general formula (1) from the viewpoint of reducing the reflection of the resulting colored layer.
* -X ₁ -Y (1)
In General Formula (1), X ₁ represents a single bond or a divalent linking group. Y represents an alkyl group or a silyl group. * Represents a bonding position (for example, a position bonded to the main chain of the resin E).

  When such resin E is mix | blended with the composition of this invention, in the colored layer obtained, resin E tends to exist in the surface vicinity concentrated. As a result, a two-layer structure is formed as if a coating layer derived from the resin E was provided on the colored layer. When such a two-layer structure is formed, the light reflected at the surface of the coating layer and the light reflected at the interface between the coating layer and the colored layer are canceled out by interference, thereby realizing low reflectivity. The

In the formula (1), when X ₁ represents a divalent linking group, the divalent linking group has a substituent such as a halogen atom, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms. An alkylene group or an arylene group, —NR ¹² —, —CONR ¹² —, —CO—, —CO ₂ —, SO ₂ NR ¹² —, —O—, —S—, —SO ₂ —, or these Combinations are listed. Here, R ¹² represents a hydrogen atom or a methyl group.

In formula (1), examples of the alkyl group represented by Y include an alkyl group having 3 or more carbon atoms, and more specifically, 3 or more carbon atoms (preferably 7 to 30, more preferably 12 to 20 carbon atoms). ); A branched alkyl group having 3 or more carbon atoms (preferably 3-20, more preferably 5-15); and the like. Note that the branched alkyl group having 3 or more carbon atoms preferably has —CH (CH ₃ ) ₂ or —C (CH ₃ ) ₃ at the terminal.

In formula (1), the alkyl group represented by Y is preferably a linear, branched or cyclic alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. 3-20 are preferable, as for carbon number in the alkyl group substituted by the fluorine atom, 3-10 are more preferable, and 3-5 are more preferable. Note that the alkyl group substituted with a fluorine atom may further have a substituent other than the fluorine atom (for example, an oxygen atom).
Examples of the alkyl group substituted by a fluorine atom include a group represented by —CH (CF ₃ ) ₂ , and other examples include, for example, paragraphs [0266] to [0266] of JP 2011-100089 A 0272], the contents of which are incorporated herein.

  It is particularly preferable that the resin E has a fluorine atom. In the colored layer obtained by containing a fluorine atom, the resin E concentrates in the vicinity of the surface and is particularly likely to be present. Therefore, in addition to being excellent in low reflectivity and coating properties, the colored layer of the present invention Even when a plurality of layers are formed above and below, there are no defects and the layers can be formed.

In formula (1), examples of the silyl group represented by Y include an alkylsilyl group, an arylsilyl group, or a group containing the following partial structure (S) (* represents a bonding site with another atom). Can be mentioned.
Partial structure (S)

As for carbon number of the alkyl chain which an alkyl silyl group has, 1-20 are preferable in total, 1-10 are more preferable, and 1-6 are more preferable. A trialkylsilyl group is preferred.
Examples of the aryl group in the arylsilyl group include a phenyl group.
The group including the partial structure (S) may be a group including the partial structure (S) and forming a cyclic structure. As a preferable partial structure (S), —Si (R) ₂ —O—Si (R) ₂ — (R is an alkyl group having 1 to 3 carbon atoms) and an alkoxysilyl group are preferable. As examples of the structure including the partial structure (S), for example, paragraphs [0277] to [0279] of JP2011-100089A can be referred to, and the contents thereof are incorporated in the present specification.

  Y in the formula (1) is preferably a linear, branched or cyclic alkyl group having 3 to 15 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, and at least one hydrogen atom is a fluorine atom. A linear or branched alkyl group having 3 to 10 carbon atoms substituted by is more preferable, and a branched alkyl group having 3 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom is more preferable.

  Y in formula (1) may be linked to a polymer chain at another location in the resin E to form a crosslinked structure.

  Resin E may have only 1 type of group represented by General formula (1), and may have 2 or more types.

The resin E is preferably a resin containing a repeating unit having a group represented by the general formula (1), and further a resin containing a repeating unit having a group represented by the general formula (2). It is more preferable.
The resin E is preferably a (meth) acrylate polymer.

Examples of the repeating unit having a group represented by the general formula (1) include, but are not limited to, the following groups. In specific examples, X ¹ represents a hydrogen atom, —CH ₃ , —F or —CF _3, and more preferably a hydrogen atom or a methyl group. Me represents a methyl group.

In the above three formulas, n in the top formula is 1 to 100, and R ₂ represents 1 to 100. In the middle formula, l is 1 to 100, m is 1 to 100, and n is 1 to 100. L in the lowest formula is 1-100 each independently, m is 1-100, n is 1-100.

  In the above formula, h is 1 to 100, j is 1 to 100, and k is 1 to 100.

  The content of the repeating unit having a group represented by the general formula (1) is preferably 5 to 70 mol%, more preferably 10 to 60 mol% with respect to all repeating units in the resin E.

The resin E having the group represented by the general formula (1) described above preferably further has a group represented by the following general formula (2).
* -X ₂ -Z (2)
In general formula (2), X ₂ represents a single bond or a divalent linking group. Z represents at least one group selected from the group consisting of a (meth) acryloyl group, an allyl group, a vinyl group, an oxetanyl group, an epoxy group, and a hydroxymethylamino group. * Represents a bonding position (for example, a position bonded to the main chain of the resin E).

  Resin E has a group represented by the above general formula (2), so that in the exposed portion, resins E are cured (crosslinked) or resin E is crosslinked with polymerizable compound B, and organic development after exposure is performed. Even if (Step c1) is performed, it becomes difficult to elute. In particular, Z in the general formula (2) is preferably a (meth) acryloyl group from the viewpoints of curability and heat resistance.

In Formula (2), when X ₂ represents a divalent linking group, examples of the divalent linking group include a substituent such as a halogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms. An alkylene group or an arylene group, —NR ¹² —, —CONR ¹² —, —CO—, —CO ₂ —, SO ₂ NR ¹² —, —O—, —S—, —SO ₂ —, or these Combinations are listed. Here, R ¹² represents a hydrogen atom or a methyl group.

  The resin E may have only one type of group represented by the general formula (2), or may have two or more types.

  Examples of the repeating unit having a group represented by the general formula (2) include a repeating unit represented by the following formula (B1).

In formula (B1), R ^{1 to} R ³ each independently represents a hydrogen atom, an alkyl group, or a halogen atom. X ₂ represents a single bond or a divalent linking group. Z represents at least one group selected from the group consisting of a (meth) acryloyl group, an allyl group, a vinyl group, an oxetanyl group, an epoxy group, and a hydroxymethylamino group.

In formula (B1), R ^{1 to} R ³ are preferably each independently a hydrogen atom or an alkyl group. When R < ¹ > -R < ³ > represents an alkyl group, a C1-C3 alkyl group is preferable. When R ^{1 to} R ³ represent a halogen atom, a fluorine atom is preferable.
X ₂ and Z in the formula (B1) are synonymous with X ₂ and Z in the general formula (2) described above.

