TWI699618B - Method for manufacturing colored layer, color filter, light-shielding film, solid state imaging device, and image display device - Google Patents

Abstract

The present invention provides a method for producing a colored layer in which the generation of residue is suppressed. The manufacturing method includes: a step a of forming a color sensitive radiation composition layer using a color sensitive radiation composition containing a colorant A, a polymerizable compound B, an alkali-soluble resin C, and a photopolymerization initiator D; Step b of exposing the colored radiation-sensitive composition layer into a pattern by a mask; and step c of processing the exposed colored radiation-sensitive composition layer to form a colored layer, the step c In order to implement any one of step c1 of processing using a developer containing an organic solvent and step c2 of developing using an alkaline aqueous solution, another step is performed thereafter.

Description

Manufacturing method of colored layer, color filter, shading film, solid Body imaging element and image display device

The invention relates to a method for manufacturing a coloring layer, a color filter, a light-shielding film, a solid-state photographic element and an image display device.

Previously, a colored layer was formed using a colored radiation-sensitive composition, and the colored layer can be used, for example, as 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 (coloring pattern), it is disclosed that "including... the step of applying a colored radiation composition to a substrate to form a colored radiation composition layer, ... coloring The step of exposing the radiation-sensitive composition layer into a pattern, and the step of developing the colored radiation-sensitive composition layer after exposure to form a colored pattern" method ([Scope of Patent Application No. 11]). At this time, during development, the unexposed part is eluted into the developer by performing the "alkali development treatment", and the exposed part remains ([0236]).

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2012-198408

When forming the colored layer, it is required to suppress the generation of residue after the development process. For example, when a linear pattern-like colored layer (linear pattern) is formed, if residues are generated, voids may be observed in the colored pattern (the pattern has poor linearity). In addition, the residue may adhere to the colored layer as foreign matter, and the surface roughness of the colored layer may deteriorate.

The inventors of the present invention formed the colored layer by the conventional method, and as a result, found that the suppression of the generation of residues was insufficient.

Therefore, the object of the present invention is to provide 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 using the colored layer obtained by the production method Device.

The inventors of the present invention conducted diligent studies in order to achieve the above-mentioned object, and as a result, they found that by performing a treatment using a developer containing an organic solvent before and after alkali development, the generation of residues can be suppressed, thereby completing the present invention.

That is, the inventors of the present invention found that the above-mentioned object can be achieved by the following configuration.

[1] A method of manufacturing a colored layer, comprising: forming a colored radiation composition using a colored radiation composition containing a colorant A, a polymerizable compound B, an alkali-soluble resin C, and a photopolymerization initiator D Step a of the layer; Step b of exposing the colored radiation-sensitive composition layer into a pattern through a mask; and The step c of processing the exposed colored radiation-sensitive composition layer to form a colored layer, the step c being the step c1 of performing processing using a developer containing an organic solvent, and developing using an alkaline aqueous solution Any step in step c2 is followed by another step.

[2] The method for producing a colored layer according to [1], wherein the developer containing an organic solvent contains 95% by mass or more of the organic solvent.

[3] The method for producing a colored layer as described in [1] or [2], wherein the colored radiation-sensitive composition further contains resin E having a group represented by the following general formula (1), * -X ₁ -Y...(1)

In the 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 the general formula (2), X ₂ represents a single bond or a divalent linking group; Z represents a group selected from (meth)acrylic acid, allyl, vinyl, oxetanyl, epoxy, and hydroxyl At least one group in the group consisting of methylamino groups; * indicates the bonding position.

[5] A color filter using a colored layer obtained by the method for producing a colored layer as described in any one of [1] to [4].

[6] A light-shielding film using a colored layer obtained by the method for producing a colored layer as described in 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 as described in any one of [1] to [4].

[8] An image display device having a colored layer obtained by the method for producing a colored layer as described in any one of [1] to [4].

According to the present invention, it is possible to provide a method for producing a colored layer in which the generation of residue 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.

Hereinafter, the content of the present invention will be described in detail.

In addition, in the specification of this application, "~" is used to include the numerical values described before and after it as the lower limit and the upper limit.

In addition, in the expression of the group (atomic group) in this specification, the expression that does not describe substituted and unsubstituted includes a group (atomic group) not having a substituent, and also includes a group (atomic group) having a substituent. For example, "alkyl" includes not only unsubstituted alkyl (unsubstituted alkyl) but also substituted alkyl (Substituted alkyl).

In addition, in this specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic acid" means acrylic acid and methacrylic acid, and "(meth)acryloyl" means acrylic acid. Group and methacrylic acid group. In addition, in this specification, "single body" and "monomer" have the same meaning. Monomers in the present invention are distinguished from oligomers and polymers, and refer to compounds with a weight average molecular weight of 2,000 or less. In this specification, the term "polymerizable compound" refers to a compound having a polymerizable functional group, and may be a single body or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.

The "radiation" in the present invention refers to those including visible rays, ultraviolet rays, extreme ultraviolet rays, electron beams, X-rays, and the like.

The manufacturing method of the colored layer of the present invention (hereinafter, also simply referred to as "the manufacturing method of the present invention") is a method of manufacturing the colored layer as follows, including: using a coloring agent A, a polymerizable compound B, an alkali-soluble resin C, and The step a of forming the color sensitive radiation composition layer of the color sensitive radiation composition of the photopolymerization initiator D; the step b of exposing the color sensitive radiation composition layer into a pattern through a mask; and The step c of processing the exposed colored radiation-sensitive composition layer to form a colored layer, the step c being the step c1 of performing processing using a developer containing an organic solvent, and developing using an alkaline aqueous solution Any step in step c2 is followed by another step.

According to the manufacturing method of the present invention, when the colored layer is formed, the generation of residues can be suppressed. The reason is estimated as follows.

First, a colored radiation-sensitive composition is used to form a colored radiation-sensitive composition layer, and then it is exposed in a pattern. In the exposed portion of the colored radiation-sensitive composition layer, the polymerizable compound B is cured by the action of the photopolymerization initiator D. and. By development (alkaline development) using an alkaline aqueous solution, the unexposed part is eluted into the alkaline aqueous solution, and the exposed part remains as a patterned colored layer (coloring pattern).

At this time, in the unexposed portion, the alkali-soluble resin C is eluted into the alkaline aqueous solution, but hydrophobic components other than the alkali-soluble resin C may not be eluted and become a residue.

Therefore, in the production method of the present invention, treatment using a developer containing an organic solvent is performed before and after alkaline development (hereinafter, for convenience, it is also referred to as "organic development"). Thereby, the hydrophobic component in the unexposed part is eluted into the organic solvent, and it is considered that the generation of residue is suppressed.

Hereinafter, first, after describing the colored radiation-sensitive composition used in the method of manufacturing the colored layer of the present invention, the method of manufacturing the colored layer of the present invention will be described.

[Colored Radiation Composition]

The color-sensitive radiation composition used in the production method of the present invention (hereinafter, also referred to as "the color-sensitive radiation composition of the present invention" or "the composition of the present invention" for convenience) contains at least colorant A, Polymerizable compound B, alkali-soluble resin C, and photopolymerization initiator D.

[Colorant A]

The composition of the present invention contains coloring agent A (hereinafter also simply referred to as "coloring agent"). By containing a coloring agent, a colored radiation composition with a desired color can be obtained.

The coloring agent contained in the composition of the present invention is not particularly limited, and one selected from the group consisting of a variety of previously known dyes and pigments can be used, or two or more of them can be used in combination. These can correspond to the present invention The use of the composition is appropriately selected. For example, if the composition of the present invention is used in the manufacture of color filters, it is also possible to use coloring agents such as R, G, and B that form the color pixels of the color filter (with color Any one of black coloring agents (black coloring agents) generally used for black matrix formation.

Hereinafter, regarding the coloring agent that can be used in the composition of the present invention, a coloring agent suitable for the use of a color filter will be described in detail.

As the chromatic pigment, a variety of conventionally known inorganic pigments or organic pigments can be used. In addition, regardless of the inorganic pigment or the organic pigment, if high transmittance is considered, it is preferable to use as fine as possible. If handling is also considered, the average primary particle diameter of the pigment is preferably 0.01 μm. ~0.1μm, more preferably 0.01μm~0.05μm.

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

In the present invention, the following pigments can be preferably used. However, the present invention is not limited to these.

C.I. Pigment YELLOW 1, C.I. Pigment Yellow 2, C.I. Pigment Yellow 3, CI Pigment Yellow 4, CI Pigment Yellow 5, CI Pigment Yellow 6, CI Pigment Yellow 10, CI Pigment Yellow 11, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 18, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 32, CI Pigment Yellow 34, CI Pigment Yellow 35, CI Pigment Yellow 35:1 CI Pigment Yellow 36, CI Pigment Yellow 36:1, CI Pigment Yellow 37, CI Pigment Yellow 37:1, CI Pigment Yellow 40, CI Pigment Yellow 42, CI Pigment Yellow 43, CI Pigment Yellow 53, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61, CI Pigment Yellow 62, CI Pigment Yellow 63, CI Pigment Yellow 65, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 77, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 86, CI Pigment Yellow 93, CI Pigment Yellow 94, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 114, CI Pigment Yellow 115, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 118, CI Pigment Yellow 119, CI Pigment Yellow 120, CI Pigment Yellow 123, CI Pigment Yellow 125, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 137, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 147, CI Pigment Yellow 148, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 156, CI Pigment Yellow 161, CI Pigment Yellow 162, CI Pigment Yellow 164, CI Pigment Yellow 166, CI Pigment Yellow 167, CI Pigment Yellow 168, CI Pigment Yellow 169, CI Pigment Yellow 170, CI Pigment Yellow 171, CI Pigment Yellow 172, CI Pigment Yellow 173, CI Pigment Yellow 174, CI Pigment Yellow 175, CI Pigment Yellow 176, CI Pigment Yellow 177, CI Pigment Yellow 179, CI Pigment Yellow 180, CI Pigment Yellow 181, CI Pigment Yellow 182, CI Pigment Yellow 185, CI Pigment Yellow 187, CI Pigment Yellow 188, CI Pigment Yellow 193, CI Pigment Yellow 194, CI Pigment Yellow 199, CI Pigment Yellow 213, CI Pigment Yellow 214, etc., CI Pigment Orange 2, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 16, CI Pigment Orange 17:1, CI Pigment Orange 31, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 48, CI Pigment Orange 49, CI Pigment Orange 51. CI Pigment Orange 52, CI Pigment Orange 55, CI Pigment Orange 59, CI Pigment Orange 60, CI Pigment Orange 61, CI Pigment Orange 62, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, etc., CI Pigment Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 9, CI Pigment Red 10, CI Pigment Red 14. CI Pigment Red 17, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 31, CI Pigment Red 38, CI Pigment Red 41, CI Pigment Red 48:1, CI Pigment Red 48: 2, CI Pigment Red 48 ：3, CI Pigment Red 48:4, CI Pigment Red 49, CI Pigment Red 49:1, CI Pigment Red 49:2, CI Pigment Red 52:1, CI Pigment Red 52:2, CI Pigment Red 53:1, CI Pigment Red 57:1, CI Pigment Red 60:1, CI Pigment Red 63:1, CI Pigment Red 66, CI Pigment Red 67, CI Pigment Red 81:1, CI Pigment Red 81: 2, CI Pigment Red 81: 3. CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90, CI Pigment Red 105, CI Pigment Red 112, CI Pigment Red 119, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Yan Material Red 150, CI Pigment Red 155, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 169, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 184, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 200, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 210, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 246, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 270, CI Pigment Red 272, CI Pigment Red 279, CI Pigment Green 7, CI Pigment Green 10, CI Pigment Green 36, CI Pigment Green 37, CI Pigment Green 58, CI Pigment Green 59, CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 27, CI Pigment Violet 32, CI Pigment Violet 37. CI Pigment Violet 42, CI Pigment Blue 1, CI Pigment Blue 2, CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15: 2, CI Pigment Blue 15: 3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Blue 16, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64, CI Pigment Blue 66, CI Pigment Blue 79, CI Pigment Blue 80, CI Pigment Black ( Pigment Black)1.

These organic pigments can be used alone or in combination of multiple types to improve color purity.

In the composition of the present invention, when the coloring agent is a dye, a colored composition in a state uniformly dissolved in the composition can be obtained.

The dye that can be used as a colorant contained in the composition of the present invention is not particularly limited, and a dye that has been previously known as a color filter can be used. For example, pyrazole azo series, anilino azo series, triphenylmethane series, anthraquinone series, anthrapyridone series, benzylidene series, oxacyanine series, pyrazolotriazole azo series, Dyes such as pyridone azo series, cyanine series, phenothiazine series, pyrrolopyrazole imine series, xanthene series, phthalocyanine series, benzopyran series, indigo series, pyrromethene series, etc. In addition, multimers of these dyes can also be used.

In addition, from the viewpoint of removing unexposed portions by alkali development, there are cases where acid dyes and/or derivatives thereof can be suitably used.

In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and/or these can also be effectively used. Derivatives and so on.

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

In addition, azo-based, xanthene-based, and phthalocyanine-based acid dyes other than those described above are also preferred, and CI Solvent Blue 44, CI Solvent Blue 38; CI Solvent Orange ( Solvent orange) 45; acid dyes such as Rhodamine B and Rose Bengal 110 and derivatives of these dyes.

Among them, the coloring agent is preferably selected from the group consisting of triarylmethane series, anthraquinone series, azomethine series, benzylidene series, oxacyanine series, cyanine series, phenothiazine series, and pyrrolopyrazomethine series. Amine series, xanthene series, phthalocyanine series, benzopyran series, indigo series, pyrazole azo series, anilino azo series, pyrazolotriazole azo series, pyridone azo series, anthrapyridone Coloring agent in the series and pyrromethene series.

Furthermore, a pigment and a dye can also be combined and used.

The coloring agent usable in the present invention is preferably a dye or a pigment. It is particularly desirable that the average particle diameter (r) satisfies 20nm≦r≦300nm, preferably 125nm≦r≦250nm, particularly preferably 30nm≦r≦200nm. By using pigments with such an average particle diameter, pixels with high contrast ratio and high light transmittance can be obtained. The "average particle diameter" referred to herein refers to the average particle diameter of secondary particles formed by gathering primary particles (single crystals) of the pigment. The average primary particle size can be determined by the following method: Observe using a Scanning Electron Microscope (SEM) or Transmission Electron Microscope (TEM), and measure the part where the particles have not aggregated 100 The size of each particle to calculate the average value.

In addition, the particle size distribution of the secondary particles of the pigment usable in the present invention (hereinafter referred to as "particle size distribution") is desirably 70% by mass of the secondary particles at (average particle diameter ± 100) nm. Above, it is preferably 80% by mass or more. Furthermore, in the present invention, the particle size distribution is measured using the scattering intensity distribution.

The pigment having the average particle size and particle size distribution can be prepared by the following method: a commercially available pigment and other pigments (average particle size usually exceeding 300nm) used as appropriate, and preferably a dispersant and The pigment mixture formed by mixing the solvent is mixed with a crusher such as a bead mill (beads mill) or a roll mill (roll mill). dispersion. The pigment obtained in this manner usually takes the form of a pigment dispersion.

<Miniaturization of Pigments>

In the present invention, fine and sized organic pigments can be used as needed. The miniaturization of the pigment can be achieved by the following steps: preparing a high-viscosity liquid composition of the pigment, a water-soluble organic solvent, and a water-soluble inorganic salt, applying stress and grinding using a wet grinding device or the like.

As the water-soluble organic solvent used in the step of refining the pigment, for example, methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethyl Glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether acetate, etc.

In addition, as long as it is adsorbed on the pigment by a small amount of use and will not be lost in the wastewater, other solvents with low or insoluble water solubility can also be used, such as benzene, toluene, xylene, ethylbenzene, chlorobenzene , Nitrobenzene, aniline, pyridine, quinoline, four Hydrofuran, dioxane, ethyl acetate, isopropyl acetate, butyl acetate, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methyl ring Hexane, halogenated hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, dimethyl sulfide, N-methylpyrrolidone, etc.

The solvent used in the step of refining the pigment may be only one type, or two or more types may be mixed and used as necessary.

In the present invention, as the water-soluble inorganic salt used in the step of refining the pigment, sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate, etc. can be cited.

The amount of water-soluble inorganic salt used in the refining step is 1 mass times to 50 mass times that of the pigment, and the larger amount has a grinding effect, but from the viewpoint of productivity, the more preferable amount is 1 mass times~ 10 times the quality. In addition, it is preferable to use inorganic salts with a moisture content of 1% or less.

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

Regarding the operating conditions of the wet pulverizing device in the step of refining the pigment, there is no particular limitation. In order to effectively perform the grinding with the pulverizing medium, the operating conditions when the device is a kneader are the blades in the device. The rotation speed is preferably 10rpm~200rpm. In addition, the grinding effect of the two-axis rotation ratio is larger and better. The total operation time and dry pulverization time are preferably 1 hour to 8 hours, and the internal temperature of the device is preferably 50°C to 150°C. In addition, the water-soluble inorganic salt as the grinding medium preferably has a grinding particle size of 5 μm to 50 μm, a sharp particle size distribution and a spherical shape.

<The blending of pigments (color matching)>

These organic pigments can be used alone or in combination of multiple types in order to improve color purity. Specific examples of the combination are shown below. For example, as red pigments, anthraquinone-based pigments, perylene-based pigments, and diketopyrrolopyrrole-based pigments can be used alone, or at least one of these pigments can be used together with bisazo-based yellow pigments and isoindoline-based yellow pigments. , A mixture of quinophthalone-based yellow pigments or perylene-based red pigments, anthraquinone-based red pigments, and diketopyrrolopyrrole-based red pigments. For example, as anthraquinone pigments, CI Pigment Red 177 can be cited, as perylene pigments, CI Pigment Red 155 and CI Pigment Red 224 can be cited, and as diketopyrrolopyrrole pigments, CI Pigment Red 254 can be cited. From the viewpoint of reproducibility, mixing with CI Pigment Yellow 83, CI Pigment Yellow 139, or CI Pigment Red 177 is preferable. In addition, the quality of red pigment and other pigments is better than 100:5~100:80. Within this range, the light transmittance of 400 nm to 500 nm can be suppressed, the color purity can be improved, and sufficient color rendering power can be achieved. In particular, as the mass ratio, the range of 100:10 to 100:65 is best. Furthermore, in the case of a combination of red pigments, it can be adjusted according to chromaticity.

In addition, as a green pigment, a halogenated phthalocyanine-based pigment can be used alone, or it can be used in combination with a bisazo-based yellow pigment, a quinophthalone-based yellow pigment, an azomethine-based yellow pigment, or an isoindoline-based yellow pigment the mix of. For example, as such an example, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37, CI Pigment Green 58 and CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, A blend of CI Pigment Yellow 180 or CI Pigment Yellow 185. The quality of green pigment and yellow pigment is better than 100:5~100:200. Quality in the range Binet can suppress light transmittance from 400nm to 450nm, improve color purity, and achieve the National Television System Committee (NTSC) target corresponding to the set position without the dominant wavelength being close to the long wavelength Hue near the hue. The quality bit is in the range of 100:20 to 100:150.

As the blue pigment, one kind of phthalocyanine-based pigment may be used alone, or a mixture thereof with a dioxazine-based purple pigment may be used. As a particularly suitable example, a mixture of C.I. Pigment Blue 15:6 and C.I. Pigment Violet 23 can be cited.

The quality of blue pigment and purple pigment is preferably 100:0~100:100, and more preferably 100:70 or less.

As the pigment, inorganic pigments can be used. Examples of inorganic pigments include metal-containing inorganic pigments including metal pigments, metal compounds, metal oxides, and the like, carbon black, and metal borides.

