WO2014192716A1

WO2014192716A1 - Method for producing color filter, composition for forming base layer, and organic el display device

Info

Publication number: WO2014192716A1
Application number: PCT/JP2014/063909
Authority: WO
Inventors: 薫青柳; 秀知高橋; 誠一人見
Original assignee: 富士フイルム株式会社
Priority date: 2013-05-27
Filing date: 2014-05-27
Publication date: 2014-12-04
Also published as: TW201512709A; JP2015007766A; KR20150143679A

Abstract

The purpose of the present invention is to provide: a method for producing a color filter, wherein adhesion of a coloring layer formed therein is excellent and generation of a residue during the formation of the coloring layer is suppressed; a composition for forming a base layer; and an organic EL display device. A method for producing a color filter according to the present invention comprises: a base layer formation step wherein a base layer that has a refractive index of 1.60 or more at a wavelength of 633 nm is formed on a supporting body; and a coloring layer formation step wherein a coloring layer is formed on the base layer with use of a coloring radiation-sensitive composition that contains (A) a coloring agent, (B) a polymerization initiator and (C) a polymerizable compound.

Description

Method for producing color filter, composition for forming underlayer, organic EL display device

The present invention relates to a method for manufacturing a color filter, and more particularly to a method for manufacturing a color filter using an underlayer having a predetermined refractive index.

The color filter is an indispensable component for the display of a solid-state image sensor or a liquid crystal display device. In order to form such a color filter, a colored radiation-sensitive composition is mainly used (Patent Document 1). Patent Document 1 discloses a mode in which CT-2010 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) is used as a base layer (undercoat layer) of the colored layer.

JP 2012-198408 A

On the other hand, in recent years, with the miniaturization of the colored layer, further improvement in the adhesion of the colored layer is required. At the same time, there is a demand for further suppression of the generation of residues during the development process when forming the colored layer.
The inventors of the present invention have manufactured a color filter using the underlayer described in Patent Document 1, satisfying both the adhesion of the colored layer and the suppression of residues at the level required at the same time. It was found that further improvement is necessary.

In view of the above circumstances, an object of the present invention is to provide a method for producing a color filter that is excellent in adhesion of a colored layer to be formed and in which generation of a residue during formation of the colored layer is suppressed.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using an underlayer having a predetermined refractive index, and have completed the present invention.
That is, the present inventors have found that the above problem can be solved by the following configuration.
(1) an underlayer forming step of forming an underlayer having a refractive index of 1.60 or more at a wavelength of 633 nm on a support;
Colored layer formation which forms a colored layer on a base layer using a colored radiation-sensitive composition containing (A) a colorant (preferably a pigment), (B) a polymerization initiator, and (C) a polymerizable compound. Process,
A method for producing a color filter, comprising:
(2) The method for producing a color filter according to (1), wherein the colorant is a pigment, and the content of the pigment is 45% by mass or more based on the total mass of the colored radiation-sensitive composition.
(3) The manufacturing method of the color filter as described in (1) or (2) in which a base layer contains the organic compound whose refractive index in wavelength 633nm is 1.60 or more.
(4) The method for producing a color filter according to any one of (1) to (3), wherein the underlayer contains a triazine ring-containing polymer.
(5) The production of the color filter according to (4), wherein the triazine ring-containing polymer contains at least one selected from the group consisting of repeating units represented by formulas (1A) to (4A) described later. Method.
(6) The method for producing a color filter according to (4) or (5), wherein the content of the triazine ring-containing polymer in the underlayer is 40% by mass or more based on the total mass of the underlayer.
(7) The method for producing a color filter according to any one of (4) to (6), wherein the triazine ring-containing polymer has a weight average molecular weight of 1,000 to 100,000.
(8) The method for producing a color filter according to any one of (1) to (7), wherein the base layer is substantially free of metal particles or metal oxide particles.
(9) An underlayer forming composition used for forming an underlayer of a colored layer contained in a color filter, the underlayer forming composition containing a triazine ring-containing polymer.
(10) The composition for forming an underlayer according to (9), further comprising a compound having a fluorene structure as a high-refractive-index low-molecular compound.
(11) The composition for forming an underlayer according to (9) or (10), further comprising NaCl.
(12) An organic EL display device having an organic EL element, a base layer, and a colored layer,
An organic EL display device, wherein the underlayer is an underlayer having a refractive index of 1.60 or more at a wavelength of 633 nm.

According to the present invention, it is possible to provide a method for producing a color filter that is excellent in the adhesion of the formed colored layer and that suppresses the generation of residues when the colored layer is formed.