  Moreover, as a repeating unit which has group represented by General formula (2), the group shown below is mentioned, for example, However, It is not limited to these.

  The content of the repeating unit having a group represented by the general formula (2) is preferably 30 to 95 mol%, more preferably 45 to 90 mol%, based on all repeating units in the resin E.

<Preferred embodiment of resin E>
As a preferred embodiment of the resin E, a repeating unit similar to the repeating unit A represented by the structural formula (I) described in JP 2010-164965 A and a general formula (II) is used. The curable compound which has a repeating unit similar to the repeating unit B is mentioned.
More specifically, a curable compound having a repeating unit represented by the following formula (A1) and a repeating unit represented by the following formula (A2) can be given.

In formula (A1), R ^a represents a hydrogen atom or a methyl group.
In formula (A2), R ^b each independently represents a hydrogen atom or a methyl group.

In the formula (A2), R ⁷¹ represents a partial structure having one or more repeating units a to e represented by the following structural formulas (71a) to (71e).
In formula (A2), X and Y each independently represent any of the following structural formulas (K1) to (K3). Note that w in the following structural formula (K2) represents an integer of 1 to 20.

  Examples of the curable compound having the repeating unit represented by the formula (A1) and the repeating unit represented by the formula (A2) as described above include Megafac RS-718-K manufactured by DIC Corporation, Examples include Mega-Fuck RS-72-K.

As a commercial item of the said sclerosing | hardenable compound, as a sclerosing | hardenable compound which has a fluorine atom, for example, MegaFac RS-72-K, MegaFac RS-75, MegaFac RS-76-E, MegaFac RS by DIC -76-NS, Megafax RS-77, BYK-UV 3500, BYK-UV 3530, BYK-UV3570, BYK-UV3570 manufactured by BYK, TEGO Rad 2010, TEGO Rad 2011 manufactured by EVONIK, TEGO Rad 2100, TEGO Rad 2200N, TEGO Rad 2250, TEGO Rad 2300, TEGO Rad 2500, TEGO Rad 2600, TEGO Rad 2650, TEGO Rad 2700, and the like can be used.
Among these, from the viewpoint of reducing the reflectance, a curable compound having a fluorine atom is preferable.

It is preferable that the curable compound can form a film having a refractive index of 1.1 to 1.5 at a wavelength of 550 nm using only the curable compound. That is, the refractive index at a wavelength of 550 nm of a film formed only from the curable compound is preferably 1.1 to 1.5.
The preferred range of the refractive index is preferably 1.2 to 1.5, more preferably 1.3 to 1.5, from the viewpoint of low reflectivity of the light shielding film.

  Moreover, as one aspect | mode of resin E, it represents with following formula (A-1-1) described in Paragraph [0141]-[0145] (Synthesis example 1) of Unexamined-Japanese-Patent No. 2015-117327, for example. “Fluorosurfactant (I)” having a repeating unit derived from a polymerizable monomer is also preferred.

  In formula (A-1-1), X is a perfluoromethylene group and a perfluoroethylene group, and an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups are present per molecule. The number of fluorine atoms is 46 on average.

The weight average molecular weight (Mw) of the resin E is preferably 5,000 to 100,000, and more preferably 7,000 to 50,000.
Further, the dispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the resin E is preferably 1.80 to 3.00, and more preferably 2.00 to 2.90.

In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are polystyrene conversion values determined by the following GPC method.
The GPC (gel permeation chromatography) method uses HLC-8020GPC (manufactured by Tosoh Corporation), and TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (4.6 mm ID × 15 cm) manufactured by Tosoh Corporation as columns. Based on a method using THF (tetrahydrofuran) as an eluent.

Resin E may be used individually by 1 type, and may use 2 or more types together.
When the composition of this invention contains resin E, 0.1-20 mass% is preferable with respect to the total solid in the composition of this invention, and, as for content of resin E, 0.5-15 mass % Is more preferable, and 1.0 to 10% by mass is more preferable. When the composition of this invention contains 2 or more types of resin E, the sum total should just be in the said range.

〔solvent〕
The composition of the present invention may further contain a solvent. The solvent is basically not particularly limited as long as the solubility of each component and the coating property of the composition are satisfied.
Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, Alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-oxypropionate (Eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)) ), 2-Oki Propionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropion) Propyl acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example, 2-methoxy-2-methyl Methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. As ethers, For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc. Preferred examples of the aromatic hydrocarbon include xylene. Two or more of these solvents may be used in combination.

  The content of the solvent in the composition of the present invention is preferably such that the total solid concentration of the composition of the present invention is 5 to 80% by mass, and 5 to 60% by mass from the viewpoint of applicability. More preferred is an amount of 10 to 50% by mass.

[Dispersant]
When the colored radiation-sensitive composition of the present invention contains a pigment, it can contain a dispersant.
Examples of the dispersant include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic type Copolymer, naphthalenesulfonic acid formalin condensate], surfactants such as polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanolamine, and pigment derivatives.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.

  Examples of the terminal-modified polymer having an anchor site to the pigment surface include polymers having a phosphate group at the terminal described in JP-A-3-112992, JP-T2003-533455, and the like. Examples thereof include polymers having a sulfonic acid group at the end described in JP-A-273191, and polymers having a partial skeleton of organic dye and a heterocyclic ring described in JP-A-9-77994. In addition, a high molecular weight terminal having two or more anchor sites (acid group, basic group, organic dye partial skeleton, heterocycle, etc.) to the surface of the polymer described in JP-A-2007-277514 is introduced. Molecules are also preferred because of their excellent dispersion stability.

  Examples of the graft polymer having an anchor site to the pigment surface include a polyester-based dispersant, and specific examples thereof include, for example, JP-A-54-37082 and JP-A-8-507960. And reaction products of poly (lower alkyleneimines) and polyesters described in JP-A-2009-258668, etc .; reaction products of polyallylamine and polyesters described in JP-A-9-169821; Copolymers of macromonomers and nitrogen atom monomers described in Kaihei 10-339949, JP-A-2004-37986, etc .; JP-A-2003-238837, JP-A-2008-9426, and And grafts having a partial skeleton and / or heterocycle of an organic dye described in JP-A-2008-81732 Polymer; a copolymer of a macromonomer and acid group-containing monomers described in JP 2010-106268 Publication, and the like. In particular, the amphoteric dispersion resin having a basic group and an acidic group described in JP-A-2009-203462 includes a dispersibility of a pigment dispersion, a dispersion stability, and a colored radiation-sensitive composition using the pigment dispersion. Is particularly preferable from the viewpoint of developability.