In addition, the composition of the present invention can be used not only for the formation of colored regions (pixels) of color filters, but also for the formation of black matrices and light-shielding films, etc., as a composition for forming a black matrix and a composition for forming a light-shielding film In addition to carbon, titanium black, iron oxide, titanium oxide, silver tin, silver, tungsten compounds, metal borides, etc., black or infrared-shielding pigments used in other materials can also be used including metals containing titanium oxide Pigments such as oxides and metal mixtures. From the viewpoint of excellent light-shielding properties, carbon, titanium black, tungsten compound, and metal boride are preferable, and from the viewpoint of excellent sensitivity, titanium black, tungsten compound, and metal boride are more preferable.

These pigments can be used in combination of two or more, and can also be combined with the dyes and The aforementioned dyes and organic pigments are used together. In order to adjust the color, or to improve the light-shielding properties in a desired wavelength region, for example, black or a pigment having infrared light-shielding properties may be mixed with the color pigments listed in the column of "pigment mixing". It is preferable to include a red pigment or dye, and a purple pigment or dye in black or a pigment having infrared light-shielding properties, and it is particularly preferable to include a red pigment in black or a pigment having infrared light-shielding properties.

Hereinafter, the titanium black dispersion will be described in detail.

The titanium black dispersion is a dispersion containing titanium black as a colored material.

By including titanium black as a titanium black dispersion prepared in advance in the composition of the present invention, the dispersibility and dispersion stability of titanium black are improved.

Hereinafter, titanium black will be described.

<Titanium Black>

The so-called titanium black refers to black particles having titanium atoms. Preferred are low-order titanium oxide and titanium oxynitride. For purposes such as improving dispersibility and suppressing cohesion, the surface of the titanium black particles may be modified as necessary. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. In addition, treatment using a water-repellent substance shown in Japanese Patent Laid-Open No. 2007-302836 can also be performed.

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

The specific surface area of titanium black is not particularly limited. In order to make the water repellency after surface treatment of the titanium black with a water repellent agent become a predetermined performance, it is measured by the Brunauer-Emmett-Teller (BET) method The value is usually about 5m ² /g~150m ² /g, particularly preferably about 20m ² /g~100m ² /g.

As an example of a commercially available product of titanium black, for example, titanium black (titanium black) 10S, 12S, 13R, 13M, 13M-C, 13R-N manufactured by Mitsubishi Materials Co., Ltd., and Thai Tilack D etc., but the present invention is not limited to these.

Hereinafter, the tungsten compound and metal boride will be described in detail.

The composition of the present invention can use tungsten compounds and/or metal borides.

Tungsten compounds and metal borides are infrared shielding materials that have high absorption of infrared rays (light with a wavelength of about 800 nm to 1200 nm) (that is, high light-shielding properties (shielding properties) for infrared rays) and low absorption of visible light. Therefore, the composition of the present invention can form a pattern with high light-shielding properties in the infrared region and high light-transmitting properties in the visible light region by containing a tungsten compound and/or a metal boride.

In addition, tungsten compounds and metal borides also have a small absorption of light in the visible region used in exposure of high-pressure mercury lamps, KrF, ArF, etc., which have a shorter wavelength than that used in image formation. Therefore, by combining with the polymerizable compound, alkali-soluble resin, and photopolymerization initiator described later, it is possible to obtain an excellent pattern while further suppressing residues during pattern formation.

Examples of the tungsten compound include tungsten oxide-based compounds, tungsten boride-based compounds, tungsten sulfide-based compounds, and the like, and are preferably tungsten oxide-based compounds represented by the following general formula (composition formula) (I).

M _x W _y O _z …(I)

M represents metal, W represents tungsten, and O represents oxygen.

0.001≦x/y≦1.1

2.2≦z/y≦3.0

Examples of the metal of M include alkali metals, alkaline earth metals, 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, etc., preferably alkali metals. The metal of M may be one type or two or more types.

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, the generation of impurity phases in the tungsten compound can be more reliably avoided.

When z/y is 2.2 or more, the 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, and Cs _0.33 WO _{3 is} preferred. Or Rb _0.33 WO ₃ , more preferably Cs _0.33 WO ₃ .

The tungsten compound is preferably fine particles. The average particle size of the tungsten fine particles is preferably 800 nm or less, more preferably 400 nm or less, and still more preferably 200 nm or less. By averaging With a particle size in this range, it is difficult for the tungsten fine particles to block visible light due to light scattering, and therefore the light transmittance in the visible light region can be made more reliable. From the viewpoint of avoiding light scattering, the smaller the average particle size is, the better, but for reasons such as ease of handling during production, the average particle size of the tungsten fine particles is usually 1 nm or more.

In addition, two or more types of tungsten compounds can be used.

Tungsten compounds can be obtained as commercially available products. When the tungsten compound is a tungsten oxide compound, the tungsten oxide compound can be obtained by heat-treating the tungsten compound in an inert gas atmosphere or a reducing gas atmosphere ( (Refer to Japanese Patent No. 4096205).

In addition, the tungsten oxide compound can also be obtained as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd., for example.

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

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 size is in this range, the metal boride fine particles are difficult to block visible light due to light scattering, and therefore, the light transmittance in the visible light region can be made more reliable. From the viewpoint of avoiding light scattering, the smaller the average particle size, the better, but it is easy to handle during manufacturing For reasons such as performance, the average particle size of the metal boride fine particles is usually 1 nm or more.

In addition, two or more types of metal borides can be used.

The metal boride can be obtained as a commercially available product, for example, it can also be obtained as a dispersion of metal boride fine particles such as KHF-7 manufactured by Sumitomo Metal Mining Co., Ltd.

In the total solid content of the composition of the present invention, the content of the coloring agent contained in the composition of the present invention is preferably 20% by mass to 95% by mass, more preferably 25% by mass to 90% by mass, and still more preferably 30% to 80% by mass.

<Dye>

Hereinafter, the dye which can be contained in the colored radiation composition of this invention is demonstrated in detail.

The dye is not particularly limited, and dyes previously known as color filters can be used. For example, single dyes and dye multimers can be used. Specifically, pyrazole azo series, anilino azo series, triphenylmethane series, anthraquinone series, anthrapyridone series, benzylidene series, oxacyanine series, pyrazolotriazole azo series can be used. Series, pyridone azo series, cyanine series, phenothiazine series, pyrrolopyrazolimide series, xanthene series, phthalocyanine series, benzopyran series, indigo series, pyrromethene series, sub Methyl-based dyes. In addition, multimers of these dyes can also be used.

In addition, in the case of water or alkali development, from the viewpoint of completely removing the binder and/or dye in the light-unirradiated area by development, there are cases where acid dyes and/or derivatives thereof can be suitably used .

The dye used in the present invention preferably has a color derived from dipyrromethene Partial structure of pigments in pigments, azo pigments, anthraquinone pigments, triphenylmethane pigments, xanthene pigments, cyanine pigments, squaraine pigments, quinophthalone pigments, phthalocyanine pigments and subphthalocyanine pigments .

Furthermore, the dye used in the present invention is preferably a multimer having a partial structure and a polymerizable group, and more 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 nm to 780 nm. This dye functions as a coloring agent in the coloring radiation composition of this invention, for example.

In addition, the "partial structure derived from a pigment" refers to a specific pigment (hereinafter, also referred to as a pigment compound) that can form a pigment structure described later by removing hydrogen atoms that can be connected to a pigment polymer ( A structure in which polymer chains or dendrimer cores, etc.) are connected.

(Partial structure derived from pigment)

As the partial structure derived from the pigment in the dye used in the coloring radiation composition of the present invention (hereinafter, also referred to as "pigment structure"), for example, a dye structure selected from the following dyes and the like: quinone dye ( Benzoquinone dye, naphthoquinone dye, anthraquinone dye, anthrapyridone dye, etc.), carbonium dye (diphenylmethane dye, triphenylmethane dye, xanthene dye, acridine dye, etc.), quinoneimine dye ( Oxazine pigments, thiazine pigments, etc.), azine pigments, polymethine pigments (oxocyanine pigments, merocyanine pigments, arylene pigments, styryl pigments, cyanine pigments, etc.) Squaraine ylide pigment, croconium pigment, etc.), quinophthalone pigment, phthalocyanine pigment, subphthalein Cyanine pigments, periconone pigments, indigo pigments, thioindigo pigments, quinoline pigments, nitro pigments, nitroso pigments, dipyrromethene pigments, azo pigments, and metal complex pigments thereof.

Among these dye structures, in terms of color separation, substrate adhesion, and surface roughness, it is particularly preferred to be selected from the group consisting of dipyrromethene dyes, azo dyes, anthraquinone dyes, triphenylmethane dyes, The pigment structure of xanthene pigments, cyanine pigments, squaraine pigments, quinophthalone pigments, phthalocyanine pigments, and subphthalocyanine pigments.

The dye used in the present invention may be substituted for the hydrogen atom in the dye structure by a substituent selected from the following substituent group A.

(Substituent Group A)

Examples of substituents that the dye multimer may have include halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, and carboxyl groups. , Alkoxy, aryloxy, silanyloxy, heterocyclic oxy, acyloxy, carbamoyloxy, amine (including alkylamino, anilino), acylamino, aminocarbonylamine Group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group or arylsulfonylamino group, mercapto, alkylthio, arylthio, hetero Sulfonyl, sulfasulfonyl, sulfo, alkylsulfinyl or arylsulfinyl, alkylsulfinyl or arylsulfonyl, sulfonyl, aryloxycarbonyl, alkoxycarbonyl , Carboxamide, arylazo or heterocyclic azo, imino, phosphino, phosphinyl, phosphinyloxy, phosphinylamino, silyl, etc.

For details, for example, paragraph 0027 to paragraph 0038 of JP 2013-29760 A can be referred to, and the content can be incorporated into the specification of this application.

Hereinafter, a particularly preferable pigment skeleton will be described.

(Anthraquinone Pigment)

Those having a partial structure derived from an anthraquinone dye (anthraquinone compound) are preferably those derived from compounds (anthraquinone compounds) represented by the following general formulas (AQ-1) to (AQ-3) structure. In the present invention, the term "anthraquinone compound" refers to a general term for compounds having a dye site including an anthraquinone skeleton in the molecule.

In the 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 represent a hydrogen atom, an alkyl group, or an aryl group. Rq ₁ to Rq ₄ represent substituents. The substituents that can be used for Rq ₁ to Rq ₄ are the same as those listed in the Substituent Group A section. Ra and Rb each independently represent a hydrogen atom, an alkyl group, or an aryl group.

In general formula (AQ-2), C and D have the same meanings as A and B in general formula (AQ-1). Xqb represents ORqb ₁ or NRqb ₂ Rqb ₃ . Rqb ₁ to Rqb ₃ each independently represent a hydrogen atom, an alkyl group, or an aryl group. Rq ₅ to Rq ₈ represent substituents. The meanings of Rq ₅ to Rq ₈ are the same as Rq ₁ to Rq ₄ in the general formula (AQ-1). The meaning of Rc is the same as that of Ra or Rb in the general formula (AQ-1).

In the general formula (AQ-3), the meanings of E and F are the same as those of A and B in the general formula (AQ-1). Xqc represents ORqc ₁ or NRqc ₂ Rqc ₃ . Rqc ₁ to Rqc ₃ each independently represent a hydrogen atom, an alkyl group, or an aryl group. The meanings of Rq ₉ to Rq ₁₂ are the same as Rq ₁ to Rq ₄ in the general formula (AQ-1). The meaning of Rd is the same as Ra or Rb in the general formula (AQ-1).

As a preferable range of the general formula (AQ-1), the general formula (AQ-2), and the general formula (AQ-3), for example, reference may be made to paragraphs 0045 to 0047 of Japanese Patent Laid-Open No. 2013-29760, which The content can be incorporated into the description of this application.

As a specific example of the anthraquinone dye, for example, paragraph 0049 and paragraph 0050 of JP 2013-29760 A can be referred to, and the content can be incorporated into the specification of this application.

(Triphenylmethane pigment)

The one having a partial structure derived from a triphenylmethane dye (triphenylmethane compound) is preferably a partial structure derived from a compound (triphenylmethane compound) represented by the following general formula (TP). In the present invention, the term “triphenylmethane compound” refers to a general term for compounds having a dye site including a triphenylmethane skeleton in the molecule.

Formula (TP) [化2]

In formula (TP), Rtp ¹ to Rtp ⁴ each independently represent 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 represent a hydrogen atom, an alkyl group, or an aryl group). Rtp ⁶ , Rtp ⁷ and Rtp ⁸ represent substituents. a, b, and c represent an integer of 0-4. When a, b, and c are 2 or more, Rtp ⁶ , Rtp ⁷ and Rtp ⁸ may be connected to each other to form a ring. X ^- represents an anionic structure. In the absence of X ^- , at least one of Rtp ¹ to Rtp ⁷ contains an anion.

As a preferred range of the general formula (TP), for example, paragraph 0055 to paragraph 0062 of Japanese Patent Laid-Open No. 2013-29760 can be referred to, and the content can be incorporated into the specification of this application.

(Xanthene pigment)

The one having a partial structure derived from a xanthene dye (xanthene compound) is preferably a partial structure derived from a xanthene compound represented by the following general formula (J).

[化3]

In the general formula (J), R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ each independently represent a hydrogen atom or a monovalent substituent, R ⁸⁵ each independently represents a monovalent substituent, and m represents an integer from 0 to 5 . X ^- represents an anion. In the absence of X ^- , at least one of R ⁸¹ to R ⁸⁵ includes an anion.

As a preferable range of the general formula (J), for example, paragraph 0066 to paragraph 0073 of JP 2013-29760 A can be referred to, and the content can be incorporated into the specification of this application.

(Anthocyanin)

The one having a partial structure derived from an cyanine pigment (cyanine compound) is preferably a partial structure derived from a compound (cyanine compound) represented by the following general formula (PM). In the present invention, the term "cyanine compound" refers to a general term for compounds having a pigment site including a cyanine skeleton in the molecule.

[化4]

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, paragraph 0077 to paragraph 084 of JP 2013-29760 A can be referred to, and the content can be incorporated into the specification of this application.

(Squaraine ylide pigment)

The one having a partial structure derived from a squarylium dye (squaraine ylide compound) is preferably a partial structure derived from the compound represented by the following general formula (K) (squaraine salt compound) . In the present invention, the term “squaraine ylide compound” refers to a general term for compounds having a dye site including a squaraine salt skeleton in the molecule.

[化5]

In the 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, and examples thereof include phenyl and naphthyl. The heterocyclic group is preferably a five-membered or six-membered heterocyclic group, for example, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, triazol-1-yl , Thienyl, furyl, thiadiazolyl, etc.

As a preferable range of the general formula (K), for example, paragraph 0088 to paragraph 0106 of JP 2013-29760 A can be referred to, and the content can be incorporated into the specification of this application.

(Quinophthalone pigment)

The one having a partial structure derived from a quinophthalone dye (quinophthalone compound) is preferably a partial structure derived from a compound (quinophthalone compound) represented by the following general formula (QP). In the present invention, the term "quinophthalone compound" refers to a general term for compounds having a dye site including a quinophthalone skeleton in the molecule.

[化6]

In the general formula (QP), Rqp ₁ to Rqp ₆ each independently represent a hydrogen atom or a substituent. When at least two of Rqp ₁ to Rqp ₆ are in adjacent positions, they may be bonded to each other to form a ring, and the ring may further have a substituent.

As a preferred range of the general formula (QP), for example, paragraph 0110 to paragraph 0114 of JP 2013-29760 A can be referred to, and the content can be incorporated into the specification of this application.

(Phthalocyanine pigment)

Those having a partial structure derived from a phthalocyanine dye (phthalocyanine compound) are preferably those having a partial structure derived from a compound (phthalocyanine compound) represented by the following general formula (F). In the present invention, the term "phthalocyanine compound" refers to a general term for compounds having a dye site including a phthalocyanine skeleton in the molecule.

[化7]

In the general formula (F), M ¹ represents metals, and Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent 6 members composed of atoms selected from hydrogen, carbon, and nitrogen. The group of atoms required for the ring.

As a preferable range of the general formula (F), for example, paragraph 0118 to paragraph 0124 of JP 2013-29760 A can be referred to, and the content can be incorporated into the specification of this application.

(Subphthalocyanine compound)

The one having a partial structure derived from the subphthalocyanine dye (subphthalocyanine compound) is preferably one having a partial structure derived from the compound (subphthalocyanine compound) represented by the following general formula (SP). In the present invention, the term "subphthalocyanine compound" refers to a general term for compounds having a dye site including a subphthalocyanine skeleton in the molecule.

[化8]

In the general formula (SP), Z ¹ to Z ¹² each independently represent a hydrogen atom, an alkyl group, an aryl group, a hydroxyl group, a mercapto group, an amino group, an alkoxy group, an aryloxy group, and a thioether group. X represents an anion.

As a preferable range of the general formula (SP), for example, paragraph 0128 to paragraph 0133 of JP 2013-29760 A can be referred to, and the content can be incorporated in the specification of this application.

In addition, regarding dipyrromethene dyes and azo dyes, for example, paragraph 0033 to paragraph 0135 of JP 2011-95732 A can be referred to, and the content can be incorporated in the specification of this application.

(Structure of the dye used in the colored radiation composition of the present invention)

The dye used in the color-sensitive radiation composition of the present invention may be a single pigment having a partial structure derived from the pigment in the molecule, or it may be a molecule There are two or more pigment oligomers or pigment multimers of the partial structure derived from the pigment.

(Pigment Monomer)

The dye monomer preferably contains a polymerizable group.

By setting it as such a structure, there exists a tendency for heat resistance to improve. The polymerizable group may contain only one type or two or more types. As the polymerizable group, a known polymerizable group that can be crosslinked by radicals, acid, or heat can be used. Examples include groups containing ethylenically unsaturated bonds, cyclic ether groups (epoxy groups, oxa Cyclobutanyl), methylol, etc., especially preferably a group containing an ethylenically unsaturated bond, more preferably a (meth)acryloyl group, particularly preferably derived from glycidyl (meth)acrylate and The (meth)acryloyl group of 3,4-epoxy-cyclohexyl methyl (meth)acrylate.

As a method of introducing a polymerizable group, there is a method of copolymerizing a dye monomer and a polymerizable group-containing compound to introduce it. For these methods, for example, paragraph 0181 to paragraph 0188 of JP 2013-29760 A can be referred to, and the content can be incorporated in the specification of this application.

The number of polymerizable groups in one molecule of the dye monomer is preferably 1 to 4, more preferably 1 to 2.

The pigment monomer may have an alkali-soluble group. As an alkali-soluble group, a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group can be illustrated.

In addition, as a method of introducing an alkali-soluble group into a dye monomer, a method of introducing an alkali-soluble group into a dye monomer in advance can be cited.

The number of alkali-soluble groups in one molecule of the pigment monomer is preferably 1~ 4. More preferably, 1~2.

In addition, functional groups that the dye monomer may have include: lactones, acid anhydrides, amides, -COCH ₂ CO-, cyano groups, and other development promoting groups, long-chain and cyclic alkyl groups, and aralkyl groups , Aryl, polyalkylene oxide, hydroxyl, maleimide, amine and other hydrophilic and hydrophobic adjusting groups, etc., can be suitably introduced.

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

(Pigment oligomer)

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

General formula (I)(R) _m -Q-(D) _n

(In the general formula (I), Q represents a linking group with (m+n) valence, R represents a substituent, and D represents the dye structure. m represents an integer from 0 to 6, n represents an integer from 2 to 8, (m +n) represents an integer of 2 to 8. When m is 2 or more, multiple Rs may be different from each other, and when n is 2 or more, multiple Ds may be different from each other)

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

As the linking group of (m+n) valence represented by Q, preferably A linking group represented by general formula (Q-1) or general formula (Q-2).