It is a partial sectional view of one mode of an organic EL display of the present invention.

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

A feature of the method for producing a color filter of the present invention is that an underlayer having a predetermined refractive index is used. When this base layer is used, irregular reflection at the time of exposure when forming the colored layer is reduced, the residue of the unexposed portion due to leaked light is reduced, and the adhesion of the colored layer is also improved.
In particular, when the underlayer contains a triazine ring-containing polymer as described later, the triazine skeleton has a planar structure, so the benzene ring structure in the colored layer and the planar structure in the colorant interact with each other. It is easy and the adhesion of the colored layer is further improved.

The method for producing a color filter of the present invention includes at least a base layer forming step and a colored layer forming step.
Hereinafter, materials and procedures used in each step will be described in detail.

<Underlayer formation process>
The base layer forming step is a base layer forming step of forming a base layer having a refractive index of 1.60 or more at a wavelength of 633 nm on the support.
First, the support used in this step is described in detail, and then the underlayer is described in detail.

(Support)
The type of the support is not particularly limited as long as it is a base material that can support the base layer. For example, a photoelectric conversion element substrate (a substrate for a solid-state imaging element) (for example, a silicon substrate, an oxide film, silicon nitride, or the like) used for a solid-state imaging element or the like can be given. Further, other layers such as an intermediate layer may be provided between the support and the colored layer described later as long as the effects of the present invention are not impaired.
In addition, the coloring layer to be described later may be formed on the imaging element formation surface side (front surface) of the solid-state imaging element substrate, or may be formed on the imaging element non-formation surface side (back surface).
A light-shielding film may be provided between the image sensors on the solid-state image sensor substrate or on the back surface of the solid-state image sensor substrate.

(Underlayer)
The base layer has a refractive index of 1.60 or more at a wavelength of 633 nm, and the adhesion of the colored layer is further improved, or the generation of residue is further suppressed (hereinafter simply referred to as “the effect of the present invention is more excellent. 1.65 or more is preferable, and 1.70 or more is more preferable. The upper limit is not particularly limited, but is usually 2.0 or less in many cases.
The refractive index can be measured using an ellipsometer manufactured by JA Woollam Japan. The measurement conditions are 633 nm, 25 ° C., and an average value of 5 points is adopted.

The thickness of the undercoat layer is not particularly limited, but is preferably 0.2 to 1.0 μm and more preferably 0.2 to 0.4 μm from the viewpoint that the effects of the present invention are more excellent.

The component contained in the underlayer is not particularly limited as long as it is a material exhibiting the above-described refractive index, but an organic compound having a refractive index of 1.60 or more at a wavelength of 633 nm is preferable, and contains a triazine ring, because the effects of the present invention are more excellent. Polymers are preferred.
In addition, it is preferable that a metal particle or a metal oxide particle is not substantially contained in a base layer at the point which the effect of this invention is more excellent. “Not substantially contained” means that the total content of metal particles and metal oxide particles in the underlayer is 0.01% by mass or less, and preferably 100 ppm or less. By substantially not including metal particles or metal oxide particles, the surface flatness of the underlayer is further improved, and as a result, the adhesion with the colored layer disposed on the underlayer is further improved.
Hereinafter, the triazine ring-containing polymer will be described in detail.

(Triazine ring-containing polymer (hereinafter also simply referred to as polymer))
The triazine ring-containing polymer is a polymer containing a triazine ring in its structure, and is selected from the group consisting of repeating units represented by the following formulas (1A) to (4A) in that the effect of the present invention is more excellent. A triazine ring-containing polymer having at least one of the above is preferable. In the formula, * indicates a bonding position.
In the triazine ring-containing polymer, the total content of the repeating units represented by the formulas (1A) to (4A) is not particularly limited, but in the triazine ring-containing polymer, the effect of the present invention is more excellent. The total repeating unit is preferably 50 to 100 mol%, more preferably 80 to 100 mol%.

In the above formula (1A) or formula (2A), R ^1A and R ^2A each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group.
R ^3A represents an alkyl group, an aralkyl group, an aryl group, an alkylamino group, an alkoxysilyl group-containing alkylamino group, an aralkylamino group, an arylamino group, an alkoxy group, an aralkyloxy group, or an aryloxy group.