  A known macromonomer can be used as the macromonomer used when the graft polymer having an anchor site to the pigment surface is produced by radical polymerization. Macromonomer AA-6 (terminal) manufactured by Toa Gosei Co., Ltd. Polymethyl methacrylate whose group is a methacryloyl group), AS-6 (polystyrene whose terminal group is a methacryloyl group), AN-6S (a copolymer of styrene and acrylonitrile whose terminal group is a methacryloyl group), AB-6 ( Polybutyl acrylate whose end group is a methacryloyl group), PLACEL FM5 manufactured by Daicel Chemical Industries, Ltd. (5 molar equivalent addition product of ε-caprolactone of 2-hydroxyethyl methacrylate), FA10L (2-hydroxyethyl acrylate) ε-caprolactone 10 molar equivalent addition product), and JP-A 2-2 And polyester macromonomers described in Japanese Patent No. 72009. Among these, the polyester-based macromonomer that is particularly excellent in flexibility and solvophilicity is from the viewpoint of the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the colored radiation-sensitive composition using the pigment dispersion. Particularly preferred are polyester macromonomers represented by polyester macromonomers described in JP-A-2-272009.

  As the block polymer having an anchor site to the pigment surface, block polymers described in JP-A Nos. 2003-49110 and 2009-52010 are preferable.

  The dispersant is also available as a commercial product. Specific examples thereof include “DA-7301” manufactured by Kashiwagi Kasei Co., Ltd., “Disperbyk-101 (polyamideamine phosphate)” manufactured by BYK Chemie, 107 (carboxylic acid). Ester), 110 (copolymer containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight) Unsaturated carboxylic acid), "EFKA 4047, 4050 to 4010 to 4165 (polyurethane type), EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (manufactured by EFKA) High molecular weight polycarboxylate), 6220 (fatty acid polyester) Tel), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative), “Ajispur PB821, PB822, PB880, PB881” manufactured by Ajinomoto Fan Techno Co., Ltd., “Floren TG-710 (urethane oligomer)” manufactured by Kyoeisha Chemical Co., Ltd., “Polyflow” No. 50E, No. 300 (acrylic copolymer) ”,“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyether ester), DA, manufactured by Enomoto Kasei Co., Ltd. -703-50, DA-705, DA-725 "," Demol RN, N (naphthalene sulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "manufactured by Kao Corporation. "Homogenol L-18 (polymeric polycarboxylic acid)", "Emulgen 920" 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”,“ acetamine 86 (stearylamine acetate) ”,“ Solsperse 5000 (phthalocyanine derivative) ”, 22000 (azo pigment derivative), 13240 (polyester) manufactured by Nippon Lubrizol Co., Ltd. Amine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) "," Nikkor T106 (polyoxyethylene sorbitan monooleate) "manufactured by Nikko Chemical. , MYS-IEX (polyoxyethylene monostearate) ”, Kawano Fine Chemical Co., Ltd. Hinoact T-8000E, Shin-Etsu Chemical Co., Ltd., Organosiloxane Polymer KP341, Yusho Co., Ltd.“ W 01: Cationic surfactant ", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate Nonionic surfactants such as sorbitan fatty acid esters, anionic surfactants such as “W004, W005, W017”, “EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100 manufactured by Morishita Sangyo Co., Ltd.” EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 "," Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, manufactured by San Nopco Co., Ltd. Polymer dispersing agents such as "ISPARSE AID 9100", "ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L94, P103, manufactured by ADEKA Corporation F108, L121, P-123 ”,“ Ionet (trade name) S-20 ”manufactured by Sanyo Chemical Co., Ltd., and the like.

  A dispersing agent may be used independently and may be used in combination of 2 or more type. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant. The dispersant of the present invention may be used in combination with an alkali-soluble resin together with a terminal-modified polymer, a graft polymer, or a block polymer having an anchor site to the pigment surface. Alkali-soluble resins include (meth) acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and carboxylic acid in the side chain. Examples of the acid cellulose derivative include a resin having a hydroxyl group modified with an acid anhydride, and a (meth) acrylic acid copolymer is particularly preferable. Further, N-substituted maleimide monomer copolymers described in JP-A-10-300902, ether dimer copolymers described in JP-A-2004-300204, and polymerizable groups described in JP-A-7-319161. An alkali-soluble resin containing is also preferred.

As content of the dispersing agent in a colored radiation sensitive composition, it is preferable that it is 1-80 mass parts with respect to 100 mass parts of pigments, 5-70 mass parts is more preferable, and it is 10-60 mass parts. More preferably.
Specifically, when a polymer dispersant is used, the amount used is preferably in the range of 5 to 100 parts in terms of mass with respect to 100 parts by mass of the pigment, and in the range of 10 to 80 parts. It is more preferable that
Moreover, when using a dispersing agent and a pigment derivative together, as the usage-amount of a pigment derivative, the range of 1-30 parts is preferable in conversion of mass with respect to 100 mass parts of pigments, 3-20 parts is more preferable, 15 parts is particularly preferred.

In the colored radiation-sensitive composition of the present invention, when a dye and a pigment are used, the concentration of the colorant containing the dye and the pigment with respect to the total solid content of the colored radiation-sensitive composition is 50 from the viewpoint of curing sensitivity and color density. The content is preferably at least mass%, more preferably at least 60 mass%, and even more preferably at least 70 mass%. Moreover, it is preferable that the density | concentration of the coloring agent with respect to the total solid of a coloring radiation sensitive composition is 90 mass% or less, and it is more preferable that it is 85 mass% or less.
Further, in the colored radiation-sensitive composition of the present invention, when a pigment is used, the concentration of the pigment with respect to the total solid content of the colored radiation-sensitive composition is preferably 25% by mass or more, and 35% by mass or more. Is more preferable, and it is further more preferable that it is 45 mass% or more. Moreover, it is preferable that the density | concentration of the pigment with respect to the total solid of a colored radiation sensitive composition is 65 mass% or less, and it is more preferable that it is 55 mass% or less.

[Surfactant]
The composition of the present invention may contain various surfactants from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. In addition, the resin E mentioned above is not contained in the said surfactant.

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 PF6520, PF7002 (manufactured by OMNOVA), and the like.

Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Onin D-6112-W (produced by Takemoto Oil & Fat Co., Ltd.), SOLSPERSE 20000 (manufactured by Nippon Lubrizol Co., Ltd.)), and the like.
Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.
Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.
Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. “Silicone SH29PA”, “Toresilicone SH30PA”, “Toresilicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF” manufactured by Momentive Performance Materials, Inc. -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by Big Chemie.

Surfactant may be used individually by 1 type and may use 2 or more types together.
When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.001% by mass to 2.0% by mass with respect to the total mass of the composition of the present invention. 005% by mass to 1.0% by mass is more preferable.

[Photoacid generator]
The composition of the present invention may further contain a photoacid generator (acid generator) that is a compound that generates an acid upon irradiation with radiation.
In the case where the composition of the present invention contains the resin E having the group represented by the general formula (2), Z in the group is an oxetanyl group, an epoxy group, or hydroxymethyl. In the case of representing an amino group, these groups are easily decomposed and crosslinked by the acid action generated by the photogenerator.
The photoacid generator is not particularly limited, and a known photoacid generator can be used as appropriate, but a compound that generates an organic acid such as sulfonic acid, bis (alkylsulfonyl) imide, tris (alkylsulfonyl) methide, and the like. Etc.
When the photoacid generator is in the form of a low molecular compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.
As examples of the photoacid generator, for example, paragraphs [0168] to [0214] of JP-A-2015-138232 can be referred to, and the contents thereof are incorporated in the present specification.
A photo-acid generator may be used individually by 1 type, and may use 2 or more types together.
When the composition of the present invention contains a photoacid generator, the content of the photoacid generator is preferably 0.1 to 50% by mass based on the total solid content of the composition of the present invention, 0.5 -40 mass% is more preferable.