(In the general formula (Q-1), R ¹ to R ⁴ each independently represent a linking group or a substituent. Among them, at least two of R ¹ to R ⁴ are linking groups)

The substituent represented by R ¹ to R ⁴ is preferably 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), and a carbon number of 6 ~20 aryl group (preferably an aryl group with 6 to 14 carbons, more preferably an aryl group with 6 to 10 carbons), more preferably an alkyl group with 1 to 10 carbons, more preferably methyl, ethyl基, propyl.

The linking group represented by R ¹ to R ⁴ preferably contains 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 group having 1 to 5 carbon atoms or a hydrogen atom), and a combination of two or more of these groups , More preferably a group containing a combination of two or more of alkylene, -O-, -CO-, and -NRa-.

The number of atoms connecting R or D to the center C of the linking group represented by R ¹ to R ⁴ is preferably 1-15, and more preferably 1-10, 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 to the center C is 5.

(In the general formula (Q-2), A ¹ to A ⁴ each independently represent a carbon atom or a nitrogen atom. R ¹¹ to R ¹⁶ each independently represent a hydrogen atom, =0 or a linking group. The dotted line represents a single bond or a double bond )

The 6-membered ring containing A ¹ to A ⁴ in the general formula (Q-2) includes 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 has the same meaning as the linking group represented by R ¹ to R ⁴ in the general formula (Q-1), and the preferable range is also the same.

The following shows a specific example of the (m+n) valence linking group represented by Q. However, in the present invention, these restrictions are not imposed.

[化11]

R in general formula (I) each independently represents a substituent, and when m is 2 or more, a plurality of Rs may be different from each other.

Examples of the substituent represented by R include halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, carboxyl groups, Alkoxy, aryloxy, silanoxy, heterocyclic oxy, acyloxy, amine Formoxy, amine (including alkylamino and anilino), amide, aminocarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfamoylamino, Alkylsulfonylamino or arylsulfonylamino, sulfhydryl, alkylthio, arylthio, heterocyclic thio, sulfamsulfonyl, sulfo, alkylsulfinyl or arylsulfinyl Acetyl, alkylsulfonyl or arylsulfonyl, acyl, aryloxycarbonyl, alkoxycarbonyl, aminomethanyl, arylazo or heterocyclic azo, animino, Phosphine group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphinyl group, silyl group, etc.

In addition, 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, acid, and heat. For example, a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetanyl group), a hydroxymethyl group, etc. may be mentioned. Preferably, a group containing an ethylenically unsaturated bond is more preferred ( The meth)acryloyl group is particularly preferably a (meth)acryloyl group derived from glycidyl (meth)acrylate and 3,4-epoxy-cyclohexylmethyl (meth)acrylate.

Examples of alkali-soluble groups include acid groups such as carboxyl groups, sulfo groups, and phosphoric acid groups. Preferably it is a carboxyl group.

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 to 8, preferably an integer of 2 to 7, and more preferably an integer of 3 to 6.

(Pigment polymer)

The pigment multimer has two or more partial structures derived from the pigment in the molecule. The pigment multimer is preferably a pigment multimer comprising at least one of the structural units represented by the following general formula (A), general formula (B), and general formula (C), or a general formula ( D) The pigment multimer represented. According to the production method of the present invention, even in the case of using a pigment polymer whose residue is likely to remain, the residue is reduced, the pattern linearity is also excellent, the deterioration of the surface roughness can be suppressed, and the desired product of the present invention can be obtained more significantly Effect.

The structural unit represented by the general formula (A)

In the 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 pigment structure.

Hereinafter, the general formula (A) will be described in detail.

In the general formula (A), X ₁ represents a linking group formed by polymerization. That is, it means a part formed by a polymerization reaction that forms a structural unit corresponding to the main chain. Furthermore, the part indicated 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, and particularly preferably a linking group represented by the following (XX-1) to (XX-24), and more preferably Choose from (XX-1) and (XX-2) (meth)acrylic link chains, (XX-10)~(XX-17) styrene link chains, (XX-18) ), (XX-19), and (XX-24), more preferably selected from (meth)acrylic links represented by (XX-1) and (XX-2) Chain, the styrene-based link chain represented by (XX-10)~(XX-17), and the vinyl-based link chain represented by (XX-24), more preferably (XX-1) and ( The (meth)acrylic linking chain represented by XX-2) and the styrene linking chain represented by (XX-11).

(XX-1) ~ (XX -24) , the location indicated by the * coupled to L _1. Me represents methyl. In addition, R in (XX-18) and (XX-19) represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

[化14]

[化15]

In the general formula (A), L ₁ represents a single bond or a divalent linking group. As the divalent linking group when L ₁ represents a divalent linking group, it represents a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (for example, methylene, ethylene, trimethylene, ethylene Propyl, butylene, etc.), substituted or unsubstituted arylene groups having 6 to 30 carbons (for example, phenylene, naphthylene, etc.), substituted or unsubstituted heterocyclic linking groups, -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 of these. In addition, L _{1 is} also preferably a composition containing an anion. 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 each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. The example when L ₁ contains an anion will be described later.

In the general formula (A), DyeI represents the dye structure.

A dye multimer having a structural unit represented by the general formula (A) can be synthesized by the following method: (1) a method of synthesis by addition polymerization of a monomer having a dye residue; (2) using Method of reacting polymers with highly reactive functional groups such as isocyanate groups, acid anhydride groups, or epoxy groups, and dyes having functional groups that can react with highly reactive groups (hydroxyl, primary or secondary amine groups, carboxyl groups, etc.) .

The well-known addition polymerization (radical polymerization, anionic polymerization, cationic polymerization) can be used in addition polymerization. Among them, especially the synthesis by free radical polymerization can stabilize the reaction conditions without causing the pigment structure Decomposed, so better. Known reaction conditions can be applied to radical polymerization. That is, the dye multimer used in the present invention is preferably an addition polymer.

Among them, from the viewpoint of heat resistance, the dye multimer having a structural unit represented by the general formula (A) is preferably obtained by radical polymerization using a dye monomer having an ethylenically unsaturated bond Free radical polymer.

For details of the general formula (A), refer to paragraph 0138 to paragraph 0152 of JP 2013-29760 A, the content of which can be incorporated into the specification of this application.

The structural unit represented by the general formula (B)

[化16]

In the general formula (B), X _{2 has} the same meaning as X ₁ in the general formula (A). L L is the same meaning as in general _{formula. 1} (A) ₂ in. Y ₂ represents a group that can be ionically bonded or coordinately bonded to DyeII. DyeII represents the pigment structure. For details of the general formula (B), refer to paragraph 0156 to paragraph 0161 of JP 2013-29760 A, the content of which can be incorporated into the specification of this application.

The structural unit represented by the general formula (C)

In the general formula (C), L ₃ represents a single bond or a divalent linking group. DyeIII represents the pigment structure. m represents 0 or 1. For details of the general formula (C), refer to paragraphs 0165 to 0167 of JP 2013-29760 A, the content of which can be incorporated into the specification of this application.

Pigment polymer represented by general formula (D)

In the general formula (D), L ₄ represents an n-valent linking group. n represents an integer of 2-20. When n is 2 or more, the structure of DyeIV may be the same or different. DyeIV represents the pigment structure. For details of the general formula (D), refer to paragraph 0173 to paragraph 0178 of JP 2013-29760 A, the content of which can be incorporated into the specification of this application.

Pigment multimers having structural units represented by general formula (A), general formula (B) and/or general formula (C), and pigment multimers represented by general formula (D), having The dye multimers of the constituent units represented by the general formula (A) and the general formula (C) and the dye multimers represented by the general formula (D) are linked by covalent bonds, and therefore contain the dye multimers The color-sensitive radiation composition has excellent heat resistance, and when the color-sensitive radiation composition is applied to the formation of colored patterns of multiple colors, it is effective in suppressing color shift to other adjacent colored patterns, so Better. In addition, in particular, the compound represented by the general formula (A) is easy to control the molecular weight of the dye multimer. Better.

When all the constituent units in the pigment multimer are set to 100 mol%, the content of the constituent units having a pigment structure of the pigment multimer is preferably 15 mol% to 60 mol%, and more preferably 20 mol% Ear%~50 mol%, particularly preferably 20 mol%~45 mol%.

"Other functional groups or other constituent units"

The dye multimer may have a functional group and other structural units other than the structural unit having a dye structure.

The functional group may be included in a structural unit having a dye structure, or may be included in the form of another structural unit including a functional group, unlike the structural unit having a dye structure.

Examples of the functional group include a polymerizable group and an alkali-soluble group.

Hereinafter, these details will be described.

"The Cohesion Base"

The polymerizable group may contain only one type or two or more types.

As the polymerizable group, a known polymerizable group that can be crosslinked by free radicals, acid, or heat can be used, for example, groups containing ethylenic unsaturated bonds, cyclic ether groups (epoxy groups, oxa Cyclobutanyl), hydroxymethyl, etc., especially preferably a group containing an ethylenically unsaturated bond, more preferably a (meth)acrylic acid group, and still more preferably derived from glycidyl (meth)acrylate And the (meth)acrylic group of 3,4-epoxy-cyclohexyl methyl (meth)acrylate.

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

In the 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.

L ₁ are the same as the general formula (P) in the meaning of ₁ and ₁ X L with the formula (A) and of X _1, preferred ranges are also the same.

As a method for introducing a polymerizable group, there are: (1) a method of modifying (a) a structural unit to be introduced into a polymerizable group by a compound containing a polymerizable group and introducing it; (2) a method of introducing a polymerizable group-containing compound The method of introducing the compound by copolymerization, etc.

In the case where the dye monomer contains a polymerizable group, the amount of the polymerizable group contained in the dye monomer is preferably 0.1 mmol to 2.0 mmol, and more preferably 0.2 mmol to 1.5 mmol relative to 1 g of the dye structure. Especially preferred is 0.3mmol~1.0mmol.

In addition, when other structural units contain polymerizable groups, the amount of polymerizable groups contained in other structural units is, for example, preferably 10% by mass to 40% by mass, more preferably 15% by mass relative to 100% by mass of all structural units. Mass%~35 mass%.

As the structural unit having a polymerizable group, the following specific examples can be given. However, the present invention is not limited to these.

[化21]

""Alkali Soluble Base""

As an example of the alkali-soluble group which a dye multimer may have, an acid group is mentioned. As an acid group, a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group can be illustrated.

In the present invention, it is preferable that the alkali-soluble group is contained in the dye multimer as a structural unit having the alkali-soluble group. More specifically, it is preferable that in the general formula (P), P is a repeating unit of an alkali-soluble group.

As a method of introducing alkali-soluble groups into pigment multimers, it can be listed in A method of introducing an alkali-soluble group into a dye monomer in advance, and a monomer other than the dye monomer having an alkali-soluble group ((meth)acrylic acid, acrylic acid caprolactone modified product, (meth)acrylic acid 2- Modified product of hydroxyethyl succinic anhydride, modified product of phthalic anhydride of 2-hydroxyethyl (meth)acrylate, modified product of 1,2-cyclohexanedicarboxylic acid anhydride of 2-hydroxyethyl (meth)acrylate Substances, carboxylic acid-containing monomers such as styrene carboxylic acid, itaconic acid, maleic acid, norbornene carboxylic acid, phosphoric acid-containing monomers such as methacrylic acid phosphatidyloxyethyl, vinyl phosphonate, etc. A method of copolymerizing a monomer, a sulfonic acid-containing monomer such as vinyl sulfonate and 2-propenamide-2-methylsulfonic acid, is more preferably a method using both.

The amount of alkali-soluble groups (acid value) possessed by the pigment polymer is preferably 15mgKOH/g~130mgKOH/g, more preferably 25mgKOH/g~100mgKOH/g, and still more preferably 25mgKOH/g relative to 1g of the pigment polymer. g~80mgKOH/g. The amount of alkali-soluble groups (acid value) can be measured by titration using a 0.1N sodium hydroxide aqueous solution.

In addition, in the case where the pigment multimer contains a structural unit including a pigment monomer and a structural unit having an acid group, the ratio of the structural unit having an acid group relative to 100 moles of the structural unit including the pigment monomer is, for example It is preferably 5 mol to 70 mol, more preferably 10 mol to 50 mol.

Examples of functional groups possessed by the dye polymer include: lactones, acid anhydrides, amides, -COCH ₂ CO-, cyano groups and other development promoting groups, long-chain and cyclic alkyl groups, aralkyl groups, aryl groups, Hydrophilicity and hydrophobicity adjusting groups such as polyalkylene oxide, hydroxyl, maleimide, and amine groups, etc., can be appropriately introduced.

As the method of introduction, the method of pre-introducing into the mono-pigment body, and A method of copolymerizing the monomer having the functional group.

"The Structure Represented by Formula (1) ~ Formula (5)"

The structural unit having a dye structure of the dye multimer may include the structure represented by formula (1) to formula (5).

The structure represented by formula (1) is collectively called a hindered amine system. The structure represented by formula (2) is collectively called a hindered phenol system. The structure represented by the formula (3) is collectively called a benzotriazole series. The structure represented by formula (4) is collectively called a hydroxybenzophenone series. The structure represented by formula (5) is collectively called a triazine series.

Among the structures represented by formula (1) to formula (5), the structure represented by formula (1) and the structure represented by formula (2) are preferred, and the structure represented by formula (1) is particularly preferred structure. The dye multimer used in the present invention has a dye structure and a structure represented by formula (1) in the same molecule, whereby the amine group in the structure represented by formula (1) interacts with the substrate, Therefore, the adhesion can be further improved.

In the formula (1), R ¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group, or an oxygen radical. R ² and R ³ each independently represent 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 the bond between the structure represented by formula (1) and the polymer backbone.

In the formula (1), R ¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbons, an aryl group, or an oxygen radical, preferably an alkyl group having 1 to 18 carbons.

The alkyl group having 1 to 18 carbon atoms may be linear, branched, or cyclic, and is preferably linear. The carbon number of the alkyl group having 1 to 18 carbon atoms is preferably from 1 to 12, more preferably from 1 to 8, further preferably from 1 to 3, and particularly preferably from 1 or 2. 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.

The carbon number of the aryl group may be 6-18, 6-12, or 6. Specifically, a phenyl group can be mentioned.

When R ¹ in the formula (1) represents an alkyl group or aryl group having 1 to 18 carbon atoms, the alkyl group and aryl group having 1 to 18 carbon atoms may have a substituent or may be unsubstituted. Examples of the substituent that may be possessed include substituents selected from the substituent group A.

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 the bond between the structure represented by formula (1) and the polymer backbone. The bonding bond may be directly or via a linking group to bond to the polymer backbone, or may be directly or via a linking group to bond to the pigment structure. It is particularly preferred that the "*" in the formula (1) is directly or via a linking group bonded to the polymer backbone.

Below, although the specific example of the structure represented by Formula (1) is shown, it is not limited to these. In the following structures, "*" represents the structure represented by formula (1) and polymer bone The bonding key of the frame.

In the formula (2), R ⁴ represents the following formula (2A), an alkyl group or an aryl group having 1 to 18 carbon atoms. R ⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. "*" represents the bond between the structure represented by formula (2) and the polymer backbone.

In the formula (2), R ⁴ represents the aforementioned formula (2A), an alkyl group or aryl group having 1 to 18 carbon atoms, and is preferably represented by the formula (2A). The meanings of the alkyl group and aryl group having 1 to 18 carbon atoms are the same as the alkyl group and aryl group having 1 to 18 carbon atoms described in R ¹ in the formula (1). In addition, the meaning of "*" is the same as the bond described in formula (1).

[化26]

In the formula (2A), R ⁶ each independently represents an alkyl group having 1 to 18 carbon atoms. "*" represents the bonding bond between the structure represented by formula (2A) and the structure represented by formula (2).

In formula (2A), R ^{6 has} the same meaning as the alkyl group having 1 to 18 carbon atoms described in R ¹ in formula (1). In addition, the meaning of "*" is the same as the bond described in formula (1).

Hereinafter, specific examples of the structure represented by formula (2) are shown, but it is not limited to these. In the following structures, "*" represents the bond between the structure represented by formula (2) and the polymer backbone.

In the formula (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, R ⁷ may be the same or different. "*" represents the bond between the structure represented by formula (3) and the polymer backbone.

In formula (3), R ^{7 has} the same meaning as the alkyl group having 1 to 18 carbon atoms explained in R ¹ in formula (1).

In formula (3), n1 represents an integer of 0 to 3, preferably an integer of 0 to 2, and preferably 0 or 1.

In the formula (3), the meaning of "*" is the same as the bond described in the formula (1).

Below, although the specific example of the structure represented by Formula (3) is shown, it is not limited to these. In the following structures, "*" represents the bond between the structure represented by formula (3) and the polymer backbone.

[化29]

In the formula (4), R ⁸ and R ⁹ each independently represent an alkyl group having 1 to 18 carbon atoms. n2 represents an integer from 0 to 3. n3 represents an integer from 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 the bond between the structure represented by formula (4) and the polymer backbone.

In the formula (4), R ⁸ and R ^{9 have} the same meanings as the alkyl group having 1 to 18 carbon atoms described in R ¹ in the formula (1).

In formula (4), n2 represents an integer of 0-3, preferably an integer of 0-2, and more preferably 0 or 1.

In formula (4), n3 represents an integer of 0-4, preferably an integer of 0-2, and more preferably 0 or 1.

In the formula (4), the meaning of "*" is the same as the bond described in the formula (1).

Hereinafter, specific examples of the structure represented by formula (4) are shown, but it is not limited to these. In the following structures, "*" represents the bond between the structure represented by formula (4) and the polymer backbone.

[化32]

In formula (5), R ¹⁰ to R ¹² each independently represent an alkyl group having 1 to 18 carbons or an alkoxy group having 1 to 8 carbons. n4 to n6 each independently represent an integer of 0 to 5. n7 to n9 each independently represent 0 or 1, and at least one of n7 to n9 represents 1. "*" represents the bond between the structure represented by formula (5) and the polymer backbone.

In the case where R ¹⁰ in the formula (5) represents an alkyl group having 1 to 18 carbons, the meaning is the same as the alkyl group having 1 to 18 carbons described in R ¹ in the formula (1), and is preferably a carbon number The alkyl group of 1 to 3 is more preferably a methyl group. When R ¹⁰ represents an alkoxy group having 1 to 8 carbon atoms, the carbon number of the alkoxy group is preferably 1 to 6, more preferably 1 to 5, and still more preferably 1 to 4.

N4 in formula (5) represents an integer of 0-5, preferably an integer of 1-4, more preferably 2 or 3. When n4 represents an integer of 2 to 5, each R ¹⁰ may be the same or different.

The meaning of R ¹¹ in formula (5) is the same as that of R ¹⁰ in formula (5), and the preferred range is also the same.

In formula (5), n5 represents an integer of 0-5, preferably an integer of 1-3, more preferably 1 or 2. When n5 represents an integer of 2 to 5, each R ¹¹ may be the same or different.

The meaning of R ¹² in the formula (5) is the same as that of R ¹⁰ in the formula (5), and the preferred range is also the same.

N6 in formula (5) represents an integer of 0-5, preferably an integer of 0-3, more preferably 0 or 1. When n6 represents an integer of 2 to 5, each R ¹² may be the same or different.

In formula (5), n7 to n9 each independently represent 0 or 1, and at least one of n7 to n9 represents 1. It is particularly preferable that only n7 represents 1, or only n8 and n9 represent 1, or only any one of n7, n8, and n9 represents 1.