The number of carbon atoms in the alkyl group is preferably 1-20, and in view of further improving the heat resistance of the polymer, the number of carbons is more preferably 1-10, and even more preferably 1-3. Further, the structure may be any of a chain, a branch, and a ring.
The number of carbon atoms in the alkoxy group is preferably 1 to 20, and more preferably 1 to 10 carbon atoms, and still more preferably 1 to 3 carbon atoms in consideration of further improving the heat resistance of the polymer. Further, the structure of the alkyl moiety may be any of a chain, a branch, and a ring.
The number of carbon atoms in the aryl group is preferably 6 to 40. In view of further improving the heat resistance of the polymer, the number of carbon atoms is more preferably 6 to 16, and more preferably 6 to 13.
The aralkyl group preferably has 7 to 20 carbon atoms, and the alkyl moiety may be linear, branched or cyclic.
As specific examples of the alkyl group, alkoxy group, aryl group, aralkyl group, alkylamino group, aralkylamino group, and arylamino group, the description in paragraphs 0020 to 0025 of WO 2010/128661 can be referred to, and the contents thereof are described in this application. Incorporated in the description.

The alkoxysilyl group-containing alkylamino group may be any of monoalkoxysilyl group-containing alkylamino group, dialkoxysilyl group-containing alkylamino group, trialkoxysilyl group-containing alkylamino group, and specific examples thereof include WO2010 / 128661. And the groups described in paragraph 0026 of the No.
Specific examples of the aryloxy group and the aralkyloxy group include the groups described in paragraph 0027 of WO2010 / 128661.

Ar represents a divalent organic group containing one or both of an aromatic ring and a heterocyclic ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring. The heterocyclic ring includes pyridine ring, pyrazole ring, triazole ring, thiazole ring, isothiazole ring, oxazole ring, thiadiazole ring, pyrrole ring, isoxazole ring, thiophene ring, quinoline ring, isoquinoline ring, pyridazine ring, pyrimidine ring. Etc. Ar represents a divalent aliphatic hydrocarbon group (preferably having a carbon number of 1 to 8), —O—, —S—, —SO ₂ —, —N (R) — (in addition to an aromatic ring and a heterocyclic ring. R: an alkyl group), —CO—, —NH—, —COO—, —CONH—, or a combination thereof (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, etc.) Also good.
Among these, as Ar, groups represented by formulas (3) to (19) are preferable. In particular, groups represented by formulas (6) to (19) are preferred, and groups represented by formulas (6), (8), (9), (12), (13) and (15) to (19) are preferred. More preferred.

R ¹ to R ¹²⁸ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. An alkoxy group which may have a branched structure is represented.
W ¹ , W ² and W ³ are each independently a single bond, CR ¹³⁰ R ¹³¹ (R ¹³⁰ and R ¹³¹ are each independently a hydrogen atom or a branched structure having 1 to 10 carbon atoms. An alkyl group (which may be combined together to form a ring), —C (═O) —, —O—, —S—, —SO—, — SO ₂ — or —NR ¹²⁹ — (R ¹²⁹ represents a hydrogen atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms).
Examples of these alkyl groups and alkoxy groups are the same as those described above.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
X ¹ and X ² each independently represent a single bond, an alkylene group which may have a branched structure having 1 to 10 carbon atoms, or a group represented by the formula (20).

R ¹³² to R ¹³⁵ are independently of each other a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. An alkoxy group which may have a branched structure is represented.
Y ¹ and Y ² each independently represent an alkylene group which may have a single bond or a branched structure having 1 to 10 carbon atoms.
Examples of the halogen atom, alkyl group and alkoxy group are the same as those described above.
Examples of the alkylene group that may have a branched structure having 1 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group.

Suitable Ar includes a divalent organic group containing a fluorene ring. For example, a divalent organic group represented by the following formula (21) or (22) is preferable.

In the formula, R ¹³⁶ to R ¹⁵⁹ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, or an alkyl group which may have a branched structure having 1 to 10 carbon atoms (provided that R ¹⁵⁸ and R ¹⁵⁹ may ^combine together to form a ring.), Or represents an alkoxy group which may have a branched structure having 1 to 10 carbon atoms.
Here, as a halogen atom, the same thing as the above is mentioned.
Examples of the alkyl group which may have a branched structure having 1 to 10 carbon atoms include the same ones as described above.
Examples of the ring formed by R ¹⁵⁸ and R ¹⁵⁹ together include a cyclopentyl ring and a cyclohexyl ring.
Examples of the alkoxy group which may have a branched structure having 1 to 10 carbon atoms include the same groups as described above.
Among these, R ¹³⁶ to R ¹⁵⁹ are preferably hydrogen atoms.