[Other ingredients]
In the composition of the present invention, in addition to the essential components and optional components described above, other components may be appropriately selected according to the purpose as long as the effects of the present invention are not impaired.
Examples of other components that can be used in combination include a binder polymer, a dispersant, a sensitizer, a crosslinking agent, a curing accelerator, a filler, a thermosetting accelerator, a thermal polymerization inhibitor, a plasticizer, an ultraviolet absorber, and a silane coupling. Furthermore, adhesion promoters to the substrate surface and other auxiliaries (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, etc. , Surface tension adjusting agents, chain transfer agents, etc.) may be used in combination.
By appropriately containing these components, properties such as stability of the film to be formed and film physical properties can be adjusted.
These components are described, for example, in paragraphs [0183] and later of JP2012-003225A (corresponding to [0237] and later of US 2013/0034812 of the corresponding specification), JP2008-250074. Paragraphs [0101] to [0102], paragraphs [0103] to [0104], paragraphs [0107] to [0109], and the like, the contents of which are incorporated herein.

(Preparation of colored radiation-sensitive composition)
Although it does not restrict | limit especially about the preparation aspect of the composition of this invention, For example, the essential component and arbitrary component which were mentioned above can be mixed and prepared.
The composition of the present invention is preferably filtered using a filter for the purpose of removing foreign substances and reducing defects.
As a filter used for filter filtration, if it is a filter conventionally used for the filtration use etc., it can use without being specifically limited.
Examples of filter materials include: fluororesins such as PTFE (polytetrafluoroethylene); polyamide resins such as nylon-6 and nylon-6, 6; polyolefin resins such as polyethylene and polypropylene (PP) (high density, super Including high molecular weight); Among these materials, polypropylene (including high density polypropylene) is preferable.
The pore size of the filter is not particularly limited, but is, for example, about 0.01 to 20.0 μm, preferably about 0.01 to 5 μm, and more preferably about 0.01 to 2.0 μm.
By setting the pore diameter of the filter in the above range, fine particles can be more effectively removed and turbidity can be further reduced.
Here, the pore size of the filter can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co. .
Moreover, it is preferable that a highly pure thing is used as a raw material used for the colored radiation sensitive composition of this invention. Mixing and generation of impurities that affect performance such as particles, metal impurities, moisture, and peroxides can be suppressed.

As a method for applying the composition of the present invention on the support, various methods such as slit coating, ink jet method, spin coating, spray coating, cast coating, roll coating, and screen printing can be used.
Of these, slit coating, spin coating, and spray coating are preferred because the thickness of the colored radiation-sensitive composition layer is uniform. Moreover, when the lower surface of the colored photosensitive composition layer is not flat, spray coating or an ink jet method is preferable from the viewpoint of uniform film thickness.

When the composition of the present invention is applied by ink jet, it preferably has physical properties suitable for application to an ink jet recording apparatus.
That is, when the composition of the present invention is used in an ink jet recording method, the ink viscosity at the temperature at the time of ejection is preferably 100 mPa · s or less, more preferably 50 mPa · s or less in consideration of ejection properties. Preferably, it is preferable to determine by adjusting the composition ratio as appropriate so as to be in the above range.
The viscosity of the composition under an environment of 25 ° C. (room temperature) is preferably 0.5 mPa · s to 200 mPa · s, more preferably 1 mPa · s to 100 mPa · s, and further preferably 2 mPa · s. It is 50 mPa · s or less. By setting the viscosity at room temperature high, even when applied to an uneven substrate, dripping of the composition is prevented, and as a result, a uniform light-shielding film can be formed. When the viscosity in a 25 ° C. environment is greater than 200 mPa · s, there may be a problem in the composition transport (liquid transport state in the apparatus).

  The surface tension of the composition of the present invention is preferably 20 mN / m to 40 mN / m, more preferably 23 mN / m to 35 mN / m. When applied to a silicon substrate or a metal wiring surface, it is preferably 20 mN / m or more from the viewpoint of dripping suppression, and 35 mN / m or less is preferable from the viewpoint of adhesion and affinity with the substrate.

[Method for producing colored layer]
Next, the manufacturing method of the colored layer of the present invention (the manufacturing method of the present invention) will be described.
The method for producing a colored layer of the present invention comprises a step a in which a colored radiation-sensitive composition layer is formed using the composition of the present invention described above, and the colored radiation-sensitive composition layer is patterned through a mask. And a step c of treating the exposed colored radiation-sensitive composition layer to form a colored layer, wherein the step c uses a developer containing an organic solvent. It is a manufacturing method of a colored layer which is a process of performing any one process among process c1 to process, and process c2 developed using alkaline aqueous solution, and then performing the other process.
Hereinafter, each process with which the manufacturing method of this invention is provided is demonstrated.

[Step a]
In step a, a colored radiation-sensitive composition layer is formed using the composition of the present invention. At this time, a colored radiation-sensitive composition layer is formed by, for example, applying the composition of the present invention to a substrate or the like.
As the substrate, for example, a photoelectric conversion element substrate or a silicon substrate in a CCD (Charge-Coupled Device) or CMOS (Complementary Metal Oxide Semiconductor) used for a solid-state imaging device; non-alkali glass, soda glass used for a liquid crystal display device, etc. Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film thereto. In some cases, a black matrix for isolating each pixel is formed on these substrates.
In addition, an undercoat layer may be provided on these substrates, if necessary, for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface.
Examples of the method for applying the composition of the present invention include various coating methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, and screen printing. The film thickness of the colored radiation-sensitive composition layer is preferably 0.1 μm to 10 μm, more preferably 0.2 μm to 5 μm, and further preferably 0.2 μm to 3 μm.
The colored radiation-sensitive composition layer may be dried (pre-baked) as necessary, and the pre-baking is performed in a temperature environment of 50 ° C. to 140 ° C. using a hot plate, oven, etc. for 10 seconds to It can be performed for 300 seconds.

[Step b]
In step b, the colored radiation-sensitive composition layer formed in step a is exposed in a pattern through a mask. At this time, for example, an exposure apparatus such as a stepper is used to perform pattern exposure through a mask having a predetermined mask pattern.
As radiation (light) that can be used for exposure, ultraviolet rays such as g-line and i-line are particularly preferable (particularly preferably i-line). Irradiation dose (exposure dose) is preferably 30~1500mJ / cm ^2, more preferably 50~1000mJ / cm ^2, more preferably 80~500mJ / cm ^2.