R ¹⁰ to R ¹² in formula (5) may each independently have a substituent or may be unsubstituted. Examples of the substituent that may be possessed include substituents selected from the substituent group A.

In the formula (5), the meaning of "*" is the same as the bond described in the formula (1).

Hereinafter, specific examples of the structure represented by formula (5) are shown, but it is not limited to these. In the following structures, "*" represents the bond between the structure represented by formula (5) and the polymer backbone.

"" "Constituent unit having at least one structure represented by formula (1) to formula (5)" ""

The structural unit having at least one structure represented by formula (1) to formula (5) is preferably represented by the following formula (E).

In the general formula (E), X ^{3 has} the same meaning as X ¹ in the general formula (A). The meaning of L ^{4 is} the same as L ¹ in the general formula (A). Z ¹ represents the structure represented by the formula (1) to (5).

Hereinafter, specific examples of the structural unit having at least one structure represented by formula (1) to formula (5) are shown, but the present invention is not limited to these.

[化35]

When all the structural units in the pigment multimer are set to 100% by mass, the content of at least one structural unit of the pigment multimer having the structure represented by formula (1) to formula (5) is preferably 0.5 Mass%-20 mass%, more preferably 1 mass%-10 mass%, particularly preferably 1 mass%-5 mass%.

In addition, the content of the structural unit having at least one of the structures represented by formula (1) to formula (5) relative to 1 mol of the structural unit including the dye structure is preferably 0.5 mol% to 25 mol% , More preferably 1 mol%~10 mol%, more preferably 1 mol%~5 mol%.

"Counter Anion"

When the dye structure used in the present invention has a cationic structure, the counter anion may be in the same structural unit of the dye multimer, or may be outside the same structural unit. The term "counter anion in the same structural unit" refers to a case where a cation and an anion are bonded via a covalent bond in a structural unit having a dye structure. On the other hand, the term "outside the same structural unit" refers to cases other than the above. For example, it refers to the case where the cation and the anion are not bonded via a covalent bond but exist as different compounds, and the case where the cation and the anion are contained as separate structural units of the dye multimer.

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 is preferably an organic anion. As an example of the counter anion used in the present invention, the well-known non-nucleophilic anion described in paragraph number 0075 of Japanese Patent Laid-Open No. 2007-310315 can be cited, and these contents can be incorporated in the specification of this application. . Here, the so-called non-nucleophilic property refers to the property that the pigment does not undergo nucleophilic attack due to heating.

When the counter anion is in the same constituent unit

The first embodiment of the anion in the present invention is the case where the counter anion is in the same structural unit, specifically, the case where the cation and the anion are bonded via a covalent bond in the structural unit having a dye structure.

The anionic portion in this case, is preferably selected from _{^{-SO 3 -, -COO -, -PO}} 4 -, structure represented by the following general formula (A1) represented by the following general formula and is represented by (A2) At least one of the structures of is more preferably at least one selected from the structure represented by the following general formula (A1) and the structure represented by the following general formula (A2).

In addition, the anion part may contain a carboxylate anion, a sulfonate anion, an anion represented by general formula (A1-1-2), or an anion represented by general formula (A1-1-3).

(In the general formula (A1), R ¹ and R ² each independently represent -SO ₂ -or -CO-)

In the general formula (A1), it is preferable that at least one of R ¹ and R ² represents -SO ₂ -, and it is more preferable that both of R ¹ and R ² represent -SO ₂ -.

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

(In the general formula (A1-1), R ¹ and R ² each independently represent -SO ₂ -or -CO-. X ¹ and X ² each independently represent an alkylene group or an aryl group)

In the general formula (A1-1), R ¹ and R the same meaning as in the general formula (A1) ² in R ¹ and R ^2, preferred ranges are also the same.

When X ¹ represents an alkylene group, the carbon number of the alkylene group is preferably from 1 to 8, and more preferably from 1 to 6. In the case where X ¹ represents an arylene group, the carbon number of the arylene group is preferably 6-18, more preferably 6-12, and still more preferably 6. When X ¹ has a substituent, it is preferably substituted by a fluorine atom.

X ² represents an alkyl group or an aryl group, preferably an alkyl group. The carbon number of the alkyl group is preferably from 1 to 8, more preferably from 1 to 6, further preferably from 1 to 3, and particularly preferably from 1. When X ² has a substituent, it is preferably substituted by a fluorine atom.

(In the general formula (A2), R ³ represents -SO ₂ -or -CO-. R ⁴ and R ⁵ each independently represent -SO ₂ -, -CO- or -CN)

In the general formula (A2), preferably at least one of R ³ to R ⁵ represents -SO ₂ -, and more preferably at least two of R ³ to R ⁵ represents -SO ₂ -.

In this embodiment, in particular, when the skeleton of the dye multimer is represented by the structural unit represented by the general formula (A), a part of L ₁ includes the part represented by the general formula (A1) The situation serves as a better example. As a specific example in this case, (a-xt-1), (a-xt-5), (a-xt-6) in the illustration of the structural unit which has a dye structure mentioned later can be illustrated.

Moreover, in this embodiment, the case where the skeleton of a dye multimer contains the structural unit represented by general formula (B) can also be mentioned as an example. As a specific example in this case, (B-dp-1), (B-mp-1), (B-xt-1), (B-xt) in the illustration of the structural unit having a dye structure described later can be exemplified -2).

When the counter anion is a different molecule

The second embodiment of the anion in the present invention is the case where the counter anion is outside the same structural unit, and the cation and the anion are not bonded via a covalent bond but exist as different molecules.

As the anion in this case, for example, a fluoride anion, a chloride anion, a bromide anion, an iodide anion, a cyanide ion, a perchlorate anion, and a non-nucleophilic anion are exemplified, and a nonnucleophilic anion is preferable.

The non-nucleophilic counter anion may be an organic anion or an inorganic anion, preferably an organic anion. As an example of the counter anion used in the present invention, the well-known non-nucleophilic anion described in paragraph number 0075 of Japanese Patent Laid-Open No. 2007-310315 can be cited. These contents can be incorporated into the specification of this application. .

Preferably include bis (sulfo acyl) acyl imide anion, tris (acyl sulfo) methyl anion, tetraarylborate _{^{anion, B - (CN) n1 (}} OR a) 4-n1 (R a represents alkyl having 1 to 10 carbon atoms or an aryl group having 6 to 10, and 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, n2 represents an integer of 1 to 6), more preferably selected from the group consisting of bis(sulfonyl)imide anion, tris(sulfonyl)methyl anion and tetraarylborate anion, and more preferably bis(sulfonyl)borate anion Group) imine anion. By using such a non-nucleophilic counter anion, there is a tendency to more effectively exhibit the effects of the present invention.

The bis(sulfonyl)imide anion which is a non-nucleophilic counter anion preferably has a structure represented by the following general formula (AN-1).

(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 may be bonded to each other to form a ring) X ¹ And X ² each independently represent a fluorine atom or a C 1-10 alkyl group having a fluorine atom, preferably a fluorine atom or a C 1-10 alkyl group having a fluorine atom, more preferably a C 1-10 alkyl group The perfluoroalkyl group is more preferably a C1-C4 perfluoroalkyl group, and particularly preferably a trifluoromethyl group.

The tris(sulfonyl)methyl anion as a non-nucleophilic counter anion is preferably a structure of the following general formula (AN-2).

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

The meanings of X ³ , X ⁴ and X ⁵ are independently the same as X ¹ and X ² , and the meanings of the preferred ranges are also the same.

Regarding the tetraarylborate anion as the non-nucleophilic counter anion, a compound represented by the following general formula (AN-5) is preferred.

(In formula (AN-5), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent an aryl group)

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently preferably an aryl group having 6 to 20 carbons, more preferably an aryl group having 6 to 14 carbons, and still more preferably an aryl group having 6 to 10 carbons.

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 carbamethan group, a sulfo group, a sulfonamide group, a nitro group, etc. can be mentioned, and halogen is preferred. The atom and the alkyl group are more preferably a fluorine atom or an alkyl group, and still more preferably a fluorine atom and a C1-C4 perfluoroalkyl group.

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

In addition, the non-nucleophilic counter anion is preferably -B(CN) _n1 (OR ^a ) _4-n1 (R ^a represents an alkyl group with 1 to 10 carbons or an aryl group with 6 to 10 carbons, and n1 represents 1 ~4 integer). ^Ra 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 1~3, more preferably 1~2.

In addition, non-nucleophilic counter anion is preferably ^{_{-PF 6 R P (6-n2}} ) - (R P represents a fluorinated alkyl group having a carbon number of 1 to 10, n2 represents an integer of 1 to 6). R ^{P is} preferably an alkyl group having 1 to 6 carbon atoms having a fluorine atom, more preferably an alkyl group having 1 to 4 carbon atoms having a fluorine atom, and still more preferably a perfluoroalkyl group having 1 to 3 carbon atoms.

n2 is preferably an integer of 1 to 4, more preferably 1 or 2.

The mass per molecule of the non-nucleophilic counter anion used in the present invention is preferably 100 to 1,000, and more preferably 200 to 500.

The pigment multimer of the present invention may include only one type of non-nucleophilic counter anion, or may include two or more types.

Hereinafter, specific examples of non-nucleophilic counter anions used in the present invention are shown, but the present invention is not limited to these.

[化43]

[化45]

In addition, in the second embodiment, the anion may be a multimer. As a multimer in this case, the multimer which contains the structural unit containing an anion and does not contain the structural unit derived from the dye structure containing a cation can be illustrated. Here, the anionic As the structural unit, a structural unit containing an anion described in the third embodiment described later can be cited 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, other repeating units that can be included in the dye multimer used in the present invention described later can be exemplified as preferred examples.

When the cation and anion are contained in different structural units of the pigment polymer

As the third embodiment of the present invention, it refers to the case where the cation and the anion are contained in the respective independent structural units of the dye multimer.

In the case of this embodiment, the anion may be included in the side chain of the dye multimer, may be included in the main chain, and may have a counter anion on both the main chain and the side chain. Preferably it is a side chain.

As a preferable example of the structural unit containing an anion, the structural unit represented by general formula (C1) and the structural unit represented by general formula (D1) can be illustrated.

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

In the general formula (C1), X ¹ represents the main chain of a constituent unit, and usually represents a linking group formed by a polymerization reaction. For example, (meth)acrylic, styrene, vinyl, etc. are preferred, and more preferably It is a (meth)acrylic system, a styrene system, and more preferably a (meth)acrylic system. Furthermore, the part indicated by two * becomes a structural unit.

When L ¹ represents a divalent linking group, it is preferably an alkylene group having 1 to 30 carbon atoms (methylene, ethylene, trimethylene, propylene, butylene, etc.), and carbon number 6~30 arylene (phenylene, naphthylene, etc.), heterocyclic linking group, -CH=CH-, -O-, -S-, -C(=O)-, -CO-,- NR-, -CONR-, -OC-, -SO-, -SO ₂ -and linking groups formed by combining two or more of these. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

Particularly preferably, L ¹ is a single bond, or an alkylene having 1 to 10 carbon atoms (preferably -(CH ₂ )n-(n is an integer of 5 to 10)), or an alkylene having 6 to 12 carbon atoms. A divalent linking group formed by a combination of two or more groups (preferably phenylene or naphthylene), -NH-, -CO ₂ -, -O- and -SO ₂ -.

Examples Specific examples of X ¹ X ¹ can be exemplified by the general formula (A) as in the preferred embodiment.

General formula (D1) [化47]

(In the 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 the general formula (D1), when L ² and L ³ represent a divalent linking group, it is preferably an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, and a 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 combining two or more of these. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

L ^{2 is} preferably an arylene group having 6 to 12 carbons (especially 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 containing a combination of an arylene group having 6 to 12 carbons (especially a phenylene group) and -O-, and preferably at least one arylene group having 6 to 12 carbons is substituted with a fluorine atom.

As the counter anion, the anion part described when the counter anion is in the same structural unit can be exemplified as a preferable anion.

The following shows specific examples of the anion-containing structural unit in this embodiment, but the present invention is not limited to these.

[化48]

The following specific examples show the state where the anion structure is not dissociated, but the state where the anion structure is dissociated is of course also within the scope of the present invention.

[化49]

[化50]

[化51]

[化52]

[化53]

(Specific examples of dyes)

Specific examples of dyes are shown below, but the present invention is not limited to these. In the following specific examples, X ^- represents an anion. In addition, arbitrary hydrogen atoms in the dye structure shown below are bonded to the polymer backbone.

As a specific example of a triphenylmethane compound, the following can be mentioned.

[化54]

[化55]

As a specific example of a xanthene compound, the following can be mentioned.

[化56]

[化57]

Hereinafter, examples of structural units having a dye structure used in the present invention are shown. X ^- represents the counter anion. In addition, a part of X is expressed in a state where the anionic structure is not dissociated, but the dissociated state is of course also included in the present invention.

[化64]

[化65]

[化67]

[化69]

[化70]

[化71]

[化72]

As the structural unit having a dye structure, a structural unit derived from any of the following exemplary compounds M-17 to M-37, M-39, M-40, and M-43 can also be cited.

[化73]

[化74]

[化75]

[化76]

(Characteristics of the dye)

The maximum absorption wavelength of the dye used in the present invention is preferably 400 nm to 650 nm, more preferably 450 nm to 600 nm.

The weight average molecular weight of the dye used in the present invention is preferably 2000 or higher, more preferably 3000 or higher, still more preferably 4000 or higher, particularly preferably 5000 or higher. In particular, when the weight average molecular weight of the dye is 5000 or more, the solubility of the color-sensitive radiation composition of the present invention in the developer is improved. In addition, the upper limit of the weight average molecular weight of the dye is not particularly limited, but it is preferably 30,000 or less, and more preferably It is 20,000 or less, more preferably 15,000 or less, and particularly preferably 10,000 or less.

In this specification, the weight average molecular weight and the number average molecular weight use the values measured by the gel permeation chromatography (Gel Permeation Chromatography, GPC) method and styrene conversion.

In addition, when the dye is a pigment polymer, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) [(Mw)/(Mn)] is preferably 1.0 to 3.0, and more preferably 1.6 to 2.5 , Especially preferred is 1.6~2.0.

The glass transition temperature (Tg) of the dye used in the present invention is preferably 50°C or higher, more preferably 100°C or higher. In addition, the 5% weight loss temperature obtained by thermogravimetric analysis (TGA (thermogravimetric analysis) measurement) is preferably 120°C or higher, more preferably 150°C or higher, and still more preferably 200°C or higher. By being in this area, when the color-sensitive radiation composition of the present invention is applied to the production of color filters and the like, the density change caused by the heating process can be reduced.

In addition, the absorbance coefficient per unit weight of the dye used in the present invention (hereinafter referred to as ε'. ε'=ε/average molecular weight, unit: L/g·cm) is preferably 30 or more, more preferably 60 or more , More preferably 100 or more. By being in this range, when a color filter is produced using the color-sensitive radiation composition of the present invention, a color filter with good color reproducibility can be produced.

From the viewpoint of tinting power, the molar absorption coefficient of the dye is preferably as high as possible.

In addition, the maximum absorption wavelength and the molar absorption coefficient were measured with a spectrophotometer cary5 (manufactured by Varian).

The dye used in the present invention is preferably a compound dissolved in the following organic solvent. Examples of organic solvents include esters (for example, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate, etc.) , Ethers (such as 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.), with respect to these solvents, it is preferable to dissolve 1% by mass or more and 50% by mass or less, more preferably It is suitable to dissolve 5% to 40% by mass, and more preferably to dissolve 10% to 30% by mass. By being in this area, when the colored radiation composition of the present invention is applied to the production of color filters, etc., it is easy to obtain suitable coating surface properties, or it is easy to reduce the elution after coating other colors. The resulting concentration drops.

In the colored radiation composition of the present invention, one type of dye may be used alone, or two or more types may be used in combination.

In the case of using the dye, relative to the total solid content of the colored radiation-sensitive composition, the content of the dye in the colored radiation-sensitive composition of the present invention is preferably 10% by mass to 70% by mass, more preferably 10% by mass to 50% by mass, particularly preferably 15% by mass to 30% by mass.

In addition, the concentration of the coloring agent containing the dye relative to the total solid content of the colored radiation-sensitive composition is preferably 50% by mass or more, and more preferably 60% by mass or more.

[Polymerizable compound B]

As the polymerizable compound B (hereinafter, also simply referred to as "polymerizable compound"), any compound polymerized by the photopolymerization initiator D described later may be used. Known polymerizable compound.

Among them, from the viewpoint of polymerizability, addition polymerizable compounds having at least one ethylenically unsaturated double bond can also be used, and it is preferable to use terminal ethylene having at least one, preferably two or more, and ten or less terminal ethylene groups. Compounds with sexually unsaturated bonds.

Among them, from the viewpoint of more excellent adhesion of the colored layer, the polymerizable compound is preferably a polymerizable compound having three or more ethylenically unsaturated double bonds (hereinafter, sometimes referred to as "polyfunctional monomer") . Such compounds are widely known in the industrial field, and in the present invention, they can be used without particular limitation. The polyfunctional monomer in the present invention may be used alone or in combination of two or more kinds. The polyfunctional monomer used in the present invention is preferably a (meth)acrylate monomer.

As these specific compounds, the compounds described in paragraph [0095] to paragraph [0108] of JP 2009-288705 A can be suitably used.

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

[化77]

In the formula, n is 0-14 and m is 1-8. Multiple R, T, and Z in a 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 0-5, more preferably 1-3.

m is preferably 1~5, more preferably 1~3.

R

更佳為

Preferably [化78]

Better

As a specific example of the radical polymerizable monomer represented by the general formula (MO-1) to the general formula (MO-6), the paragraph of Japanese Patent Laid-Open No. 2007-269779 can be suitably used [0248] ~ The compound described in paragraph [0251].

Among them, as multifunctional monomers and the like, dipentaerythritol triacrylate (commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available The product is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol penta(meth)acrylate (commercially available product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(methyl) ) Acrylate (commercially available product is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), and these (meth)acrylic acid groups are separated by ethylene glycol residues and propylene glycol residues. These oligomer types can also be used.

For example, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like can be cited.

The multifunctional monomer may have acid groups such as carboxyl groups, sulfonic acid groups, and phosphoric acid groups. Therefore, if the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, the ethylenic compound can be used directly, and if necessary, the hydroxyl group of the opposite compound can be combined with a non-aromatic The carboxylic acid anhydride reacts to introduce acid groups. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and alkylated hexahydrophthalic anhydride. Hydrogen phthalic anhydride, succinic anhydride, maleic anhydride.

In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and it is preferable to react the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride to have an acid The polyfunctional monomer of the group is particularly preferred in the ester, and the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. As a commercially available product, M-305, M-510, M-520 of the Aronix series, which are polyacid-modified acrylic oligomers manufactured by Toagosei Co., Ltd., can be cited.

The preferred acid value of the polyfunctional monomer having an acid group is 0.1 mgKOH/g-40 mgKOH/g, particularly preferably 5 mgKOH/g-30 mgKOH/g.

In the total solid content of the composition of the present invention, the content of the polymerizable compound (especially the polyfunctional monomer) is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably 7% by mass or more. The upper limit is not particularly limited, but is preferably 50% by mass or less, and more preferably 40% by mass or less.

The polymerizable compound may be used alone or in combination of two or more kinds. As a preferable example of the combination, it is preferable to combine the two types with different polymerizable groups. From the viewpoint of developability and adhesion, it is more preferable to combine a monomer with a polymerizable group of tetrafunctional or less and a monomer with a polymerizable group of pentafunctional or more.