Specific examples of the groups represented by the above formulas (3) to (19), (21) and (22) include those represented by the following formula, but are not limited thereto.

Among these, a group represented by the following formula is more preferable because a polymer having a higher refractive index can be obtained.

Furthermore, from the standpoint of developing a high refractive index, a rigid structure having a cyclic skeleton such as a fluorene skeleton or a carbazole skeleton is preferable as the Ar portion because the Ar portion tends to gather closely and the electron density is improved. In addition, since a simple benzene ring also has a small structure, it is preferable because Ar portions are easily gathered densely and the electron density is improved.
In addition, as a linking group of a benzene ring such as W ¹ , a functional group such as a carbonyl-containing group or an amine having a high hydrogen bonding ability is a hydrogen atom at the amine site (R ^1A and / or R ^2A is a hydrogen atom). In this case, a hydrogen bond is formed, and the Ar portion is more likely to gather more densely, which is preferable because the electron density is improved.
From the above viewpoints, a group represented by the following formula is preferable.

An aryl group represented by the following formula is more preferable from the viewpoint of expressing a higher refractive index.

Suitable repeating unit structures include, but are not limited to, those represented by the following formula (23) or (24).

Further, when the polymer is a hyperbranched polymer, it is preferable to include a repeating unit structure represented by the formula (25) in consideration of further increasing the solubility of the polymer in a highly safe solvent such as a resist solvent. .

In the formula, R ^1A , R ^2A , and R ⁷⁷ to R ⁸⁰ represent the same meaning as described above.
From such a viewpoint, as a particularly preferable repeating unit structure, one represented by the following formula (26) is exemplified, and a hyperbranched polymer (hyperbranched polymer) represented by the following formula (27) is optimal.

In the formula, R ^1A and R ^2A represent the same meaning as described above.

The production method of the triazine ring-containing polymer having a repeating unit represented by the above formula (1A) or (2A) is not particularly limited, and examples thereof include the methods described in paragraphs 0051 to 0069 of WO2010 / 128661.
Next, Formula (3A) will be described.

Ar in the formula (3A) is not particularly limited as long as it is a divalent organic group containing one or both of an aromatic ring and a heterocyclic ring, but in the present invention, the above formula (3) to Any of the groups represented by (19) is preferred, and any of the groups represented by formulas (10), (11), (13) and (14) is particularly preferred.
In the case of the formulas (10) and (11), those in which W ¹ and W ² are S (sulfur atom) are preferable.
Specific examples of the groups represented by the above formulas (3) to (19) include those represented by the following formula, but are not limited thereto.

Among these, an aryl group represented by the following formula is more preferable because a polymer having a higher refractive index can be obtained.

Furthermore, an aryl group represented by the following formula is more preferable from the viewpoint of expressing a higher refractive index.

Suitable examples of the repeating unit structure include those represented by the following formula, but are not limited thereto.

The production method of the triazine ring-containing polymer (hyperbranched polymer) having a repeating unit represented by the above formula (3A) is not particularly limited, and examples thereof include the methods described in paragraphs 0036 to 0048 of JP2012-97175A. It is done.
Next, Formula (4A) will be described.

In the above formula (4A), R ^4A to R ^9A each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a phenyl group optionally substituted with W. Or a naphthyl group optionally substituted by W.
Y ¹ and Y ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
Z ¹ and Z ² each independently represent an alkylene group having 1 to 10 carbon atoms or a phenylene group optionally substituted with W.
W represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxy group, and n represents 0 or an integer of 1 or more.
The alkyl group has 1 to 10 carbon atoms, but in view of further improving the heat resistance of the polymer, the carbon number is preferably 1 to 5, and more preferably 1 to 3.

The alkoxy group has 1 to 10 carbon atoms, but in view of further improving the heat resistance of the polymer, 1 to 5 carbon atoms are more preferable, and 1 to 3 carbon atoms are even more preferable. Further, the structure of the alkyl moiety may be any of a chain, a branch, and a ring.
The structure of the alkyl group or alkoxy group is not particularly limited, and the description of the alkyl group described in paragraphs 0019 and 0020 of JP2012-097176 can be referred to, and the contents thereof are incorporated in the present specification.

Specific examples of the phenyl group which may be substituted with W include a phenyl group, o-hydroxyphenyl group, m-hydroxyphenyl group, p-hydroxyphenyl group, o-methoxyphenyl group, m-methoxyphenyl group, p -Methoxyphenyl group, o-tolyl group, m-tolyl group, p-tolyl group and the like.
Specific examples of the naphthyl group which may be substituted with W include α-naphthyl group, β-naphthyl group and the like.