[Step c]
Step c is a step of forming the colored layer by processing the colored radiation-sensitive composition layer exposed in step b, and a step c1 of processing using a developer containing an organic solvent, and an alkali. In this step, one of the steps c2 of developing using the aqueous solution is performed, and then the other step is performed.
As described above, by developing with an aqueous alkali solution (alkali development), the unexposed portion of the colored radiation-sensitive composition layer is eluted into the aqueous alkaline solution, and the photocured exposed portion remains as a colored layer. At this time, in the unexposed part of the colored radiation-sensitive composition layer, a hydrophobic component other than the alkali-soluble resin C does not elute and can be a residue, but a developer containing an organic solvent before and after alkali development. By carrying out the treatment using (which is also referred to as “organic development” for the sake of convenience), the hydrophobic components in the unexposed areas are eluted into the organic solvent, and the generation of residues is suppressed.
The order of step c1 (organic development) and step c2 (alkali development) is not particularly limited. However, in the colored radiation-sensitive composition layer, a hydrophobic component (for example, resin E) tends to bleed on the surface. From the viewpoint of removing the first, it is preferable to perform step c2 after first performing step c1.

<Step c1 (organic development)>
In step c1, a developer containing an organic solvent (hereinafter also referred to as “organic developer”) is used.
The vapor pressure of the developer containing an organic solvent (the vapor pressure as a whole in the case of a mixed solvent) is preferably 5 kPa or less, more preferably 3 kPa or less, and further preferably 2 kPa or less at 20 ° C. By setting the vapor pressure of the organic solvent to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, temperature uniformity in the wafer surface is improved, and as a result, dimensional uniformity in the wafer surface is good. Turn into.

  As the organic solvent contained in the organic developer, various organic solvents are widely used and are not particularly limited. For example, ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, carbonization solvents. Examples of the solvent include a hydrogen-based solvent.

In the present invention, the ester solvent is a solvent having an ester group in the molecule.
A ketone solvent is a solvent having a ketone group in the molecule.
The alcohol solvent is a solvent having an alcoholic hydroxyl group in the molecule.
An amide solvent is a solvent having an amide group in the molecule.
The ether solvent is a solvent having an ether bond in the molecule. Among these, there is a solvent having a plurality of types of the above functional groups in one molecule. In that case, it corresponds to any solvent type including the functional group of the solvent. For example, diethylene glycol monomethyl ether corresponds to an alcohol solvent and an ether solvent in the above classification.
The hydrocarbon solvent is a hydrocarbon solvent having no substituent.
Hereinafter, specific examples of the organic solvent will be described.

  Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclopentanone, cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate, etc. it can.

  Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monoethyl ether acetate, diethylene glycol mono Butyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate Propyl lactate, butyl butanoate, methyl 2-hydroxyisobutyrate, isobutyl isobutyrate, butyl propionate and the like.

  Examples of the alcohol solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, alcohols such as n-octyl alcohol and n-decanol; glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether (also known as 1-methoxy-2-propanol), ethylene glycol mono Ethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol And the like can be given; Bruno ethyl ether, glycol ether solvents such as methoxymethyl butanol.

Examples of the ether solvent include the above glycol ether solvents, dioxane, tetrahydrofuran and the like.
Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.

  In the present invention, the organic developer is at least one selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, an ether solvent, and a hydrocarbon solvent because of the better residue generation. A developer containing a seed solvent is preferable, and a developer containing at least one solvent selected from the group consisting of a ketone solvent, an ester solvent, and an ether solvent is more preferable.

  In addition, it is preferable that the organic solvent contained in the organic developer does not contain an organic chlorine compound such as 1,1,1-trichloroethane (non-organic chlorine compound). It is because the heat resistance of the colored layer obtained may deteriorate when the organic chlorine compound acts on the colorant.

The organic solvent used in the developer may be used by mixing a plurality of types, or may be used by mixing with a solvent other than the above or water. In order to achieve the effect of the present invention more effectively, the water content of the developer as a whole is preferably 30% by mass or less, more preferably less than 10% by mass, substantially containing water. More preferably not.
The concentration of the organic solvent in the developer (total when a plurality of types are mixed) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 95% by mass or more, and particularly preferably. Is a case consisting essentially of an organic solvent. In addition, the case where it consists only of an organic solvent includes the case where a trace amount surfactant, antioxidant, a basic compound, a stabilizer, an antifoamer, etc. are contained.

The organic solvent in the developer containing the organic solvent can also be defined using an SP value (Solubility Parameter). As the SP value of the organic solvent, for example, the SP value described in VII / 675 to 714 of “POLYMER HANDBOOK FOURTH EDITION Volume 2” (more specifically, the SP value described in Table 7) can be used. The SP value is preferably 15.1 to 18.9, or 23.1 to 42.0, more preferably 15.1 to 18.0, or 26.0 to 42.0, and 15 .1 to 17.5 or 30.0 to 42.0 is more preferable, and 15.7 to 17.5 or 30.0 to 42.0 is particularly preferable.
By setting the SP value of the organic solvent to 18.9 or less and 23.1 or more, the compatibility between the organic solvent and the dye is prevented from becoming too good, and the loss of the dye from the cured portion occurs. Can be prevented. Further, by setting the SP value of the organic solvent to 15.1 or more and 42.0 or less, the affinity between the organic solvent and the dye can be improved and the developability can be improved.
Moreover, the developability of an unexposed part can be made more favorable by making SP value of an organic solvent into 15.7 or more.

  Further, a nitrogen-containing compound may be contained in the developer containing an organic solvent. As the nitrogen-containing compound, for example, the description in paragraphs [0042] to [0063] of JP2013-011833A can be referred to, and the contents thereof are incorporated in the present specification.

As a processing method (development method), for example, a method in which a substrate is immersed in a tank filled with a developer for a predetermined time (dip method), a developer is raised on the surface of the substrate by surface tension, and is developed by standing for a certain time. Method (paddle method), method of spraying developer on the substrate surface (spray method), method of continuously discharging developer while scanning the developer discharge nozzle at a constant speed on a substrate rotating at a constant speed ( Dynamic dispensing method) can be applied, and the paddle method is particularly preferable.
The processing time (development time) is not particularly limited as long as the colored layer in the unexposed area is sufficiently dissolved, and is usually 10 seconds to 300 seconds. Preferably, it is 20 seconds to 120 seconds.
The temperature of the developer is preferably from 0 ° C to 50 ° C, more preferably from 15 ° C to 35 ° C.

In the manufacturing method of this invention, after processing using the developing solution containing an organic solvent, you may wash | clean using the rinse liquid containing an organic solvent.
The vapor pressure of the rinsing liquid (the vapor pressure as a whole in the case of a mixed solvent) is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, and 0.12 kPa or more at 20 ° C. 3 kPa or less is more preferable. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling due to the penetration of the rinse solution is suppressed, and the dimensional uniformity in the wafer surface. Improves.
As the rinsing liquid, various organic solvents are used. At least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents is used. It is preferable to use a rinse solution containing
Regarding the rinsing process, for example, paragraphs [0045] to [0054] of Japanese Patent Application Laid-Open No. 2010-217884 can be referred to, and the contents thereof are incorporated in the present specification.