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

[Alkali-soluble resin C]

As the alkali-soluble resin C (hereinafter also referred to as "alkali-soluble resin"), it may have at least one molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as the main chain) that promotes alkali solubility It is suitably selected from alkali-soluble resins which are linear organic high molecular polymers. From the viewpoint of heat resistance, polyhydroxystyrene-based resins, polysiloxane-based resins, acrylic resins, acrylamide-based resins, acrylic/acrylamide copolymer resins are preferred, and from the viewpoint of controlling developability In particular, acrylic resins, acrylamide resins, and acrylic/acrylamide copolymer resins are preferred.

Examples of groups that promote alkali solubility (hereinafter, also referred to as acid groups) include carboxyl groups, phosphoric acid groups, sulfonic acid groups, and phenolic hydroxyl groups. Preferably, they are soluble in solvents and can be developed by weakly alkaline aqueous solutions. As a particularly preferred group, (meth)acrylic acid can be mentioned. These acid groups may be only one type or two or more types.

Examples of monomers that can impart acid groups after polymerization include monomers having hydroxyl groups such as 2-hydroxyethyl (meth)acrylate, monomers having epoxy groups such as glycidyl (meth)acrylate, (Meth) 2-isocyanatoethyl acrylate and others have isocyanate Monomers and so on. The monomers used to introduce acid groups may be only one type or two or more types. When introducing an acid group into an alkali-soluble resin, for example, a monomer having an acid group and/or a monomer that can impart an acid group after polymerization (hereinafter sometimes referred to as "monobody for introducing acid group" ) It is sufficient to polymerize as a single body component.

In addition, in the case where an acid group is introduced as a monomer component to a monomer capable of imparting an acid group after polymerization, for example, a treatment for imparting an acid group as described later is required after the polymerization.

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

As a linear organic high molecular polymer that can be used as an alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferred, and examples thereof include methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, and crotonic acid Alkali-soluble phenol resins such as copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, novolac type resins, etc., and acidic cellulose derivatives with carboxylic acid on the side chain, It is formed by adding acid anhydride to hydroxyl polymer. In particular, copolymers of (meth)acrylic acid and other monomers copolymerizable therewith are suitable as alkali-soluble resins. Examples of other monomers that can be copolymerized with (meth)acrylic acid include alkyl (meth)acrylate, aryl (meth)acrylate, and vinyl compounds. Examples of alkyl (meth)acrylate and aryl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (meth)acrylic acid. Butyl ester, isobutyl (meth)acrylate, Amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, cresyl (meth)acrylate, (meth)acrylate Base) naphthyl acrylate, cyclohexyl (meth)acrylate, etc. Examples of vinyl compounds include styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, and vinyl acetate , N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomers, polymethyl methacrylate macromonomers, etc., as described in Japanese Patent Laid-Open No. 10-300922 The N-substituted maleimide monomers include N-phenyl maleimide, N-cyclohexyl maleimide, and the like. Furthermore, these other monomers that can be copolymerized with (meth)acrylic acid may be only one type or two or more types.

As the alkali-soluble resin, it is also preferable to include a polymer (a) obtained by polymerizing the following monomer component, which is a compound represented by the following general formula (ED) and/or The compound represented by the general formula (ED2) (hereinafter, these compounds may also be referred to as "ether dimer") is an essential component.

In the general formula (ED), R ¹ and R ² each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 25 carbon atoms.

In the 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), reference can be made to the description in JP 2010-168539 A.

Thereby, the composition of the present invention can form a cured coating film that is extremely excellent in heat resistance and transparency. In the general formula (ED) representing 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, and examples thereof include: Straight or branched, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, tertiary pentyl, stearyl, lauryl, 2-ethylhexyl, etc. The alkyl group; aryl groups such as phenyl; cyclohexyl, tertiary butylcyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl, 2-methyl-2-adamantane Alkyl groups such as 1-methoxyethyl and 1-ethoxyethyl groups substituted by alkoxy groups; alkyl groups such as benzyl groups substituted by aryl groups. Among these, from the viewpoint of heat resistance, a substituent of a primary carbon or a secondary carbon such as a methyl group, an ethyl group, a cyclohexyl group, and a benzyl group that is not easily removed by acid or heat is particularly preferable.

As specific examples of the ether dimer, for example, dimethyl-2,2'-[oxobis(methylene)]bis-2-acrylate, diethyl-2,2'- [Oxobis(methylene)]bis-2-acrylate, di(n-propyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, di(isopropyl) Base)-2,2'-[oxobis(methylene)]bis-2-acrylate, di(n-butyl)-2,2'-[oxobis(methylene)]bis-2 -Acrylate, di(isobutyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, di(tertiary butyl)-2,2'-(oxobis (Methylene)) bis-2-acrylate, bis(third pentyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, bis(stearyl)- 2,2'-[oxobis(methylene)]bis-2-acrylate, bis(lauryl)-2,2'-[oxobis(methylene)]bis-2-acrylate, Bis(2-ethylhexyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, bis(1-methoxyethyl)-2,2'-(oxo Bis(methylene)]bis-2-acrylate, bis(1-ethoxyethyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, dibenzyl -2,2'-[oxobis(methylene)]bis-2-acrylate, diphenyl-2,2'-[oxobis(methylene)]bis-2-acrylate, two Cyclohexyl-2,2'-[oxobis(methylene)]bis-2-acrylate, bis(tertiary butylcyclohexyl)-2,2'-[oxobis(methylene)] Bis-2-acrylate, bis(dicyclopentadienyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, bis(tricyclodecyl)-2, 2'-[oxobis(methylene)]bis-2-acrylate, bis(isobornyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, two Adamantyl-2,2'-[oxobis(methylene)]bis-2-acrylate, bis(2-methyl-2-adamantyl)-2,2'-[oxobis( Methylene)] bis-2-acrylate and the like. Among these, particularly preferred are dimethyl-2,2'-[oxobis(methylene)]bis-2-acrylate, diethyl-2,2'-[oxobis(methylene) Yl)]bis-2-acrylate, dicyclohexyl-2,2'-[oxobis(methylene)]bis-2-acrylate, dibenzyl-2,2'-[oxobis( Methylene)] bis-2-acrylate. These ether dimers may be only one kind, It may be two or more types. The structure derived from the compound represented by the general formula (ED) can also be copolymerized with other monomers.

In addition, in order to improve the crosslinking efficiency of the composition in the present invention, an alkali-soluble resin having a polymerizable group may also be used. By having a polymerizable group, heat resistance, light resistance, etc. tend to be further improved. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing an allyl group, a (meth)acrylic group, an allyloxyalkyl group, or the like in a side chain is useful. Examples of the polymer containing polymer include: Dianal NR series (manufactured by Mitsubishi Rayon), Photomer 6173 (COOH-containing acrylic polyurethane oligomer (Polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co. Ltd.), Viscoat R-264, KS Resist 106 (all manufactured by Osaka Organic Chemical Industry ), Cyclomer P series, Placcel CF200 series (all manufactured by Daicel Chemical Industry), Ebecryl 3800 (made by Daicel-UCB (Daicel-UCB)), etc. . As these polymerizable group-containing alkali-soluble resins, the following resins are preferred: a urethane-modified acrylic resin containing polymerizable double bonds by reacting isocyanate groups with OH groups in advance , Obtained by the reaction of an unreacted isocyanate group and a compound containing a (meth)acrylic acid group with an acrylic resin containing a carboxyl group; by the acrylic resin containing a carboxyl group and an epoxy group in the molecule and polymerization Acrylic resin containing unsaturated groups obtained by the reaction of a compound with a functional double bond; an acid pendant epoxy acrylate resin; an acrylic resin containing an OH group and a dibasic acid anhydride having a polymerizable double bond A polymerizable double bond-containing acrylic resin obtained by the reaction; a resin obtained by reacting an OH group-containing acrylic resin with an isocyanate and a compound having a polymerizable group; according to Japanese Patent Laid-Open No. 2002-229207 And a resin obtained by alkali treatment of a resin having an ester group in a side chain described in Japanese Patent Laid-Open No. 2003-335814, the ester is based on a halogen atom or a sulfonic acid ester at the α-position or β-position The base is out of the base.

In addition, the alkali-soluble resin may also contain a structural unit derived from an ethylenically unsaturated monomer represented by the following 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 an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring. n represents an integer from 1 to 15)

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

As the alkali-soluble resin, particularly suitable is a multi-element copolymer containing benzyl (meth)acrylate/(meth)acrylic acid copolymer and/or benzyl (meth)acrylate/(meth)acrylic acid/other monomers . In addition, examples include benzyl (meth)acrylate/(meth)acrylic acid/(meth)acrylic acid-2-hydroxyethyl (meth)acrylate copolymer obtained by copolymerizing 2-hydroxyethyl methacrylate, Japanese patent 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-phenoxy acrylate described in JP-A-7-140654 Propyl 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., particularly preferably benzyl methacrylate/methacrylic acid The copolymer and so on.

As the alkali-soluble resin, refer to paragraphs 0558 to 0571 of Japanese Patent Laid-Open No. 2012-208494 (corresponding US Patent Application Publication No. 2012/0235099 [0685] to [0700]) and subsequent descriptions. The content can be incorporated into this manual.

Furthermore, it is preferable to use the copolymer (B) described in Paragraph No. 0029 to Paragraph No. 0063 described in JP 2012-32767 A, and the alkali-soluble resin used in the examples, and Japanese Patent Application Publication No. 2012- The adhesive resin described in paragraph number 0088 to paragraph number 0098 of 208474 and the adhesive resin used in the examples, and the adhesive agent described in paragraph number 0022 to paragraph number 0032 of JP 2012-137531 A The resin and the binder resin used in the examples, The adhesive resin described in the paragraph number 0132 to the paragraph number 0143 of the Japanese Patent Laid-Open No. 2013-024934 and the adhesive resin used in the examples, the paragraph number 0092 to the paragraph number of the Japanese Patent Laid-Open No. 2011-242752 The binder resin used in 0098 and the examples is the binder resin described in paragraph number 0030 to paragraph number 0072 of JP 2012-032770 A. These contents can be incorporated into this manual. More specifically, the following resins are preferable.

[化83]

The acid value of the alkali-soluble resin is preferably 30mgKOH/g~200mgKOH/g, more preferably 50mgKOH/g~150mgKOH/g, particularly preferably 70mgKOH/g~120mgKOH/g.

In addition, 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.

With respect to the total solid content of the composition of the present invention, the content of the alkali-soluble resin is preferably 0.1% by mass to 15% by mass, more preferably 0.1% by mass to 12% by mass, and still more preferably 1% by mass to 10% by mass.

The composition of the present invention may contain only one kind of alkali-soluble resin, or two or more kinds. When two or more are contained, it is preferable that the total amount falls within the said 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 the polymerizable compound, and it can be appropriately selected from known photopolymerization initiators. For example, it is preferable to have photosensitivity to the ultraviolet range to visible light. In addition, it may be an active agent that produces a certain effect with a light-excited sensitizer to generate active radicals, 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 absorption coefficient of at least about 50 in the range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), phosphine compounds such as phosphine oxide, hexaarylbiimidazole, and oxime derivatives. Oxime compounds, organic peroxides, sulfur Compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, etc. As the halogenated hydrocarbon compound having a triazine skeleton, for example, a compound described in Wakabayashi et al., "Bull. Chem. Soc. Japan", 42, 2924 (1969), British Patent No. 1388492 The compound described in the specification, the compound described in Japanese Patent Laid-Open No. 53-133428, the compound described in the German Patent No. 3337024, and the "J.Org.Chem." by FC Schaefer et al. , 29,1527 (1964), the compound described in Japanese Patent Laid-Open No. 62-58241, the compound described in Japanese Patent Laid-Open No. 5-281728, the compound described in Japanese Patent Laid-Open No. 5-34920 , The compound described in the specification of US Patent No. 4,212,976, etc.

In addition, from the viewpoint of exposure sensitivity, it is preferably selected from the group consisting of trihalomethyl triazine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, phosphine compounds, Phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene- Iron complexes and their salts, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds.

Further preferred are trihalomethyl triazine compounds, α-amino ketone compounds, phosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, styrene Ketone compounds, particularly preferably selected from trihalomethyl triazine compounds, α-amino ketone compounds, oxime compounds, triallylimidazole dimerization At least one compound in the group consisting of a benzophenone compound.

In particular, when the coloring composition of the present invention is used for the production of color filters for solid-state imaging devices, it is necessary to form a fine pattern with a sharp shape. Therefore, it is important to hardenability and no residue to unexposed Department for development. From this viewpoint, it is particularly preferable to use an oxime compound as a photopolymerization initiator. In particular, in the case of forming a fine pattern in a solid-state imaging element, a stepping exposure machine is used for exposure for curing. However, the exposure machine may be damaged due to halogen, and it is necessary to add a photopolymerization initiator The amount is also suppressed to be low. Therefore, considering these aspects, when forming a fine pattern like a solid-state imaging device, it is particularly preferable to use an oxime compound as a photopolymerization initiator. In addition, by using an oxime compound, the color shift can be further improved.

As a specific example of the photopolymerization initiator, for example, paragraph 0265 to paragraph 0268 of JP 2013-29760 A can be referred to, and the content can be incorporated in the specification of this application.

As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and phosphine compounds can also be suitably used. More specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Laid-Open No. 10-291969 and the phosphine-based initiator described in Japanese Patent No. 4225898 can also be used.

As a hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all are BASF ) Company made).

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

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

As a photopolymerization initiator, an oxime compound is more preferable. In particular, the oxime-based initiator has high sensitivity and high polymerization efficiency, and can harden independently of the concentration of the colored material, and it is easy to design the concentration of the colored material to be high, so it is preferable.

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

In the present invention, as an oxime compound that can be suitably used, for example, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one , 3-Propyloxyiminobutan-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1 -Ketone, 2-benzyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxy Carbonyloxyimino-1-phenylpropan-1-one and the like.

In addition, you can also list: "The Journal of the British Chemical Society: The Perkin II (JCSPerkin II)" (1979) pp.1653-1660, "The Journal of the British Chemical Society, The Perkin II" (1979) )pp.156-162, "Journal of Photopolymer Science and Technology (Journal of of Photopolymer Science and Technology)'' (1995) pp. 202-232, compounds described in Japanese Patent Laid-open No. 2000-66385, Japanese Patent Laid-Open No. 2000-80068, Japanese Patent No. 2004-534797, Compounds and the like described in the gazettes of JP 2006-342166 A.

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

In addition, as oxime compounds other than those described above, compounds described in Japanese Patent Publication No. 2009-519904 in which an oxime is linked to the N-position of carbazole, and those with a heterosubstituent introduced at the benzophenone site can also be used. The compound described in U.S. Patent No. 7626957, the compound described in Japanese Patent Laid-Open No. 2010-15025 and U.S. Patent Publication No. 2009-292039, and the compound described in International Publication No. 2009-131189, in which a nitro group is introduced into the pigment site A ketoxime compound containing a triazine skeleton and an oxime skeleton in the same molecule, a compound described in U.S. Patent No. 7556910, having a maximum absorption at 405 nm and having good sensitivity to g-ray light sources, Japanese Patent Laid-Open No. 2009-221114 Compounds described in the bulletin.

Preferably, for example, paragraph 0274 to paragraph 0275 of JP 2013-29760 A can be referred to, and the content can be incorporated into the specification of this application.

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

In the 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 the general formula (OX-1), the monovalent substituent represented by R is preferably a monovalent non-metal atomic group.

As a monovalent non-metal atomic group, an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, an arylthiocarbonyl group, etc. are mentioned. In addition, these groups may have one or more substituents. In addition, the substituent may be further substituted with other substituents.

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

In the 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. As a substituent, the said substituent can be illustrated.

In the general formula (OX-1), the divalent organic group represented by A is preferably an alkylene group, cycloalkylene group, and alkynylene group having 1 to 12 carbon atoms. These bases can also have a The above substituents. As a substituent, the said substituent can be illustrated.

The present invention can also use an oxime compound having a fluorine atom as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include the compound described in Japanese Patent Laid-Open No. 2010-262028, compound 24 and compound 36 to compound 40 described in Japanese Patent Publication No. 2014-500852 The compound (C-3) described in Japanese Patent Application Publication No. 2013-164471, etc. Its content can be incorporated into this manual.

The present invention can also use a compound represented by the following general formula (1) or (2) as a photopolymerization initiator.

In formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 20 carbons, an alicyclic hydrocarbon group having 4 to 20 carbons, an aryl group having 6 to 30 carbons, or a carbon number of 7 to The arylalkyl group of 30, when R ¹ and R ² are phenyl groups, the phenyl groups can be bonded to each other to form a stilbene group. R ³ and R ⁴ each independently represent a hydrogen atom and an alkane having 1 to 20 carbon atoms. Group, aryl group having 6 to 30 carbons, arylalkyl group having 7 to 30 carbons, or heterocyclic group having 4 to 20 carbons, and X represents a direct bond or a carbonyl group.

^1, R ^2, the same as in the formula (2), R ^1, R ^2, R meaning as in formula (1) ³ and R ⁴ is R R ³ and R ^4, R ⁵ represents -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 atom Or hydroxyl, R ⁶ represents an alkyl group with 1 to 20 carbons, an aryl group with 6 to 30 carbons, an arylalkyl group with 7 to 30 carbons, or a heterocyclic group with 4 to 20 carbons. X represents a direct bond Or a carbonyl group, a represents an integer of 0-4.

In the formulas (1) and (2), R ¹ and R ² are each independently preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a cyclohexyl group or a phenyl group. R ^{3 is} preferably methyl, ethyl, phenyl, tolyl or xylyl. R ^{4 is} preferably an alkyl group or phenyl group having 1 to 6 carbon atoms. R ^{5 is} preferably methyl, ethyl, phenyl, tolyl or naphthyl. X is preferably a direct bond.

As specific examples of the compound represented by the formula (1) and the formula (2), for example, the compounds described in paragraph 0076 to paragraph 0079 of JP 2014-137466 A can be cited. Its content can be incorporated into this manual.

In addition, an oxime initiator having a fluorine atom can also be used. Specific examples of such an initiator include: the compound described in JP 2010-262028 A, and the compound 24 and compound 36 described in paragraph 0345 of JP 2014-500852 A ~ Compound 40, the compound (C-3) described in paragraph 0101 of JP 2013-164471 A.

The following shows specific examples of oxime compounds that can be preferably used in the present invention, but the present invention is not limited to these.

[化86]

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

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

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

The photopolymerization initiator used in the present invention may be used in combination of two or more types as necessary.

In the total solid content of the composition of the present invention, the content of the photopolymerization initiator is preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass to 30% by mass, and still more preferably 1% by mass to 20% by mass %. If it is this range, more favorable sensitivity and pattern formability can be obtained.

The composition of the present invention may include only one type of photopolymerization initiator, or may include two or more types. When two or more are contained, it is preferable that the total amount falls within the said range.

[Resin E]

From the viewpoint of reducing the reflection of the obtained colored layer, the composition of the present invention preferably further contains resin E having a group represented by the following general formula (1).

*-X ₁ -Y…(1)

In the general formula (1), X ₁ represents a single bond or a divalent linking group. Y represents an alkyl group or a silyl group. * Indicates the bonding position (for example, the bonding position to the main chain of resin E).

When such resin E is blended in the composition of the present invention, in the obtained colored layer, the resin E tends to be concentrated in the vicinity of the surface. As a result, a two-layer structure was formed just as if a coating layer derived from resin E was provided on the upper layer of the colored layer. If such a two-layer structure is formed, the light reflected on the surface of the coating layer and the light reflected on the interface between the coating layer and the colored layer are eliminated by interference, so that low reflectivity can be achieved.