The alkylene group has 1 to 10 carbon atoms, but in view of further improving the heat resistance of the polymer, it is more preferably 1 to 5 carbon atoms, and still more preferably 1 to 3 carbon atoms. Further, the structure may be any of a chain, a branch, and a ring.
Specific examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, and a pentamethylene group.

Specific examples of the phenylene group that may be substituted with W include p-phenylene group, m-phenylene group, o-phenylene group, and at least one hydrogen atom of these phenylene groups is substituted with W, And those substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a hydroxy group.

In the above formula (4A), R ^4A to R ^9A are preferably alkyl groups having 1 to 5 carbon atoms, more preferably alkyl groups having 1 to 3 carbon atoms, and most preferably a methyl group.
Y ¹ and Y ² are preferably hydrogen atoms.
Z ¹ and Z ² are preferably an alkylene group having 1 to 5 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms.
n is not particularly limited as long as it is 0 or an integer of 1 or more, but is preferably 0 or an integer of 1 to 8.
Suitable repeating unit structures in the present invention include, but are not limited to, those represented by the following formulas.
In the formula, n is the same as described above.

The production method of the triazine ring-containing polymer having a repeating unit represented by the above formula (4A) is not particularly limited, and examples thereof include the methods described in paragraphs 0028 to 0044 of JP2012-97176A.

The triazine ring-containing polymer contained in the undercoat layer is also preferably a polymer obtained by curing a polymerizable monomer containing at least a polymerizable monomer represented by the following formula (10A).

In the formula (10A), one or two of X ⁴ to X ⁶ are the formula (11A) or the formula (12A) (in the formula (11A), R ¹⁴² is a hydrogen atom, an alkyl having 1 to 10 carbon atoms. Or the remainder of X ⁴ to X ⁶ is the group represented by formula (13A) or formula (14A) (in formula (13A), R ¹⁴³ and R ¹⁴⁴ each independently represent a phenyl group or a naphthyl group.

The weight average molecular weight of the polymer is not particularly limited, but is preferably 500 to 500,000, more preferably 1000 to 100,000, from the viewpoint of further improving heat resistance and reducing the shrinkage rate. It is preferably 2,000 or more, preferably 50,000 or less, more preferably 30,000 or less, and even more preferably 10,000 or less from the viewpoint of further increasing the solubility and decreasing the viscosity of the obtained solution.
In addition, the weight average molecular weight in this invention is an average molecular weight obtained by standard polystyrene conversion by gel permeation chromatography (henceforth GPC) analysis.
In the present invention, a commercially available high refractive index resin can be suitably used. The product names (product numbers) are listed below.
(1) Ultra-high refractive index, high heat-resistant coating material: UR-108, UR-202, UR-501, HR-102 (manufactured by Nissan Chemical Industries)
(2) High refractive index coating material for thick film: UR-108, UR-204, HR-201 (manufactured by Nissan Chemical Industries)
(3) Thioepoxy resin LPH1101 (Mitsubishi Gas Chemical Co., Ltd.)
(4) Episulfide resin MR-174 (Mitsui Chemicals)
(5) Thiourethane resin MR-7 (Mitsui Chemicals)

The content of the polymer in the underlayer is not particularly limited, but is preferably 40% by mass or more, and more preferably 70 to 95% by mass with respect to the total mass of the underlayer in terms of more excellent effects of the present invention.
In addition, other components (for example, surfactant, adhesion improving agent, etc.) other than the polymer may be contained in the underlayer. Examples of the surfactant and the adhesion improver include those described in the surfactant and adhesion improver contained in the colored radiation-sensitive composition described later.

The underlayer may further contain a high refractive index low molecular compound. The high refractive index low molecular compound may be a low molecular compound (high refractive index low molecular compound) having a structure that expresses a high refractive index, and may contain a polymerizable group. That is, the high-refractive-index low-molecular compound may be a “polymerizable monomer” (compound containing a polymerizable group) or a “low-molecular compound” (compound containing no polymerizable group), but is preferably a “low-molecular compound”. .
The molecular weight of the high refractive index low molecular compound is not particularly limited, but is preferably 3000 or less, more preferably 800 or less, and even more preferably 600 or less.
The high-refractive-index low-molecular compound also functions as a sensitivity adjusting agent in the underlayer-forming composition, and by optimizing the content, the yield can be improved in the film formation process. The content of the high refractive index low molecular compound is not particularly limited, but is preferably 10% by mass or less, more preferably 7% by mass or less, and particularly preferably 5% by mass or less based on the content of the triazine ring-containing polymer. By adding a small amount of a high-refractive-index low-molecular compound, the refractive index can be further increased as compared with the triazine ring-containing polymer alone.
The high-refractive-index low-molecular compound preferably has the same structure as the structure that expresses the high-refractive index of the triazine ring-containing polymer. Specific examples of the high refractive index and low molecular weight compound include a compound having a triazine ring structure (formula (A)) and a compound having a fluorene structure (formula (B)). In addition, the compound having a triazine ring structure and the compound having a fluorene structure may further contain a polymerizable group (for example, a radically polymerizable group (eg, (meth) acryloyl group or vinyl group)). .
Moreover, the said high refractive index low molecular weight compound may be contained in the composition for base layer formation mentioned later, and it is preferable that the content is the said range.