<Step c2 (alkali development)>
The development method in the alkali development in step c2 may be any of a dip method, a shower method, a spray method, a paddle method, etc., and a swing method, a spin method, an ultrasonic method, or the like may be combined therewith. In addition, it is possible to prevent uneven development by previously moistening the surface to be developed with water or the like before contact with the developer.
The alkaline aqueous solution that is the developer used in step c2 is preferably an organic alkali developer that does not cause damage to the underlying imaging device and circuit. The development temperature is usually 20 ° C. to 30 ° C., and the development time is, for example, 20 seconds to 90 seconds. In order to remove the residue more, in recent years, it may be carried out for 120 seconds to 180 seconds. Furthermore, in order to further improve residue removability, the process of shaking off the developer every 60 seconds and further supplying a new developer may be repeated several times.
Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5, 4, 0] -7-undecene and the like, and these alkaline agents are diluted with pure water so that the concentration becomes 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An alkaline aqueous solution is preferably used as the developer.
In addition, an inorganic alkali may be used for the developer, and as the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metaoxalate and the like are preferable.
In addition, when using the developing solution which consists of such alkaline aqueous solution, generally it wash | cleans (rinse) using the pure water after image development.

It is preferable to perform heat treatment (post-bake) after washing (rinsing) and then drying. Post-baking is a heat treatment after development for complete curing, and a heat curing treatment is usually performed at 100 ° C. to 240 ° C., preferably 200 ° C. to 240 ° C.
In this post-baking treatment, the coating film after development is continuously or batch-typed by using heating means such as a hot plate, a convection oven (hot air circulation dryer), and a high-frequency heater so as to satisfy the above conditions. Can be done by.

[Colored layer (color filter, light shielding film)]
The application of the patterned colored layer (colored pattern) obtained by the production method of the present invention is not particularly limited, and for example, it can be used as a light-shielding film or a color filter provided in a solid-state imaging device.

  For example, a solid-state imaging device mounted on a digital camera, a mobile phone with a camera, a smartphone, or the like includes a photographing lens and a CCD (charge coupled device) or CMOS (complementary metal oxide film) disposed behind the photographing lens. A solid-state imaging device such as a semiconductor) and a circuit board on which the solid-state imaging device is mounted. In such a solid-state imaging device, noise may be generated due to reflection of visible light. Therefore, noise generation is suppressed by providing a light shielding film in the solid-state imaging device. When forming a light shielding film, black pigments, such as titanium black, are used as a coloring agent contained in the composition of this invention, for example.

  Color filters, which are indispensable components for solid-state imaging devices, are formed with colored areas of multiple hues, and are usually formed with colored areas (colored patterns) of at least red, green, and blue. Is done. At this time, as a method for forming a colored pattern, first, in the first hue, a colored radiation-sensitive composition having any one of red, green and blue colorants is applied, exposed and developed. After forming the coloring pattern of one hue, the same processing is repeated in the second hue and the third hue.

  Although the thickness of a colored layer is not specifically limited, For example, when used as a light shielding film, 0.2-25 micrometers is preferable and 1.0-10 micrometers is more preferable.

Moreover, when used in a color filter, the thickness of a colored layer is 2.0 micrometers or less, for example, 1.5 micrometers or less are preferable, 0.2-1.5 micrometers is more preferable, 0.2-1. 2 μm is more preferable.
The pattern width of the colored layer is preferably 2.5 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.7 μm or less.

[Solid-state imaging device]
The solid-state imaging device of the present invention includes a colored layer (hereinafter also referred to as “colored layer of the present invention”) obtained by the production method of the present invention. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it includes the colored layer of the present invention and functions as a solid-state imaging device, and examples thereof include the following configurations.

The support has a transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.). It has a light-shielding film that is open only in the light-receiving part, and has a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part. It is the structure which has.
Further, the device has a condensing means (for example, a microlens, etc., the same applies hereinafter) on the device protective layer and below the color filter (on the side close to the support), and a constitution having the condensing means on the color filter. There may be.

[Image display device]
The colored layer of the present invention can be used for image display devices such as liquid crystal display devices and organic electroluminescence display devices.

  For the definition of display devices and details of each display device, refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Industrial Research Council 1990)”, “Display Devices (written by Junaki Ibuki, Sangyo Tosho) Issued in 1989). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

The color filter in the present invention may be used for a color TFT (Thin Film Transistor) type liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention relates to a liquid crystal display device with a wide viewing angle, such as a lateral electric field driving method such as IPS (In Plane Switching), a pixel division method such as MVA (Multi-domain Vertical Alignment), and a super-twist neutral (STN). TN (Twisted Nematic), VA (Vertical Alignment), OCS (On-chip spacer), FFS (Fringe field switching), and R-OCB (Reflective Optical Compensated).
In addition, the color filter in the present invention can be used for a bright and high-definition COA (Color-filter On Array) system. In the COA type liquid crystal display device, the required characteristics for the color filter require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the resistance to the peeling liquid, in addition to the normal required characteristics as described above. Sometimes. Since the color filter of the present invention is excellent in light resistance and the like, a COA type liquid crystal display device having high resolution and excellent long-term durability can be provided. In order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.
These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-Technology and latest trends in the market (issued by Toray Research Center Research Division 2001)".

The liquid crystal display device of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film in addition to the color filter of the present invention. The color filter of the present invention can be applied to a liquid crystal display device composed of these known members. Regarding these components, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
Regarding backlighting, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. Have been described.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” and “%” are based on mass.

<Synthesis Example 1: Synthesis of Resin (E-1)>
Under a nitrogen stream, 23 g of 1-methoxy-2-propanol was heated to 80 ° C. Next, 10 g of 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 10 g of allyl methacrylate, 2.0 g of 2,2′-azobis (methyl isobutyrate) and 23 g of 1-methoxy-2-propanol The mixed solution was added dropwise over 3 hours, stirred for another 2 hours, and then heated at 90 ° C. for 2 hours. After standing to cool, it was added dropwise to a mixed solution of 100 mL of methanol and 200 mL of ion-exchanged water, and the resulting solid was collected. This solid was dried under reduced pressure at 50 ° C. for 24 hours to obtain 18.6 g of Resin (E-1). The weight average molecular weight (Mw) of the resin (E-1) was 11,000.

<Synthesis Examples 2-7: Synthesis of Resin (E-1) to Resin (E-7)>
Resins (E-2) to (E-7) were obtained by performing the same operations as in Synthesis Example 1.

<Synthesis Example 8: Synthesis of Resin (E-8)>
Under a nitrogen stream, 23 g of 1-methoxy-2-propanol was heated to 80 ° C. Next, 10 g of methacrylic acid 1,1,1,3,3,3-hexafluoroisopropyl, 3.8 g of methacrylic acid, 1.5 g of 2,2′-azobis (methyl isobutyrate) and 1-methoxy-2-propanol 23 g of the mixed solution was added dropwise over 3 hours, and the mixture was further stirred for 2 hours, and then heated in an environment of 90 ° C. for 2 hours. Next, 0.1 g of tetrabutylammonium bromide, 7.2 g of glycidyl methacrylate, and 0.05 g of p-methoxyphenol were added and heated in an air atmosphere at 100 ° C. for 24 hours. It was confirmed by acid value measurement that the acid group had disappeared. After standing to cool, it was added dropwise to a mixed solution of 100 mL of methanol and 200 mL of ion-exchanged water, and the resulting solid was collected. By drying this solid under reduced pressure at 50 ° C. for 24 hours, the weight average molecular weight (Mw) of the resin (E-8) was 13,000.