In the formula (1), when X ₁ represents a divalent linking group, the divalent linking group includes, for example, a substituent that may have a halogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms. Alkyl or aryl group, -NR ¹² -, -CONR ¹² -, -CO-, -CO ₂ -, SO ₂ NR ¹² -, -O-, -S-, -SO ₂ -or a combination of these. Here, the R ¹² represents a hydrogen atom or a methyl group.

In the formula (1), the alkyl group represented by Y includes, for example, an alkyl group having 3 or more carbon atoms, and more specifically, an alkyl group having 3 or more carbon atoms (preferably 7-30, more preferably 12- 20) straight-chain alkyl group; branched alkyl group having 3 or more carbon atoms (preferably 3-20, more preferably 5-15), etc. Furthermore, the branched alkyl group having 3 or more carbon atoms preferably has -CH(CH ₃ ) ₂ and -C(CH ₃ ) _{3 at the end} .

In addition, in formula (1), the alkyl group represented by Y is preferably at least A linear, branched or cyclic alkyl group in which one hydrogen atom is replaced by a fluorine atom. The number of carbons in the alkyl group substituted with a fluorine atom is preferably 3-20, more preferably 3-10, and still more preferably 3-5. Furthermore, the alkyl group substituted with a fluorine atom may further have a substituent other than a fluorine atom (for example, an oxygen atom, etc.).

As an example of the alkyl group substituted with a fluorine atom, a group represented by -CH(CF ₃ ) ₂ and the like can be cited. In addition, for example, refer to the paragraph [0266]~paragraph of Japanese Patent Laid-Open No. 2011-100089 [0272], its content can be incorporated into this specification.

The resin E particularly preferably has a fluorine atom. By containing fluorine atoms, in the obtained colored layer, the resin E is easy to concentrate, especially near the surface. Therefore, in addition to the more excellent low reflectivity, the coatability is also excellent. Therefore, even in the colored layer of the present invention When multiple layers are formed up and down, the layers may be formed without defects.

In the formula (1), the silyl group represented by Y includes, for example, an alkylsilyl group, an arylsilyl group, or a group containing the following partial structure (S) (* represents a bonding site with another atom).

The total number of carbon atoms in the alkyl chain of the alkylsilyl group is preferably from 1 to 20, more preferably from 1 to 10, and still more preferably from 1 to 6. Preferably it is a trialkylsilyl group.

Examples of the aryl group in the arylsilyl group include a phenyl group.

The group including the partial structure (S) may also 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 with 1 to 3 carbons) and an alkoxysilyl group are preferable. As an example of the base including the partial structure (S), for example, paragraph [0277] to paragraph [0279] of JP 2011-100089 A can be referred to, and the content can be incorporated into this 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 replaced by a fluorine atom, and more preferably at least one hydrogen atom is replaced by a fluorine atom The substituted linear or branched alkyl group having 3 to 10 carbon atoms is more preferably a branched alkyl group having 3 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom.

Furthermore, Y in the formula (1) may be connected to a polymer chain in another part of the resin E to form a crosslinked structure.

The resin E may have only one type of group represented by the general formula (1), or may have two or more types.

Resin E is preferably a resin containing a repeating unit having a group represented by the general formula (1), and more preferably a resin containing a repeating unit having a group represented by the general formula (2).

Furthermore, the resin E is preferably a (meth)acrylate polymer.

As the repeating unit having a group represented by the general formula (1), for example, the groups shown below may be mentioned, but it is not limited to these. In a specific example, X ¹ represents a hydrogen atom, -CH ₃ , -F or -CF ₃ , and more preferably a hydrogen atom or a methyl group. Me represents methyl.

[化89]

Among the three formulas, n in the top formula is 1-100, and R ₂ represents 1-100. In the middle formula, l is 1-100, m is 1-100, and n is 1-100. In the lowermost formula, l is independently 1-100, m is 1-100, and n is 1-100.

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

[化92]

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

The resin E having a group represented by the above general formula (1) preferably further has a group represented by the following general formula (2).

*-X ₂ -Z…(2)

In the 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 (meth)acryloyl, allyl, vinyl, oxetanyl, epoxy, and hydroxymethylamino. * Indicates the bonding position (for example, the bonding position to the main chain of resin E).

Since the resin E has a group represented by the general formula (2), the resin E is hardened (crosslinked) or the resin E and the polymerizable compound B are crosslinked in the exposed portion, Therefore, even if the organic development after exposure (step c1) is performed, the resin E is difficult to elute. In particular, from the viewpoint of curability, heat resistance, etc., it is preferable that Z in the general formula (2) is a (meth)acryloyl group.

In the formula (2), when X ₂ represents a divalent linking group, the divalent linking group includes, for example, a substituent that may have a halogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms. Alkyl or aryl group, -NR ¹² -, -CONR ¹² -, -CO-, -CO ₂ -, SO ₂ NR ¹² -, -O-, -S-, -SO ₂ -or a combination of these. Here, the 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.

As the repeating unit having a group represented by the general formula (2), for example, a repeating unit represented by the following formula (B1) and the like can be cited.

In formula (B1), R ¹ to R ³ each independently represent 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 (meth)acryloyl, allyl, vinyl, oxetanyl, epoxy, and hydroxymethylamino.

In formula (B1), R ¹ to R ³ are each independently preferably a hydrogen atom or an alkyl group. When R ¹ to R ³ represent an alkyl group, it is preferably an alkyl group having 1 to 3 carbon atoms. When R ¹ to R ³ represent a halogen atom, a fluorine atom is preferable.

The same as X (2) the meaning of X ₂ and Z in the formula (B1) and Z ₂ in the general formula.

In addition, as a repeating unit having a group represented by the general formula (2), for example, the groups shown below may be mentioned, but it is not limited to these.

Relative to all repeating units in resin E, it has the formula (2) The content of the repeating unit of the indicated group is preferably 30 mol% to 95 mol%, more preferably 45 mol% to 90 mol%.

<Appropriate aspect of resin E>

As one of the suitable aspects of the resin E, there can be mentioned a repeating unit similar to the repeating unit A represented by the structural formula (I) described in Japanese Patent Laid-Open No. 2010-164965, and a repeating unit similar to the repeating unit A represented by the general formula (II) ) A curable compound of a repeating unit similar to the repeating unit B.

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 cited.

[化95]

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

In the 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 unit a to repeating unit e represented by the following structural formula (71a) to structural formula (71e).

In formula (A2), X and Y each independently represent any one of the following structural formula (K1) to structural formula (K3). In addition, w in the following structural formula (K2) represents any integer of 1-20.

[化96]

As the sclerosing compound having the repeating unit represented by the formula (A1) and the repeating unit represented by the formula (A2) as described above, for example, Megafac RS manufactured by DIC Corporation can be cited -718-K, Megafac RS-72-K, etc.

As a commercially available product of the curable compound, for example, as a curable compound having a fluorine atom, Megafac RS-72-K manufactured by DIC Corporation, Megafac RS-75, Megafac RS-76-E, Megafac RS-76-NS, Megafac RS-77, as hardening compounds with silicon atoms, BYK-UV 3500, BYK- manufactured by BYK can be used UV 3530, BYK-UV 3570, TEGO Rad 2010, TEGO Rad 2011, TEGO Rad 2100, TEGO Rad 2200N, TEGO Rad 2250, TEGO Rad 2300, TEGO Rad 2500, manufactured by Evonik (EVONIK) TEGO Rad 2600, TEGO Rad 2650, TEGO Rad 2700, etc.

Among them, from the viewpoint of reducing reflectance, a curable compound having a fluorine atom is preferred.

The curable compound is preferably a film having a refractive index of 1.1 to 1.5 at a wavelength of 550 nm formed by the curable compound alone. That is, it is preferable that the refractive index at a wavelength of 550 nm of a film formed only of the curable compound is 1.1 to 1.5.

As a suitable range of the said refractive index, from a viewpoint of the low reflectivity of a light-shielding film, 1.2-1.5 are preferable, and 1.3-1.5 are more preferable.

In addition, as an aspect of the resin E, for example, those described in paragraph [0141] to paragraph [0145] (Synthesis Example 1) of JP-A-2015-117327 can also be suitably selected from among the following "Fluorine-based surfactant (I)" which is a repeating unit of a polymerizable monomer represented by formula (A-1-1).

In formula (A-1-1), X is perfluoromethylene and perfluoroethylene. In each molecule, there are 7 perfluoromethylene groups on average, and 8 perfluoroethylene groups on average. 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, more preferably 7,000 to 50,000.

In addition, the degree of dispersion (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the resin E is preferably 1.80 to 3.00, more preferably 2.00 to 2.90.

In addition, in the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are polystyrene conversion values obtained by the following GPC method.

GPC (Gel Permeation Chromatography) method is based on the use of HLC-8020 GPC (manufactured by Tosoh (Tosoh)) and combining TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ2000 (manufactured by Tosoh) within 4.6mm The diameter (Inner Diameter, ID) x 15 cm) is used as the column, and tetrahydrofuran (THF) is used as the method of elution.

Resin E may be used individually by 1 type, and may use 2 or more types together.

In the case where the composition of the present invention contains resin E, the content of resin E is preferably 0.1% by mass to 20% by mass, and more preferably 0.5% by mass to 15% by mass relative to the total solid content in the composition of the present invention %, more preferably 1.0% by mass to 10% by mass. In the case where the composition of the present invention contains two or more kinds of resin E, it is only necessary that the total thereof is within the above-mentioned range.

[Solvent]

The composition of the present invention may further contain a solvent. The solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition.

As the solvent, esters include, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, Butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (e.g. methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g. methyl methoxyacetate, methoxy Ethyl ethoxylate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-oxypropionate (for example: methyl 3-oxypropionate , Ethyl 3-oxypropionate, etc. (e.g. methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate Esters, etc.)), 2-oxypropionic acid alkyl esters (for example: 2-oxymethyl propionate, 2-oxyethyl propionate, 2-oxypropionic acid propyl ester, etc. (for example, 2-methyl Methyl oxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2 -Oxy-2-methylpropionic acid methyl ester and 2-oxy-2-methylpropionic acid ethyl ester (e.g. 2-methoxy-2-methylpropionic acid methyl ester, 2-ethoxy-2 -Ethyl methyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, 2-oxo Ethyl butyrate and the like, and 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 acetic acid Ester, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and the ketones include, for example, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc., and, As the aromatic hydrocarbons, for example, xylene and the like can be suitably mentioned. Two or more of these solvents may be used in combination.

From the viewpoint of coatability, the content of the solvent in the composition of the present invention is preferably such that the total solid content concentration of the composition of the present invention becomes 5 mass% to 80 mass %, and more preferably becomes 5 mass% The amount of ~60% by mass is more preferably an amount of 10% by mass to 50% by mass.

[Dispersant]

The colored radiation composition of the present invention may contain a dispersant when it contains a pigment.

As the dispersant, a polymer dispersant [for example, polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, Modified poly(meth)acrylate, (meth)acrylic copolymer, naphthalenesulfonate formalin condensate], and polyoxyethylene alkyl phosphate, polyoxyethylene alkyl amine, alkanolamine, etc. Agent, and pigment derivatives.

Polymer dispersants can be further classified into linear polymers, terminal modified polymers, graft-type polymers, and block-type polymers according to their structure.

Examples of terminal-modified polymers having fixed sites on the surface of the pigment include high-density polymers described in Japanese Patent Laid-Open No. Hei 3-112992 and Japanese Patent Publication No. 2003-533455, etc., having a phosphate group at the end. Molecule, a polymer having a sulfonic acid group at the end described in Japanese Patent Laid-Open No. 2002-273191, etc., a polymer having a partial skeleton of an organic dye and a heterocyclic ring described in Japanese Patent Laid-Open No. 9-77994, etc. Wait. In addition, Japanese Patent Publication The dispersion stability of polymers with two or more fixed sites (acid groups, basic groups, partial skeletons of organic pigments, and heterocycles, etc.) on the surface of the pigment introduced into the end of the polymer described in the 2007-277514 publication is also Excellent, but better.

Examples of graft-type polymers having fixed sites on the surface of the pigment include polyester-based dispersants, and specific examples include: Japanese Patent Laid-Open No. 54-37082, Japanese Patent Publication No. Hei 8 -507960, the reaction product of poly(lower alkyleneimine) and polyester described in Japanese Patent Laid-Open No. 2009-258668, etc.; polyolefin described in Japanese Patent Laid-Open No. 9-169821, etc. The reaction product of propylamine and polyester; Japanese Patent Laid-Open No. 10-339949, Japanese Patent Laid-Open No. 2004-37986, etc. The copolymer of macromonomer and nitrogen atom monomer; Japanese Patent Special A graft-type polymer having a partial skeleton and/or heterocyclic ring of an organic dye described in Japanese Patent Application Publication No. 2003-238837, Japanese Patent Application Publication No. 2008-9426, Japanese Patent Application Publication No. 2008-81732, etc.; Japan A copolymer of a macromonomer and an acid group-containing monomer described in Japanese Patent Application Laid-Open No. 2010-106268 and the like. In particular, from the viewpoints of the dispersibility and dispersion stability of the pigment dispersion, and the developability shown by the color-sensitive radiation composition using the pigment dispersion, it is particularly preferred that it is described in Japanese Patent Laid-Open No. 2009-203462 Amphoteric dispersion resin with basic and acidic groups.

As the macromonomers used in the production of graft-type polymers with fixed sites on the pigment surface by free radical polymerization, well-known macromonomers can be used, including: Macromolecules manufactured by Toagosei Co., Ltd. Monomer AA-6 (polymethyl methacrylate with methacrylic acid end group), AS-6 (methyl propylene end group Alkenyl polystyrene), AN-6S (a copolymer of styrene and acrylonitrile with a methacrylic end group), AB-6 (polybutyl acrylate with a methacrylic end group) , PlaccelFM5 (5-mole equivalent adduct of ε-caprolactone of 2-hydroxyethyl methacrylate) manufactured by Daicel Chemical Industry (Stock), FA10L (ε-hexyl of 2-hydroxyethyl acrylate) Lactone (10 molar equivalent adduct), and the polyester-based macromonomer described in JP 2-272009 A, etc. Among these, particularly from the viewpoints of the dispersibility and dispersion stability of the pigment dispersion, and the developability exhibited by the color-sensitive radiation composition using the pigment dispersion, it is particularly preferred that it is excellent in flexibility and solvent affinity The polyester-based macromonomer is particularly preferably a polyester-based macromonomer represented by the polyester-based macromonomer described in Japanese Patent Laid-Open No. 2-272009.

As the block-type polymer having a fixed portion to the surface of the pigment, the block-type polymer described in Japanese Patent Laid-Open No. 2003-49110, Japanese Patent Laid-Open No. 2009-52010, and the like are preferred.

The dispersant can also be obtained as a commercially available product. As such specific examples, "DA-7301" manufactured by Kusumoto Chemical Co., Ltd., and "DISPARBIC (by BYK Chemie) Disperbyk)-101 (polyamide phosphate), Disperbyk-107 (carboxylate), Disperbyk-110 (copolymer containing acid groups), Disperbyk-130 (polyamide), Disperbyk-161, Disperbyk-162 , Disperbyk-163, Disperbyk-164, Disperbyk-165, Disperbyk-166, Disperbyk-170 (polymer copolymer)", "BYK-P104, BYK-P105 (high molecular weight unsaturated polycarboxylic acid)", Efka (EFKA) manufactured by the company "EFKA4047, EFKA4050~EFKA4010~EFKA4165 (polyurethane series), EFKA4330~EFKA4340 (block copolymer), EFKA4400~EFKA4402 (modified polyacrylate), EFKA5010 (polyester amide), EFKA5765 (high molecular weight polycarboxylate) Acid salt), EFKA6220 (fatty acid polyester), EFKA6745 (phthalocyanine derivative), EFKA6750 (azo pigment derivative)", manufactured by Ajinomoto Fine-Techno, "Ajisper )PB821, Ajisper PB822, Ajisper PB880, Ajisper PB881", "Florene TG-710 (urethane oligomer)" manufactured by Kyoeisha Chemical Co., Ltd., "Polyflow" No.50E, Polyflow No.300 (acrylic copolymer)", "Disparlon KS-860, Disparlon 873SN, Disparlon 874, Disparlon #2150 (aliphatic polycarboxylic acid), Disparlon #7004 (polyether ester), Disparlon DA-703-50, Disparlon DA-705, Disparlon DA-725", "Demol RN, Demol N (formalin naphthalenesulfonate condensation polymer) manufactured by Kao ), Demol MS, Demol C, Demol SN-B (aromatic sulfonic acid formalin polycondensate), "Homogenol L-18 (polymer polycarboxylic acid)", "Emalgen" 920, Emalgen930, Emalgen935, Emalgen985 (polyoxyethylene nonylphenyl ether)", "Aeetamin 86 (stearylamine acetate)", manufactured by Lubrizol (Stock) Solsperse 5000 (phthalocyanine derivative), Solsperse 22000 (azo pigment derivative), Solsperse 13240 (polyester amine), Solsperse 3000, Solsperse 17000, Solsperse 27000 (polymers with functional parts at the end), Solsperse 24000 , Solsperse28000, Solsperse32000, Solsperse38500 (grafted polymer)", "Nikkol T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) manufactured by Nikko Chemicals Acid esters)", Hinoact T-8000E manufactured by Kawaken Fine Chemicals (Stock), etc., organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd., Yushang (Stock) "W001: Cationic Surfactant", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene Non-ionic surfactants such as nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters, anionic surfactants such as "W004, W005, and W017" Surfactant, "EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer400, EFKA Polymer401, EFKA Polymer450" manufactured by Morishita Industry Co., Ltd., San Nopco ( "Disperse Aid (Disperse Aid) 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100" and other polymer dispersants manufactured by Sannopco (Stock); Adeka Pluronic) L31, Adeka Pluronic F38, Adeka Pluronic L42, Adeka Pluronic L44, Adeka Pluronic L61, Adeka Pluronic L64, Adeka Pluronic F68, Adeka Pluronic L72, Adeka Pluronic P95, Adeka Pluronic F77, Adeka Pluronic 87, Adeka Pluronic Pluronic P94, Adeka Pluronic L101, Adeka Pluronic P103, Adeka Pluronic F108, Adeka Pluronic L121, Adeka Pluronic P-123, and "Ionet" manufactured by Sanyo Chemical Co., Ltd. Name) S-20" and so on.

The dispersant can be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant. In addition, the dispersant of the present invention can also be used in combination with terminally modified polymers, graft-type polymers, block-type polymers, and alkali-soluble resins having fixed sites on the pigment surface. Examples of alkali-soluble resins include (meth)acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, etc., and side chains A resin obtained by modifying an acidic cellulose derivative having a carboxylic acid group and an acid anhydride in a polymer having a hydroxyl group is particularly preferably a (meth)acrylic copolymer. In addition, the N-substituted maleimide monomer copolymer described in Japanese Patent Laid-Open No. 10-300922, the ether dimer copolymer described in Japanese Patent Laid-Open No. 2004-300204, and the Japanese Patent Alkali-soluble resins containing polymerizable groups described in JP-A-7-319161 are also preferable.

The content of the dispersant in the color-sensitive radiation composition is preferably 1 part by mass to 80 parts by mass, more preferably 5 parts by mass to 70 parts by mass, and still more preferably 10 parts by mass relative to 100 parts by mass of the pigment. 60 parts by mass.

Specifically, in the case of using a polymer dispersant, the amount used is preferably in the range of 5 parts to 100 parts, more preferably 10 parts to 80 parts based on mass conversion, relative to 100 parts by mass of the pigment range.

In addition, in the case of using a dispersant and a pigment derivative in combination, the amount of the pigment derivative used is preferably in the range of 1 part to 30 parts in terms of mass per 100 parts by mass of the pigment, and more preferably 3 parts to 20 parts. Servings, particularly preferably 5 to 15 servings.