(Formation method of underlayer)
The formation method in particular of a base layer is not restrict | limited, A well-known method is employable. For example, a composition for forming an underlayer containing a material for forming an underlayer such as the polymer described above is applied onto a support, and a curing treatment (for example, a heat treatment and / or an exposure treatment) is performed as necessary. The method of implementation can be adopted.
The coating method is not particularly limited, and examples thereof include a spray method, a roll coating method, a spin coating method (spin coating method), and a bar coating method.
The underlayer-forming composition is preferably a transparent composition. More specifically, when an underlayer having a thickness of 1.0 μm is formed from the composition, light transmission in the thickness direction of the underlayer is achieved. It is preferable that the composition has a rate of 90% or more over the entire wavelength region of 400 to 700 nm.
That is, the base layer is preferably a film having a light transmittance of 90% or more over the entire wavelength region of 400 to 700 nm when the film thickness is 1.0 μm.
The light transmittance is preferably 95% or more, more preferably 99% or more, and most preferably 100% over the entire wavelength region of 400 to 700 nm.
It is preferable that the underlayer-forming composition does not substantially contain a colorant described later. More specifically, the content of the colorant is preferably 0% by mass with respect to the total solid content of the composition.
In addition, the underlayer forming composition may contain a crosslinking agent, a solvent, a surfactant, an adhesion improver, and the like, if necessary. Examples of each of the solvent, the surfactant, and the adhesion improver include those described in the solvent, surfactant, and adhesion improver contained in the colored radiation-sensitive composition described later.

In addition, as a crosslinking agent, if it is a compound which has a substituent which can react with the polymer mentioned above, it will not specifically limit.
Examples of such compounds include melamine compounds having a crosslinkable substituent such as a methylol group and methoxymethyl group, substituted urea compounds, compounds containing a crosslinkable substituent such as an epoxy group or an oxetane group, and blocked isocyanates. A compound containing acid, a compound having an acid anhydride, a compound having a (meth) acrylic group, a phenoplast compound, etc., from the viewpoint of heat resistance and storage stability, an epoxy group, a blocked isocyanate group, (meth) A compound having an acrylic group is preferred.

In addition, it is preferable that there is little content of salts, such as NaCl, in the composition for base layer formation, 100 mass ppm or less is preferable, and 50 mass ppm or less is more preferable. 1 mass ppm or more is preferable, and 5 mass ppm or more is more preferable. When the salt content is less than or equal to the predetermined value, the occurrence of film defects is further suppressed. Further, by adding a small amount of salt, it functions as a pattern shape adjusting agent, and it is easy to form a desired pattern when forming a pattern with photolithography. The salt content can be adjusted by filtration.

<Colored layer forming step>
In the colored layer forming step, a colored radiation-sensitive composition containing (A) a colorant (preferably a pigment), (B) a polymerization initiator, and (C) a polymerizable compound is formed on the base layer described above. It is the process of forming a colored layer using. The color of the colored layer is not particularly limited and can be appropriately adjusted depending on the type of the colorant used, and examples thereof include a red colored layer, a green colored layer, a blue colored layer, and the like. Also good.
Below, the colored radiation sensitive composition used at this process is explained in full detail first, and the procedure of the post process is explained in full detail.

(Colored radiation-sensitive composition (hereinafter also simply referred to as “composition” or “composition of the present invention”)
The colored radiation-sensitive composition contains at least (A) a colorant (preferably a pigment), (B) a polymerization initiator, and (C) a polymerizable compound.
First, each component will be described in detail.