<Synthesis Example 9: Synthesis of Resin (E-9)>
Under a nitrogen stream, 23 g of 1-methoxy-2-propanol was heated to 80 ° C. Next, 10 g of 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 4.6 g of 2-hydroxyethyl methacrylate, 1.0 g of 2,2′-azobis (methyl isobutyrate) and 1-methoxy A mixed solution of 23 g of 2-propanol was added dropwise over 3 hours, and the mixture was further stirred for 2 hours, and then heated in an environment of 90 ° C. for 2 hours. Next, 0.1 g of Neostan U-600 (Nitto Kasei Co., Ltd.), 5.7 g of 2-isocyanatoethyl methacrylate, and 0.05 g of p-methoxyphenol are added, and the atmosphere is kept at 80 ° C. for 24 hours under a nitrogen atmosphere. Heated. The disappearance of the isocyanate group was confirmed by NMR measurement. After standing to cool, it was added dropwise to a mixed solution of 100 mL of methanol and 200 mL of ion-exchanged water, and 17.9 g of Resin (E-9) was obtained by collecting the resulting solid. The weight average molecular weight (Mw) of the resin (E-9) was 16,000.

  The weight average molecular weights (Mw) of the synthesized resins (E-1) to (E-9) are collectively shown in Table 1 below.

<Preparation of pigment dispersion>
In accordance with Table 2 below, a mixed solution consisting of 40 parts of pigment, 5 parts of pigment derivative, 60 parts of a propylene glycol monomethyl ether acetate solution of polymer dispersant (18 parts in solid conversion), and 300 parts of propylene glycol monomethyl ether acetate was added to a bead mill. A pigment dispersion was prepared by mixing and dispersing for 3 hours using (zirconia beads 0.3 mm diameter).
In addition, when using 2 types of pigments together, mass ratio was 70/30.
The following pigment derivative A was used as the pigment derivative, and the following polymer dispersant A was used as the polymer dispersant.

In Table 2, PR254, PG36, PG58, PY139, PB15: 6, and PV23 are respectively C.I. I. Pigment red 254, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment yellow 139, C.I. I. Pigment Blue 15: 6.
Further, 13M-T manufactured by Mitsubishi Materials was used as titanium black, and Nexex 35 manufactured by Degussa was used as carbon black.

<Composition of resist solution for undercoat layer>
Components of the following composition were mixed and dissolved to prepare an undercoat layer resist solution.
Solvent: propylene glycol monomethyl ether acetate (PGMEA) 19.20 parts Solvent: ethyl lactate 36.67 parts Alkali-soluble resin: benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate copolymer (molar ratio = 60/22/18, weight average molecular weight 15,000, number average molecular weight 9,000) 40% PGMEA solution
30.51 parts Dipentaerythritol hexaacrylate (KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)) 12.20 parts Polymerization inhibitor: p-methoxyphenol 0.0061 parts Fluorosurfactant: F-475, DIC 0.83 parts manufactured by company ・ Photopolymerization initiator: trihalomethyltriazine-based photopolymerization initiator (TAZ-107, manufactured by Midori Chemical Co., Ltd.) 0.586 parts

<Production of silicon wafer substrate with undercoat layer>
A 6-inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes. Next, the undercoat layer resist solution is applied onto the silicon wafer so that the dry film thickness is 1.5 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer. A layered silicon wafer substrate was obtained.

<Preparation of colored radiation-sensitive compositions (compositions of Examples 1 to 20 and Comparative Example 1)>
The following components were mixed, dispersed, dissolved, and filtered using a 0.45 μm nylon filter to obtain compositions of Examples 1 to 20 and Comparative Example 1.
・ Pigment dispersion 600 parts when no dye is added
When adding dye 400 parts ・ Dye 20 parts ・ Cyclohexanone 100 parts ・ Alkali-soluble resin (following (J1) or (J2)) 5 parts ・ Solsperse 20000 (1% cyclohexane solution, manufactured by Nihon Lubrizol) 1 part ・ Light Polymerization initiator (below (I-1) to (I-9)) 1 part Photoacid generator (below (I-10)) 0.5 part Polymerizable compound (below (M-1) to (M -3) 10 parts-Glycerol propoxylate (1% cyclohexane solution) 0.1 part-Resin E (the above (E-1) to (E-9) or DIC's Megafax RS-72-K) 5 parts

  The following (I-1) is IRGACURE (registered trademark) -OXE01, the following (I-2) is IRGACURE (registered trademark) -OXE02, the following (I-3) is IRGACURE (registered trademark) -379, and the following (I-4) ) DAROCUR (registered trademark) -TPO (all of which are manufactured by BASF).

<Synthesis of Dye (A)>
A dye (A) represented by the following formula was synthesized by the method described in JP-A-2014-199436.
Acid value = 1.01 mmol / g
a / b / c / d = 36/12/32/20 (mol%)
n = 2
Mw = 13,000

<Synthesis of Dye (B)>
First, according to Synthesis Example 1 of JP 2000-162429 A, a compound represented by the following formula (b) was synthesized. Next, 6.0 g (10 mmol) of a compound represented by the following formula (b) was added to 50 mL of methylene chloride and 10 mL of water and stirred. Next, 3.19 g (10 mmol) of potassium bis (trifluoromethanesulfonyl) imide was added and stirred for 2 hours. Thereafter, the aqueous layer was removed and the methylene chloride layer was concentrated to obtain 8.2 g of a dye (B) represented by the following formula (B).

<Preparation of colored layer (colored pattern)>
Each of the compositions of Examples and Comparative Examples prepared as described above was applied on the undercoat layer of the silicon wafer substrate with the undercoat layer prepared above to form a colored radiation-sensitive composition layer. And it heat-processed for 120 second (prebaking) using the 100 degreeC hotplate so that the dry film thickness of this coloring radiation sensitive composition layer might be 0.6 micrometer.

Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon), exposure was carried out at various exposure doses of 50 to 1200 mJ / cm ² through an Island pattern mask having a pattern of 1.0 μm square at a wavelength of 365 nm.
Then, the silicon wafer substrate on which the exposed colored radiation-sensitive composition layer was formed was placed on a horizontal rotary table of a spin shower developer (DW-30 type, manufactured by Chemtronics), and the following Table 2 Paddle development was performed at 23 ° C. for 60 seconds using the organic solvent described in 1 above. In addition, when processing (development) was not performed using an organic solvent, “-” was described in the item of organic solvent in Table 2 below (the same applies hereinafter). Next, paddle development was performed for 60 seconds in a 23 ° C. environment using CD-2000 (manufactured by FUJIFILM Electronics Materials) to form a colored pattern on the silicon wafer substrate.