In the coloring radiation composition of the present invention, when dyes and pigments are used, in terms of curing sensitivity and color density, the dye and pigment are contained relative to the total solid content of the coloring radiation composition The concentration of the coloring agent is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more. In addition, the concentration of the coloring agent with respect to the total solid content of the coloring radiation composition is preferably 90% by mass or less, and more preferably 85% by mass or less.

In addition, in the coloring radiation composition of the present invention, when a pigment is used, the concentration of the pigment relative to the total solid content of the coloring radiation composition is preferably 25% by mass or more, more preferably 35 Mass% or more, more preferably 45% by mass or more. In addition, the concentration of the pigment with respect to the total solid content of the color-sensitive radiation composition is preferably 65% by mass or less, and more preferably 55% by mass or less.

[Surfactant]

From the viewpoint of further improving coatability, the composition of the present invention may contain various surfactants. As the surfactant, various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. Furthermore, the resin E is not included in the surfactant.

Examples of the fluorine-based surfactant include: Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F482, Megafac F554, Megafac F780, Megafac F781 (above, Di Ai Health (manufactured by shares), Fluorad FC430, Fluorad FC431, Fluorad FC171 (above, manufactured by Sumitomo 3M (Stock)), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 , PF6520, PF7002 (manufactured by OMNOVA), etc.

Specific examples of nonionic surfactants include glycerin, trimethylolpropane, trimethylolethane, and these ethoxylates and propoxylates (for example, glycerol propoxylate, Glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene Ethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters (Pluronic L10, Pluronic L31, Pluronic L61, Pluronic L62, Pluronic 10R5, manufactured by BASF) Pluronic 17R2, Pluronic 25R2, Tetronic 304, Tetronic 701, Tetronic 704, Tetronic 901, Tetronic 904, Tetronic 150R1, Pionin D-6112-W (manufactured by Takemoto Oil Co., Ltd.), Solsperse 20000 (Made by Lubrizol (Japan) Co., Ltd.)) and so on.

Specific examples of cationic surfactants include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) , (Meth)acrylic (co)polymer Polyflow No.75, Polyflow No.90, Polyflow No.95 (Kyoeisha Chemicals (manufactured by shares), W001 (manufactured by Yushang (shares)), etc.

As an anionic surfactant, specifically, W004, W005, W017 (manufactured by Yushang (Co., Ltd.)) etc. are mentioned.

As silicone-based surfactants, for example, Toray. "Toray Silicone DC3PA", "Toray Silicone SH7PA", "Toray Silicone DC11PA", "Toray Silicone SH21PA", "Toray Silicone SH28PA", "Toray Silicone" manufactured by Dow Corning (Stock) "SH29PA", "Toray Silicone SH30PA", "Toray Silicone SH8400", "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460" manufactured by Momentive Performance Materials , "TSF-4452", "KP341", "KF6001", "KF6002" manufactured by Shin-Etsu Silicone Co., Ltd., "BYK307", "BYK323", "BYK330" manufactured by BYK Chemicals, etc.

Surfactants may be used alone or in combination of two or more.

When the composition of the present invention contains a surfactant, relative to the total mass of the composition of the present invention, the content of the surfactant is preferably 0.001% by mass to 2.0% by mass, more preferably 0.005% by mass to 1.0% by mass %.

[Photo Acid Generator]

The composition of the present invention may further contain a photoacid generator (acid generator) that is a compound that generates an acid by irradiation with radiation.

When the composition of the present invention contains resin E having a group represented by the general formula (2), Z in the group represents an oxetanyl group, an epoxy group, or a hydroxyl group. In the case of a methylamino group, these groups are easily decomposed and crosslinked by the acid action of the photoacid generator.

The photoacid generator is not particularly limited, and well-known photoacid generators can be suitably used. Examples thereof include sulfonic acid, bis(alkylsulfonyl)imide, and tris(alkylsulfonyl). Methyl compounds and other compounds.

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 still more preferably 1000 or less.

As an example of the photoacid generator, for example, paragraph [0168] to paragraph [0214] of JP 2015-138232 A can be referred to, and the content can be incorporated in this specification.

One kind of photoacid generator may be used alone, or two or more kinds may be used in combination.

In the case where the composition of the present invention contains a photoacid generator, based on the total solid content of the composition of the present invention, the content of the photoacid generator is preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass %~40% by mass.

[Other ingredients]

In the composition of the present invention, in addition to the above-mentioned essential components and optional components, other components may be appropriately selected and used according to the purpose as long as the effects of the present invention are not impaired.

Other components that can be used in combination include, for example, binder polymers, dispersants, sensitizers, crosslinkers, hardening accelerators, fillers, thermosetting accelerators, thermal polymerization inhibitors, plasticizers, ultraviolet absorbers, Silane coupling agent, etc., and further, adhesion promoters and other auxiliary agents (such as conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling promoters, antioxidants, spices, Surface tension regulator, chain transfer agent, etc.).

By suitably containing these components, the stability of the formed film and the properties of the film can be adjusted.

For these ingredients, for example, reference can be made to the description of paragraph [0183] and subsequent (corresponding U.S. Patent Application Publication No. 2013/0034812 specification [0237] and subsequent) of Japanese Patent Laid-Open No. 2012-003225, Japanese Patent Laid-Open No. 2008-250074 Bulletin No. [0101] ~ paragraph [0102], paragraph [0103] ~ paragraph [0104] and paragraph [0107] ~ paragraph [0109], etc., these contents can be incorporated into the specification of this application.

[Preparation of colored radiation composition]

The preparation aspect of the composition of the present invention is not particularly limited, and for example, it can be prepared by mixing the essential components and optional components.

The composition of the present invention is preferably filtered with a filter for the purpose of removing foreign matter and reducing defects.

As a filter used for filter filtration, as long as it is a filter used for a filtering purpose etc., it can use without a restriction|limiting in particular.

Examples of the material of the filter include: fluororesins such as polytetrafluoroethylene (PTFE); polyamide resins such as nylon-6, nylon-6, 6; polyethylene, polypropylene (Polypropylene, PP) Polyolefin resins (including high density and ultra-high molecular weight), etc. Among these raw materials, polypropylene (including high-density polypropylene) is preferred.

The pore size of the filter is not particularly limited, and is, for example, about 0.01 μm to 20.0 μm, preferably about 0.01 μm to 5 μm, and more preferably about 0.01 μm to 2.0 μm.

By setting the pore size of the filter in the above range, fine particles can be removed more effectively, 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, available from Pall Co., Ltd., Advantec Toyo Co., Ltd., Nihon Entegris Co., Ltd. (formerly Nihon Entegris) Choose from various filters provided by Mykrolis Co., Ltd. or Kitz Microfilter Co., Ltd.

In addition, as the raw material used in the colored radiation composition of the present invention, it is preferable to use a high-purity raw material. It can suppress the mixing and generation of impurities such as particles, metal impurities, moisture and peroxides that affect performance.

As a method of applying the composition of the present invention to the support, various methods such as slit coating, inkjet method, spin coating, spray coating, cast coating, roll coating, and screen printing can be used.

Among them, from the viewpoint of making the film thickness of the colored radiation-sensitive composition layer uniform, slit coating, spin coating, and spray coating are preferred. In addition, in the case where the lower surface of the colored radiation-sensitive composition layer is uneven, from the viewpoint of making the film thickness uniform, spray coating or inkjet methods are preferred.

When the composition of the present invention is applied by inkjet, it preferably has suitable physical properties for application to an inkjet recording device.

That is, in the case where the composition of the present invention is used in an inkjet recording method, in consideration of ejectability, it is preferable that the ink viscosity at the temperature of ejection is 100 mPa. s below, More preferably, 50mPa. s or less, it is preferable to appropriately adjust and determine the composition ratio so as to be in the above range.

Furthermore, the viscosity of the composition at 25°C (room temperature) is preferably 0.5 mPa. Above s, 200mPa. s or less, more preferably 1mPa. Above s, 100mPa. s or less, more preferably 2mPa. Above s, 50mPa. s or less. By setting the viscosity in a room temperature environment high, even when it is applied to a substrate having unevenness, dripping of the composition can be prevented, and as a result, a uniform light-shielding film can be formed. When the viscosity at 25℃ is greater than 200mPa. In the case of s, there may be a problem in the transportation of the composition (the transportation state of the liquid in the device).

The surface tension of the composition of the present invention is preferably 20 mN/m to 40 mN/m, more preferably 25 mN/m to 35 mN/m. When applied to the surface of a silicon substrate or metal wiring, it is preferably 20 mN/m or more from the viewpoint of suppressing dripping, and 35 mN/m from the viewpoint of adhesion and affinity with the substrate, etc. m or less.

[Method of manufacturing colored layer]

Next, the manufacturing method of the colored layer of this invention (the manufacturing method of this invention) is demonstrated.

The manufacturing method of the coloring layer of the present invention is the following method for manufacturing the coloring layer, including: forming a coloring radiation composition layer using the composition of the present invention; and radiating the coloring radiation through a mask The step b of exposing the composition layer into a pattern; and the step c of processing the exposed colored radiation-sensitive composition layer to form a colored layer, and the step c is implementing the use of a developer containing an organic solvent In step c1 of processing and step c2 of developing using alkaline aqueous solution Any step of the next step is performed thereafter.

Hereinafter, each step included in the manufacturing method of the present invention will be described.

[Step a]

In step a, the composition of the present invention is used to form a colored radiation-sensitive composition layer. At this time, by coating the composition of the present invention on, for example, a substrate, a color-sensitive radiation composition layer is formed.

As the substrate, for example, a charge-coupled device (CCD) used in a solid-state imaging device or a photoelectric conversion element substrate or a silicon substrate in a complementary metal oxide semiconductor (Complementary Metal Oxide Semiconductor, CMOS) can be cited; Alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used in liquid crystal display devices, etc., and those with a transparent conductive film attached thereto. These substrates may also be formed with black matrices that separate pixels.

In addition, in order to improve the adhesion with the upper layer, to prevent the diffusion of substances, or to flatten the surface of the substrate, if necessary, an undercoat layer may be provided on these substrates.

As a method of applying the composition of the present invention, for example, various coating methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, and screen printing methods can be cited.

The 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 still more preferably 0.2 μm to 3 μm

For the color-sensitive radiation composition layer, drying (pre-baking) may be implemented as needed. The pre-baking can be performed using a hot plate and an oven at a temperature equal to 50°C to 140°C for 10 seconds to 300 seconds.

[Step b]

In step b, the colored radiation composition layer formed in step a is exposed into a pattern through a mask. At this time, for example, an exposure device such as a stepper is used to perform pattern exposure through a mask having a predetermined mask pattern.

As the radiation (light) that can be used for exposure, ultraviolet rays such as g-rays and i-rays (particularly preferably i-rays) can be preferably used. Irradiation amount (exposure amount) is preferably ^{30mJ / cm 2 ~ 1500mJ / cm} 2, more preferably ^{50mJ / cm 2 ~ 1000mJ / cm} 2, and further is excellent ^{80mJ / cm 2 ~ 500mJ / cm} 2.

[Step c]

Step c is a step of processing the colored radiation-sensitive composition layer exposed in step b to form a colored layer, and is a step c1 of performing processing using a developer containing an organic solvent, and developing using an alkaline aqueous solution Any step in step c2 of step c2 is followed by another step.

As described above, by the development (alkaline development) using an alkaline aqueous solution, the unexposed portion of the colored radiation-sensitive composition layer is eluted into the alkaline aqueous solution, and the light-cured exposed portion remains as a colored layer. At this time, in the unexposed part of the colored radiation-sensitive composition layer, the hydrophobic components other than the alkali-soluble resin C are not eluted and may become residues. However, by performing development containing an organic solvent before and after the alkali development In liquid treatment (also referred to as "organic development" for convenience), the hydrophobic components in the unexposed area are eluted into the organic solvent, and the generation of residue is suppressed.

The order of step c1 (organic development) and step c2 (alkali development) is not particularly limited, but in the coloring radiation-sensitive composition layer, the hydrophobic component (for example, resin E) It is easy to appear on the surface, so it is removed first. From this point of view, it is better to perform step c1 first and then step c2.

<Step c1 (Organic Development)>

In step c1, a developer containing an organic solvent (hereinafter, also referred to as an "organic developer") is used.

The vapor pressure of the developer containing an organic solvent (in the case of a mixed solvent, the vapor pressure of the whole) is preferably 5 kPa or less at 20°C, more preferably 3 kPa or less, and still more preferably 2 kPa or less. By setting the vapor pressure of the organic solvent to 5 kPa or less, the evaporation of the developer on the substrate or in the developing cup is suppressed, and the temperature uniformity in the wafer surface is improved. As a result, the dimensional uniformity in the wafer surface is improved.

As the organic solvent contained in the organic developer solution, a wide variety of organic solvents can be used without particular limitation. Examples include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. Solvents such as solvents.

In the present invention, the term "ester-based solvent" refers to a solvent having an ester group in the molecule.

The ketone solvent refers to a solvent having a ketone group in the molecule.

The alcohol-based solvent means a solvent having an alcoholic hydroxyl group in the molecule.

The term "amide-based solvent" refers to a solvent having an amide group in the molecule.

The term "ether-based solvent" refers to a solvent having an ether bond in the molecule. Among these, there are also solvents having multiple types of the functional groups in one molecule, and in this case, it is set to correspond to any solvent type including the functional groups of the solvent. For example, it is assumed that diethylene glycol monomethyl ether corresponds to an alcohol solvent and an ether solvent in the above classification.

The term "hydrocarbon-based solvent" means a hydrocarbon solvent that does not have a substituent.

Hereinafter, specific examples of organic solvents will be described.

Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methylpentyl ketone), 4-heptanone, 1- Hexanone, 2-hexanone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetone, Acetone acetone, ionone, diacetone alcohol, acetyl methanol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, etc.

Examples of ester-based solvents include: methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, and amyl acetate , Isoamyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene two Alcohol 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 butyrate, methyl 2-hydroxyisobutyrate, isobutyl isobutyrate, butyl propionate, etc. .

Examples of alcohol-based solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, and n-hexyl alcohol. Alcohol such as base alcohol, n-heptyl alcohol, n-octyl alcohol, n-decyl alcohol; glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether ( Alias: 1-methoxy-2-propanol), ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol Glycol ether solvents such as monomethyl ether, triethylene glycol monoethyl ether, and methoxymethyl butanol.

Examples of ether solvents include the aforementioned glycol ether solvents, dioxane, and tetrahydrofuran.

As the amide-based solvent, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphatidylamine, 1,3-Dimethyl-2-imidazolidinone, etc.

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, as an organic developer, it is preferable to include a solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, ether solvents, and hydrocarbon solvents for the reason that the generation of residues is more excellent. The developer containing at least one solvent in the group is more preferably a developer containing at least one solvent selected from the group consisting of ketone solvents, ester solvents, and ether solvents.

Furthermore, the organic solvent contained in the organic-based developer is preferably free of organic chlorine compounds (non-organic chlorine compounds) such as 1,1,1-trichloroethane. The reason for this is that the heat resistance of the obtained colored layer may be deteriorated due to the action of the organochlorine compound and the coloring agent.

The organic solvent used in the developer may be used in combination of multiple types, or may be used in combination with solvents or water other than the above. In order to achieve the effect of the invention more effectively, the moisture content of the entire developer is preferably 30% by mass or less, more preferably less than 10% by mass, and still more preferably substantially free of water.

Concentration of organic solvents in the developer (total when multiple types are mixed) It 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 when it contains substantially only an organic solvent. In addition, the case where only the organic solvent is contained substantially includes the case where a trace amount of surfactant, antioxidant, basic compound, stabilizer, defoamer, etc. are contained.

The organic solvent in the developer containing the organic solvent may also be specified using the SP value (Solubility Parameter). As the SP value of the organic solvent, for example, the SP value described in VII/675~714 of "Polymer Handbook Fourth Edition Volume 2 (POLYMER HANDBOOK FOURTH EDITION Volume 2)" (more specifically, the SP value described in Table 7 SP value). 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, still more preferably 15.1 to 17.5 or 30.0 to 42.0, particularly preferably 15.7 to 17.5 or 30.0 to 42.0.

By setting the SP value of the organic solvent to 18.9 or less and 23.1 or more, it is possible to prevent the compatibility of the organic solvent and the dye from becoming too good, and it is possible to prevent the generation of dye fading in the self-hardening part. In addition, 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 increased, and the developability can be improved.

In addition, by setting the SP value of the organic solvent to 15.7 or more, the developability of the unexposed part can be made more favorable.

In addition, the developer containing an organic solvent may contain a nitrogen-containing compound. As the nitrogen-containing compound, for example, the description of paragraph [0042] to paragraph [0063] of JP 2013-011833 A can be referred to, and the content can be incorporated into the description of this application. In the book.

As a processing method (development method), for example, a method of immersing the substrate in a bath filled with developer for a certain period of time (dipping method), and development by depositing the developer on the surface of the substrate using surface tension and standing still for a certain period of time can be used. Method (liquid coating method), method of spraying developer on the surface of the substrate (spray method), method of continuously spraying developer on the surface of the substrate rotating at a certain speed while scanning the developer spray nozzle at a certain speed (dynamic distribution method), etc. , Especially preferred is the liquid covering method.

The processing time (development time) is not particularly limited as long as the coloring layer of the unexposed part is fully dissolved, and it is usually 10 seconds to 300 seconds. It is preferably 20 seconds to 120 seconds.

The temperature of the developer is preferably 0°C to 50°C, and more preferably 15°C to 35°C.

In the manufacturing method of the present invention, after processing with a developer containing an organic solvent, washing may be performed with an eluent containing an organic solvent.

The vapor pressure of the eluent (in the case of a mixed solvent, the vapor pressure of the whole) at 20°C is preferably 0.05kPa or more and 5kPa or less, more preferably 0.1kPa or more and 5kPa or less, and still more preferably 0.12kPa or more, Below 3kPa. By setting the vapor pressure of the eluent to 0.05kPa or more and 5kPa or less, the temperature uniformity in the wafer surface is improved, and the swelling caused by the penetration of the eluent is suppressed, and the dimensional uniformity in the wafer surface Get better.

As the eluent, a variety of organic solvents can be used, preferably containing at least one organic solvent or water selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. Of eluent.

Regarding the rinsing treatment, for example, paragraph [0045] to paragraph [0054] of JP 2010-217884 A can be referred to, and the content can be incorporated into the specification of this application.

<Step c2 (Alkaline Development)>

The development method in the alkali development in step c2 may be any one of immersion method, spray method, spray method, liquid coating method, etc., and these methods may be combined with swing method, rotation method, ultrasonic method, etc. In addition, it is also possible to wet the surface to be developed with water or the like before contact with the developer solution to prevent uneven development.

The alkaline aqueous solution as the developer used in the step c2 is preferably an organic alkaline developer that does not damage the photographic elements and circuits of the substrate. 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 further remove the residue, in recent years, it has also been carried out for 120 to 180 seconds. Furthermore, in order to further improve the residue removal properties, there are cases where the following steps are repeated multiple times: the developer is shaken off every 60 seconds, and the developer is supplied again.

As the alkali agent used in the developer, for example, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1, An organic basic compound such as 8-diazabicyclo[5.4.0]-7-undecene, etc., is preferably used as a developer at a concentration of 0.001% to 10% by mass, preferably 0.01% by mass to The 1% by mass method is an alkaline aqueous solution obtained by diluting these alkaline agents with pure water.

In addition, inorganic bases can also be used in the developer. As inorganic bases, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, and sodium metasilicate are preferred. Wait.

Furthermore, when a developer containing such an alkaline aqueous solution is used, it is usually washed (rinsed) with pure water after development.