((A) Colorant)
The type of the colorant is not particularly limited, and chromatic pigments (red, magenta, yellow, blue, cyan, green, etc.) or black pigments or dyes are used.
As the chromatic pigment, various conventionally known inorganic pigments or organic pigments can be used. Further, considering that it is preferable to have a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a finer one as much as possible, and considering the handling properties, the average primary particle diameter of the pigment is 0.01 μm. Is preferably 0.1 μm, more preferably 0.01 μm to 0.05 m.
Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, Mention may be made of metal oxides such as silver, and composite oxides of metals. Titanium nitrides, silver tin compounds, silver compounds, and the like can also be used.

Examples of the pigment that can be preferably used in the present invention include the following. However, the present invention is not limited to these.
C. I.

Pigment Yellow

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

C. I. Pigment Green 7, 10, 36, 37, 58
C. I. Pigment Violet 1,19,23,27,32,37,42
C. I. Pigment Blue Blue 1,2,15,15: 1,15: 2,15: 3,15: 4,15: 6,16,22,60,64,66,79,80
C. I. Pigment Black 1
These organic pigments can be used alone or in various combinations in order to increase color purity.

As described above, an inorganic pigment may be used as the pigment, and examples of the inorganic pigment include a metal pigment, a metal-containing inorganic pigment made of a metal compound or a metal oxide, and carbon black.
The composition may be used not only for the formation of colored regions (pixels) of a color filter, but also for the formation of a black matrix. Examples of black pigments used in a composition for forming a black matrix include carbon, titanium black, oxidation In addition to iron, titanium oxide, silver tin, silver, and the like, a pigment made of a metal mixture containing a metal oxide such as titanium oxide can be used. Examples of commercially available titanium black include, for example, Titanium Black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, Ako Kasei Co., Ltd., Tilac D, manufactured by Mitsubishi Materials Corporation. .

As the pigment, a pigment having an average particle diameter (r) satisfying 20 nm ≦ r ≦ 300 nm, preferably 125 nm ≦ r ≦ 250 nm, particularly preferably 30 nm ≦ r ≦ 200 nm is desirable. By using a pigment having such an average particle diameter, a pixel having a high contrast ratio and a high light transmittance can be obtained. Here, the “average particle size” means the average particle size of secondary particles in which primary particles (single crystallites) of the pigment are aggregated. The average primary particle diameter can be determined by observing with an SEM or TEM, measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating an average value.
The particle size distribution of the secondary particles of the pigment that can be used in the present invention (hereinafter, simply referred to as “particle size distribution”) is 70% by mass of secondary particles having an average particle size of ± 100 nm. As mentioned above, it is desirable that it is 80 mass% or more. In the present invention, the particle size distribution was measured using the scattering intensity distribution.
The pigment having the above average particle size and particle size distribution is preferably a commercially available pigment mixed with a dispersant and a solvent together with other pigments used (the average particle size is usually more than 300 nm). The pigment mixture can be prepared by mixing and dispersing while pulverizing using a pulverizer such as a bead mill or a roll mill. The pigment thus obtained is usually in the form of a pigment dispersion.

The content (concentration) of the pigment contained in the composition is preferably 40% by mass or more and more preferably 45% by mass or more in the total solid content of the composition in that the effect of the present invention is more excellent. Preferably, 50 mass% is more preferable. Although there is no restriction | limiting in particular about an upper limit, Preferably it is 75 mass% or less.
There is no restriction | limiting in particular as dye, A well-known dye can be selected suitably and can be used. For example, JP-A 64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, JP 2592207, US Pat. No. 4,808,501 Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-2111599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP-A-2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. No. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 The dyes described in JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like.
The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, A dye such as xanthene, phthalocyanine, benzopyran, or indigo can be used. These dyes may be multimers.

(Dispersant)
In the composition of the present invention, a dispersant is preferably added from the viewpoint of further improving the dispersibility of the pigment.
Dispersants (hereinafter sometimes referred to as “pigment dispersants”) include polymer dispersants (eg, polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, and modified polyesters). , Modified poly (meth) acrylates, (meth) acrylic copolymers, naphthalenesulfonic acid formalin condensates), polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, pigment derivatives, etc. Can do.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.
The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

Specific examples of pigment dispersants that can be used in the present invention include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide) manufactured by BYK Chemie. ), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), BYK2001 ”,“ EFKA 4047, 4050 ”manufactured by EFKA. 4010, 4165 (polyurethane series), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative) , 6750 (azo pigment derivative) ”,“ Ajisper PB821, PB822 ”manufactured by Ajinomoto Fine Techno Co.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co., Ltd.,“ Polyflow No. 50E, No. 300 (acrylic co-polymer). "Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725" manufactured by Enomoto Kasei Co., Ltd. "Demol RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)", "Homogenol L-18 (polymeric polycarboxylic acid)" ) "," Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ) ”,“ Acetamine 86 (stearylamine acetate) ”,“ Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (functional part at the terminal part) manufactured by Lubrizol. 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ”manufactured by Nikko Chemical Co., Ltd. Can be mentioned.
These dispersants may 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.