The silicon wafer on which the colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotational speed of 50 r. p. m. While being rotated, pure water was supplied from the upper side of the rotation center in a shower form to perform a rinsing treatment, and then spray-dried.
As described above, a monochromatic color filter having a colored pattern formed from the colored radiation-sensitive composition of Example or Comparative Example was produced.
Thereafter, the size of the colored pattern was measured using a length measuring SEM (scanning electron microscope) “S-9260A” (manufactured by Hitachi High-Technologies). The exposure amount at which the pattern size was 1.0 μm was determined as the optimum exposure amount.

<Evaluation>
The evaluation described below was performed. The results are shown in Table 2 below.

(Residue)
20 places outside the colored pattern formation region (unexposed portion) were observed using a scanning electron microscope (SEM) (magnification 10,000 times), and the residues were counted. The smaller the number of residues, the better and the good developability.

(Pattern linearity)
20 colored patterns were observed using a scanning electron microscope (magnification 10,000 times), and pattern linearity was evaluated based on the following criteria. If it is A or B, it can be evaluated that deterioration of the pattern linearity due to the generation of the residue is suppressed.
A: A pattern with a line width of 1.0 μm was formed with good linearity.
B: Roughness was observed in the pattern having a line width of 1.0 μm, but it was at a level causing no practical problem.
C: Raggedness was observed in the pattern having a line width of 1.0 μm, and the linearity was poor.

(Surface roughness)
In the same manner as described above, a colored radiation-sensitive composition layer having a dry film thickness of 1 μm was formed on an undercoat layer of a silicon wafer with an undercoat layer, and then the entire surface of the substrate was 200 mJ / cm ² (illuminance 20 mW / cm ² ) exposure.
Thereafter, the silicon wafer substrate on which the exposed colored radiation-sensitive composition layer is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemtronics) and described in Table 2. Paddle development was performed at 23 ° C. for 60 seconds using the above organic solvent. Next, paddle development was performed for 60 seconds in a 23 ° C. environment using CD-2000 (manufactured by Fuji Film Electronics Materials), and then dried for 5 minutes in a 200 ° C. environment. The surface roughness (Ra) of the obtained colored layer was measured using an AFM (Atomic Force Microscope) (Digital Instruments, Nano Scope) under the following conditions (unit: nm). The smaller the value of the surface roughness Ra of the colored layer, the lower the generation of the residue.
-Measurement conditions-
・ Measurement area: 10μm square ・ Scan Rate: 1Hz

(defect)
About the board | substrate with which the colored layer which measured surface roughness was formed, the foreign material of a magnitude | size of 2.0 micrometers or more was counted using the defect evaluation apparatus ComPLUS (made by Applied Materials). It can be evaluated that the smaller the value, the more the generation of residue is suppressed.

(Heat-resistant)
The obtained colored radiation-sensitive composition was applied on a glass substrate so that the dry film thickness was 0.6 μm, and the substrate surface (the surface on which the colored radiation-sensitive composition was not applied) The sample was placed on a hot plate at 260 ° C. so as to be in contact with the plate and heated for 1 hour, and then the color difference (ΔE * ab value) before and after heating was measured with a chromaticity meter MCPD-1000 (manufactured by Otsuka Electronics). Evaluated. A smaller ΔE * ab value indicates better heat resistance.

(Reflectance)
With respect to the substrate on which the colored layer whose surface roughness was measured was formed, an incident angle was set to 5 degrees, and light having a wavelength of 400 to 700 nm was incident, and the reflectance was measured with a spectroscope UV4100 manufactured by Hitachi High Technology (unit: %). It can be evaluated that the lower the reflectance value, the lower the reflection of the colored layer.

  As is clear from the results shown in Table 2 above, in comparison with Comparative Example 1 in which the treatment using the organic solvent was not performed, in Examples 1 to 20 in which the treatment using the organic solvent was performed, the generation of residues was suppressed. I understood that it was done.

  Further, when Examples 1 to 20 are compared, PGMEA, cyclohexanone, cyclopentanone, and 1-methoxy-2-but are used as organic solvents rather than Examples 6, 7, 12, and 13 using ethylene glycol or decane as the organic solvent. In Examples 1 to 5, 8 to 11, and 14 to 20 using propanol, methyl ethyl ketone, or butyl acetate, generation of residues was further suppressed.

Moreover, when Examples 1-20 were contrasted, the direction of Examples 9-20 which used resin E was that the colored layer was made low-reflection rather than resin 1-8 which did not use resin E.
In addition, when Examples 9 to 20 are compared, Examples using other resins E are more preferable than Examples 10 to 12 using resins (E-2) to (E-4) as the resin E. In particular, Examples 16 to 20 using the resins (E-8), (E-9), or Megafac RS-72-K were further reduced in reflection.

(Example 18-1)
Development was performed in the same manner as in Example 18 except that the order of organic development and alkali development using CD-2000 was changed. As a result, although the development speed was slightly slow, the level of residue equivalent to that in Example 18 could be achieved by setting the paddle time to 90 seconds.

(Example 18-2)
Except that the organic solvent used in the development processing was changed from 1-methoxy-2-propanol to a mixed solvent of 1-methoxy-2-propanol and cyclohexanone (mass ratio 1: 1), the same as in Example 18. As a result, evaluation results equivalent to those in Example 18 were obtained.

(Comparative Example 2)
Development was performed in the same manner as in Example 18 except that the alkali development treatment using CD-2000 was not performed. As a result, the residue is 100 or more, the pattern linearity is C, the surface roughness is 50 nm or more, the number of defects is 2000 or more, the heat resistance is 4.0, and the reflectance is 15%. there were.

Claims (4)

Forming a colored radiation-sensitive composition layer using a colored radiation-sensitive composition containing a coloring agent A, a polymerizable compound B, an alkali-soluble resin C, and a photopolymerization initiator D; and
A step b of exposing the colored radiation-sensitive composition layer to a pattern through a mask;
Treating the exposed colored radiation-sensitive composition layer to form a colored layer; c.
With
The step c performs any one of the step c1 of processing using a developer containing 50% by mass or more of an organic solvent and the step c2 of developing using an alkaline aqueous solution, and then the other step. The manufacturing method of a colored layer which is the process of implementing.   The manufacturing method of the colored layer of Claim 1 with which the developing solution containing the said organic solvent contains 95 mass% or more of organic solvents. The method for producing a colored layer according to claim 1 or 2, wherein the colored radiation-sensitive composition further contains a resin E having a group represented by the following general formula (1).
* -X ₁ -Y (1)
In General Formula (1), X ₁ represents a single bond or a divalent linking group. Y represents an alkyl group or a silyl group. * Represents a bonding position. The method for producing a colored layer according to claim 3, wherein the resin E further has a group represented by the following general formula (2).
* -X ₂ -Z (2)
In general formula (2), X ₂ represents a single bond or a divalent linking group. Z represents at least one group selected from the group consisting of a (meth) acryloyl group, an allyl group, a vinyl group, an oxetanyl group, an epoxy group, and a hydroxymethylamino group. * Represents a bonding position.