After washing (rinsing), and then, heat treatment (post-baking) may be performed after drying. Post-baking is a heat treatment after development to achieve complete hardening, and a thermal hardening treatment is usually performed at 100°C to 240°C, preferably 200°C to 240°C.

Heating means such as a heating plate, a convection oven (hot air circulation dryer), and a high-frequency heating machine can be used to achieve the above conditions by continuous or batch method to perform the developed coating film. Post-baking treatment.

[Colored layer (color filter, shading film)]

The use of the pattern-shaped coloring layer (coloring pattern) obtained by the manufacturing method of the present invention is not particularly limited, and it can be used as a light-shielding film or color filter provided in a solid-state imaging device or the like, for example.

For example, a solid-state imaging device mounted in a digital camera, a mobile phone with a camera, or a smart phone includes a photographic lens, a charge-coupled device (CCD) or a complementary metal oxide film semiconductor (CMOS) arranged on the back of the photographic lens. ) And other solid-state imaging devices, and circuit boards on which the solid-state imaging devices are mounted. In such a solid-state imaging device, noise caused by the reflection of visible light may be generated. Therefore, by providing a light-shielding film in the solid-state imaging device, the generation of noise is suppressed. When forming a light-shielding film, as a coloring agent contained in the composition of this invention, black pigments, such as titanium black, can be used, for example.

The color filter, which is an indispensable component of a solid-state imaging device, is formed in a colored area including a plurality of hues, and is usually formed in a colored area (colored pattern) including at least red, green, and blue. At this time, as a method of forming a coloring pattern, first, apply a color-sensitive radiation composition with any of red, green, and blue coloring agents to the first hue, and perform exposure and development to form the color of the first hue After patterning, the same process is repeated for the second hue and the third hue.

The thickness of the colored layer is not particularly limited. For example, when used as a light-shielding film, it is preferably 0.2 μm to 25 μm, more preferably 1.0 μm to 10 μm.

In addition, when used in a color filter, the thickness of the colored layer is, for example, 2.0 μm or less, preferably 1.5 μm or less, more preferably 0.2 μm to 1.5 μm, and still more preferably 0.2 μm to 1.2 μm.

In addition, 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 Photographic Components]

The solid-state imaging device of the present invention includes a colored layer obtained by the manufacturing method of the present invention (hereinafter, also referred to as "the colored layer of the present invention"). The structure of the solid-state imaging element 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 element. For example, the following structures can be cited.

The structure is as follows: on a support, there are a plurality of photodiodes that constitute the light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) and a transmission electrode including polysilicon, etc., in the photodiode and The transmission electrode has only The light-shielding film that opens to the light-receiving part of the photodiode has an element protection film including silicon nitride and the like formed to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode on the light-shielding film. There are color filters on it.

Furthermore, it may also be the following structure: on the element protection layer, and under the color filter (close to the support body) a light condensing means (such as microlens, etc.; the same below), in the color filter The chip has the composition of light-concentrating means.

[Image display device]

The coloring layer of the present invention can be used in image display devices such as liquid crystal display devices and organic electroluminescence display devices.

For the definition of display devices and the details of each display device, for example, "Electronic Display Components (by Akio Sasaki, issued by Kogyo Chosakai Publishing (stock) 1990)", "Display Components (by Jun Akio Ibuki) , Industrial Books (Sangyo Tosho (shares) issued in 1989)" and so on. In addition, the liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (Edited by Tatsuo Uchida, issued by the Industrial Research Council (Stock) 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, it can be applied to various types of liquid crystal display devices described in the "Next Generation Liquid Crystal Display Technology".

The color filter of the present invention can be used in a color thin film transistor (Thin Film Transistor, TFT) type liquid crystal display device. The color TFT liquid crystal display device is described in, for example, "Color TFT Liquid Crystal Display (published by Kyoritsu Publishing Co., Ltd. in 1996)". Furthermore, the present invention can also be applied to lateral electric field driving methods such as In Plane Switching (IPS), and multi-domain vertical alignment (Multi-domain Vertical Alignment, MVA) and other pixel division methods such as liquid crystal display devices with enlarged viewing angles, Super-Twist Nematic (STN), Twisted Nematic (TN), vertical alignment ( Vertical Alignment, VA), Optically Compensated Splay (OCS), fringe field switching (FFS), and Reflective Optically Compensated Bend (R-OCB), etc.

In addition, the color filter of the present invention can also be used in a bright and high-definition color filter array (COA) method. In the COA-based liquid crystal display device, in addition to the usual required characteristics for color filters as described above, the required characteristics for interlayer insulating films, namely low dielectric constant and resistance to peeling liquid, are sometimes required. . Since the color filter of the present invention is excellent in light resistance and the like, it can provide a COA-type liquid crystal display device with high resolution and excellent long-term durability. Furthermore, in order to meet the required characteristics of low dielectric constant, a resin film may be provided on the color filter layer.

Regarding these image display methods, for example, "Electroluminescence (EL), Plasma Display Panel (PDP), LCD display-the latest trends in technology and market-(Toray Research Center) Center) Research and Research Department (issued in 2001)" on page 43 and so on.

In addition to the color filter of the present invention, the liquid crystal display device of the present invention also includes various components such as electrode substrates, polarizing films, retardation films, backlights, spacers, and viewing angle protection films. The color filter of the present invention can be applied to include these In the liquid crystal display device of a well-known member. Regarding these components, for example, "'94 Liquid Crystal Display Peripheral Materials. Chemical Market (Issued by Shima Kentaro CMC Co., Ltd. in 1994)", "2003 Liquid Crystal Related Market Status and Future Prospects (Volume 2)" (Table Ryoshi Fuji It is recorded in "Fuji Chimera Research Institute (shares), issued in 2003)".

Regarding the backlight, please refer to the "SID (The Society for Information Display) meeting Digest" page 1380 (2005) (A. Konno et al.), and "Monthly Display" )" December 2005 issue from pages 18 to 24 (Yasuhiro Shima), "Monitor Monthly" December 2005 issue from pages 25 to 30 (Yagi Takaaki) and so on.

[Example]

Hereinafter, the present invention will be explained more specifically with examples, but the present invention is not limited to the following examples as long as it does not exceed the gist. In addition, as long as there is no special explanation in advance, "parts" and "%" are the quality standards.

<Synthesis Example 1: Synthesis of Resin (E-1)>

Under a nitrogen stream, 23 g of 1-methoxy-2-propanol was heated to 80°C. Then, 10g of 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 10g of allyl methacrylate, 2,2'-azobis(methyl isobutyrate) were added dropwise over 3 hours. Ester) A mixed solution of 2.0 g and 23 g of 1-methoxy-2-propanol was further heated in an environment of 90°C for 2 hours after stirring for 2 hours. After being left to cool, it was added dropwise to a mixed solution of 100 mL of methanol and 200 mL of ion-exchange water, and the obtained solid was collected. 18.6 g of resin (E-1) was obtained by drying this solid under a reduced pressure and an environment of 50°C for 24 hours. Resin (E-1) The weight average molecular weight (Mw) is 11,000.

<Synthesis example 2~Synthesis example 7: Synthesis of resin (E-2)~resin (E-7)>

Resin (E-2) to resin (E-7) were obtained by performing the same operation 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. Then, 10 g of 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 3.8 g of methacrylic acid, and 2,2'-azobis(methyl isobutyrate) were added dropwise over 3 hours A mixed solution of 1.5 g and 23 g of 1-methoxy-2-propanol was further heated for 2 hours in an environment of 90° C. after stirring 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 heating was performed in an air atmosphere at 100°C for 24 hours. It was confirmed by the acid value measurement that the acid group had disappeared. After being left to cool, it was added dropwise to a mixed solution of 100 mL of methanol and 200 mL of ion-exchange water, and the obtained solid was collected. The resin (E-8) was obtained by drying the solid under a reduced pressure at 50°C for 24 hours, and 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. Then, 10 g of 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 4.6 g of 2-hydroxyethyl methacrylate, 2,2'-azobis(isopropyl methacrylate) were added dropwise over 3 hours. A mixed solution of 1.0 g of methyl butyrate and 23 g of 1-methoxy-2-propanol was further heated for 2 hours in an environment of 90°C after stirring for 2 hours. Then, 0.1 g of Neostann U-600 (Nitto Chemicals Co., Ltd.), 5.7 g of ethyl 2-isocyanate methacrylate, and 0.05 g of p-methoxyphenol were added, and the mixture was placed at 80°C under a nitrogen atmosphere. It is heated for 24 hours under the environment. The disappearance of isocyanate groups was confirmed by nuclear magnetic resonance (NMR) measurement. After being left to cool, it was added dropwise to a mixed solution of 100 mL of methanol and 200 mL of ion-exchanged water, and the obtained solid was collected to obtain 17.9 g of resin (E-9). The weight average molecular weight (Mw) of the resin (E-9) was 16,000.

[化102]

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

<Preparation of Pigment Dispersion>

According to the following table 2, using a bead mill (zirconia beads, 0.3mm in diameter), 60 parts of propylene glycol monomethyl ether acetate solution (solid) containing 40 parts of pigment, 5 parts of pigment derivative, and polymer dispersant Converted to 18 parts) and 300 parts of propylene glycol monomethyl ether acetate mixed solution for 3 hours. Disperse to prepare a pigment dispersion.

In addition, when two types of pigments are used in combination, the mass ratio is set to 70/30.

In addition, as the pigment derivative, the following pigment derivative A was used, and as the polymer dispersant, the following polymer dispersant A was used.

[化104]

In addition, PR254, PG36, PG58, PY139, PB15: 6, PV23 in the following Table 2 respectively represent CI Pigment Red 254, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Yellow 139, CI Pigment Blue 15: 6 , CI Pigment Violet 23.

In addition, as titanium black, 13M-T manufactured by Mitsubishi Materials Corporation was used, and as carbon black, Nipex 35 manufactured by Degussa was used.

<Composition of resist solution for primer layer>

The components of the following composition are mixed and dissolved to prepare a resist solution for undercoat layer.

<Production of silicon wafer substrate with primer>

Heat a 6-inch silicon wafer in an oven at 200°C for 30 minutes. Then, the resist solution for the primer layer was coated on the silicon wafer so that the dry film thickness became 1.5 μm, and then heated and dried in an oven at 220°C for 1 hour to form the primer layer, thereby obtaining Silicon wafer substrate with primer.

<Preparation of colored radiation-sensitive composition (compositions of Examples 1 to 20, and Comparative Example 1)>

The following components were mixed, dispersed and dissolved, and filtered using a 0.45 μm nylon filter, thereby obtaining the respective compositions of Examples 1 to 20 and Comparative Example 1.

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, the following (I-4) is DAROCUR (registered trademark)-TPO (all the above are made by BASF).

[化106]

[化107]

<Synthesis of Dye (A)>

Synthesized by the method described in Japanese Patent Laid-Open No. 2014-199436 Dye (A) represented by the following formula.

Acid value=1.01mmol/g

a/b/c/d=36/12/32/20(mol%)

n=2

Mw=13,000

<Synthesis of Dye (B)>

First, the compound represented by the following formula (b) was synthesized in accordance with Synthesis Example 1 of JP 2000-162429 A. Then, 6.0 g (10 mmol) of the compound represented by the following formula (b) was added to 50 mL of dichloromethane and 10 mL of water, and stirred. Then, 3.19 g (10 mmol) of potassium=bis(trifluoromethanesulfonyl)imidine was added, and the mixture was stirred for 2 hours. After that, the water layer was removed, and the methylene chloride layer was concentrated to obtain 8.2 g of the dye (B) represented by the following formula (B).

[化111]

<Production of colored layer (coloring pattern)>

The compositions of the above-prepared examples and comparative examples were coated on the primer layer of the silicon wafer substrate with primer layer prepared before to form a color-sensitive radiation composition layer. Then, using a hot plate at 100° C., heat treatment (pre-baking) was performed for 120 seconds so that the dry film thickness of the colored radiation-sensitive composition layer became 0.6 μm.

Then, using the i-ray stepping exposure device FPA-3000i5+ (manufactured by Canon), at a wavelength of 365nm, the transmission pattern is a square island pattern mask with a 1.0μm side on each side, with a 50mJ/cm ² Exposure at various exposure levels of ~1200mJ/cm ² .

After that, the silicon wafer substrate on which the exposed color-sensitive radiation composition layer is formed is placed on the rotation. On the horizontal rotating table of a spray developing machine (Model DW-30, manufactured by Chemitronics), the organic solvent described in Table 2 below was used to perform liquid-covering development at 23°C for 60 seconds. In addition, when no organic solvent is used for processing (development), enter it in the organic solvent item in Table 2 below Set as "-" (the same below). Then, CD-2000 (manufactured by Fujifilm Electronic Materials) was used for 60 seconds of liquid coating and development at 23°C to form a colored pattern on the silicon wafer substrate.

The silicon wafer with the colored pattern is fixed on the horizontal rotating table by a vacuum chuck method, and the silicon wafer substrate is rotated at a speed of 50 rpm by a rotating device, and from above the center of rotation , Pure water is supplied in a spray form from a spray nozzle to perform a rinsing treatment, and then spray drying is performed.

In the above manner, a monochromatic color filter having a coloring pattern formed by the coloring radiation composition of the embodiment or the comparative example is produced.

After that, a length measuring SEM (scanning electron microscope) "S-9260A" (manufactured by Hitachi High-Technologies) was used to measure the size of the colored pattern. The exposure amount at which the pattern size becomes 1.0 μm is set as the optimal exposure amount.

<evaluation>

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

(Residue)

Using a scanning electron microscope (SEM) (magnification: 10000 times), 20 locations outside the formation area (unexposed portion) of the colored pattern were observed, and the residue was counted. The smaller the number of residues, the better, indicating that the developability is better.

(Pattern linearity)

Using a scanning electron microscope (magnification: 10000 times), 20 locations of the colored pattern were observed, and the linearity of the pattern was evaluated based on the following criteria. If it is A or B, it can be evaluated The deterioration of the linearity of the pattern caused by the generation of residues is suppressed.

A: A pattern with a line width of 1.0 μm is formed with good linearity.

B: A void was observed in a pattern with a line width of 1.0 μm, but it was at a level with no practical problems.

C: A void is observed in a pattern with a line width of 1.0 μm, and the linearity is poor.

(Surface roughness)

In the same manner as described above, apply the primer layer on the primer layer of the silicon wafer with the primer layer to form a color-sensitive radiation composition layer with a dry film thickness of 1 μm, and then apply 200 mJ/cm ² to the entire surface of the substrate. (Illumination is 20mW/cm ² ) for exposure.

After that, the silicon wafer substrate on which the exposed color-sensitive radiation composition layer is formed is placed on the rotation. On the horizontal rotating table of the spray developing machine (Model DW-30, manufactured by Kewei High Electronics), the organic solvent described in Table 2 was used for 60 seconds of liquid coating development at 23°C. Then, a CD-2000 (manufactured by Fujifilm Electronic Materials) was used for 60 seconds of liquid coating development in an environment of 23°C, and thereafter, it was dried for 5 minutes in an environment of 200°C. Using an Atomic Force Microscope (AFM) (manufactured by Digital Instruments, Nano Scope), the surface roughness (Ra) of the obtained colored layer was measured under the following conditions (unit: nm). The smaller the value of the surface roughness Ra of the colored layer, the more it can be evaluated that the generation of residue is suppressed.

-Measurement conditions-

. Measuring area: 10μm square

. Scan Rate: 1Hz

(defect)

Regarding the substrate on which the coloring layer whose surface roughness has been measured is formed, a defect evaluation device ComPLUS (manufactured by Applied Materials) was used to count foreign objects with a size of 2.0 μm or more. The smaller the value, the more it can be evaluated that the generation of residue is suppressed.

(Heat resistance)

On a glass substrate, the obtained colored radiation-sensitive composition is coated so that the dry film thickness becomes 0.6 μm, and the surface of the substrate (the surface on the side where the colored radiation-sensitive composition is not coated ) Placed on a hot plate at 260°C and heated for 1 hour in a contacting manner, and then measured the color difference (△E*ab value) before and after heating with a colorimeter MCPD-1000 (manufactured by Otsuka Electronics) to evaluate the heat resistance . Regarding the ΔE*ab value, a smaller value indicates good heat resistance.

(Reflectivity)

For the substrate with the coloring layer whose surface roughness has been measured, the incident angle is set to 5 degrees and the light is incident from 400nm to 700nm, and the reflectance (unit: %) is measured by the UV4100 spectroscope manufactured by Hitachi Advanced Technology. The smaller the reflectance value, the more it can be evaluated that the low reflectance of the colored layer is achieved.

[Table 2]

As is clear from the results shown in Table 2 above, it can be seen that the residues of Examples 1 to 20 that were treated with an organic solvent were generated in comparison with Comparative Example 1 where the treatment with an organic solvent was not performed. It was suppressed.

In addition, when comparing Examples 1 to 20, compared to Example 6, Example 7, Example 12, and Example 13 using ethylene glycol or decane as the organic solvent, PGMEA and cyclohexane are used. Example 1 to Example 5, Example 8 to Example 11, and Example 14 in which ketone, cyclopentanone, 1-methoxy-2-propanol, methyl ethyl ketone, or butyl acetate are used as organic solvents ~The generation of residue in Example 20 was further suppressed.

In addition, when comparing Examples 1 to 20, the colored layers of Examples 9 to 20 using Resin E are reduced in reflectance compared to Examples 1 to 8 where resin E is not used. .

In addition, if comparing Example 9 to Example 20, compared to Example 10 to Example 12 using resin (E-2) to resin (E-4) as resin E, other resin E is used The embodiment of is further low-reflective, especially the resin (E-8), resin (E-9) or the embodiment 16-20 of the Megafac RS-72-K is further low-reflective.

(Example 18-1)

The development was performed in the same manner as in Example 18, except that the order of organic development and alkaline development using CD-2000 was changed. As a result, the development speed was slightly slow, but by setting the coating time to 90 seconds, the degree of residue equivalent to that of Example 18 was achieved.

(Example 18-2)

In addition to changing the organic solvent used in the development process from 1-methoxy-2-propanol to a mixed solvent of 1-methoxy-2-propanol and cyclohexanone (the mass ratio is 1:1), and Example 18 was evaluated in the same manner, and as a result, an evaluation result equivalent to that of Example 18 was obtained.

(Comparative example 2)

The 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 was 100 or more, the pattern linearity was C, the surface roughness was 50 nm or more, the defects were 2000 or more, the heat resistance was 4.0, and the reflectance was 15%.

Claims (4)

A method for manufacturing a coloring layer, comprising: forming a coloring radiation composition layer using a coloring radiation composition containing a colorant A, a polymerizable compound B, an alkali-soluble resin C, and a photopolymerization initiator D a; Step b of exposing the colored radiation-sensitive composition layer into a pattern through a mask; and step c of processing the exposed colored radiation-sensitive composition layer to form a colored layer, The step c is a step of implementing any one of step c1 of processing using a developer containing 50% by mass or more of an organic solvent, and step c2 of developing using an alkaline aqueous solution, and then implementing another step. The method for manufacturing a coloring layer as described in the first item of the scope of patent application, wherein the developer contains 95% by mass or more of an organic solvent. The method for producing a colored layer as described in item 1 or item 2 of the scope of patent application, 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 the 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 as described in item 3 of the scope of patent application, wherein the resin E further has a group represented by the following general formula (2), *-X ₂ -Z...(2) general formula (2) ), X ₂ represents a single bond or a divalent linking group; Z represents a group selected from (meth)acrylic, allyl, vinyl, oxetanyl, epoxy, and hydroxymethylamino groups At least one group in the group; * indicates the bonding position.