The content of the dispersant in the composition of the present invention is preferably 1 to 100% by mass, more preferably 3 to 100% by mass, and further preferably 5 to 80% by mass with respect to the pigment. Further, it is preferably 10 to 30% by mass with respect to the total solid content of the composition.

<Polymerization initiator>
The composition of the present invention contains a polymerization initiator. Only one type of polymerization initiator may be used, or two or more types may be used, and in the case of two or more types, the total amount falls within the following range. For example, the content of the polymerization initiator is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass, and more preferably 0.1 to 15% by mass with respect to the solid content of the composition of the present invention. Is more preferable. Within this range, good sensitivity and pattern formability can be obtained.
The polymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound by either or both of light and heat, and can be appropriately selected according to the purpose. It is preferable that When polymerization is initiated by light, those having photosensitivity to visible light from the ultraviolet region are preferred.
In addition, when the polymerization is initiated by heat, a polymerization initiator that decomposes at 150 to 250 ° C. is preferable.

The polymerization initiator that can be used in the present invention is preferably a compound having at least an aromatic group. For example, an acylphosphine compound, an acetophenone compound, an α-aminoketone compound, a benzophenone compound, a benzoin ether compound, a ketal derivative compound, a thioxanthone Compounds, oxime compounds, hexaarylbiimidazole compounds, trihalomethyl compounds, azo compounds, organic peroxides, diazonium compounds, iodonium compounds, sulfonium compounds, azinium compounds, benzoin ether compounds, ketal derivative compounds, metallocene compounds and other onium salt compounds , Organic boron salt compounds, disulfone compounds and the like.
From the viewpoint of sensitivity, oxime compounds, acetophenone compounds, α-aminoketone compounds, trihalomethyl compounds, hexaarylbiimidazole compounds, and thiol compounds are preferred.

Specific examples of acetophenone compounds, trihalomethyl compounds, hexaarylbiimidazole compounds, and oxime compounds include paragraphs 0506 to 0510 of JP2012-208494A (corresponding to [ 0622 to 0628]) and the like can be referred to, and the contents thereof are incorporated in the present specification.
The photopolymerization initiator is more preferably a compound selected from the group consisting of oxime compounds, acetophenone compounds, and acylphosphine compounds. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969, an acylphosphine oxide initiator described in Japanese Patent No. 4225898, and the oxime initiator described above, As the oxime initiator, the compounds described in JP-A No. 2001-233842 can also be used.
As the oxime-based initiator, commercially available products IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) can be used. As the acetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF Japan Ltd.) can be used. As the acylphosphine initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF Japan Ltd.) can be used.
As the oxime initiator (oxime polymerization initiator), the following formula (OX-1) of paragraph 0513 of JP2012-208494A (corresponding to [0632] of the corresponding US Patent Application Publication No. 2012/235099) ), (OX-2) or (OX-3) can be referred to, and the contents thereof are incorporated herein.
Examples of oxime initiators include TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD) Commercial products can also be used. In addition, the description of the polymerization initiator described in paragraphs 0092 to 0096 of JP2012-113104A can be referred to, and the contents thereof are incorporated in the present specification. By using such an oxime initiator, a resin composition having high curing sensitivity and good developability can be provided. The oxime initiator is a compound described in JP 2012-113104 A and after column 0030. The general formula is represented by the general formula (I) described in claim 1 of the method of JP 2012-113104 A, more preferably represented by the general formula (IA) described in claim 3. These descriptions can be referred to, and the contents thereof are incorporated in the present specification.

In the present invention, a sensitizer may be contained for the purpose of improving the radical generation efficiency of the polymerization initiator and increasing the photosensitive wavelength. As the sensitizer that can be used in the present invention, a sensitizer that sensitizes the polymerization initiator by an electron transfer mechanism or an energy transfer mechanism is preferable.
Examples of the sensitizer include compounds described in paragraph numbers 0101 to 0154 of JP-A-2008-32803.
When blended, the content of the sensitizer in the composition of the present invention is 0.1% by mass to 20% by mass in terms of solid content from the viewpoint of light absorption efficiency to the deep part and starting decomposition efficiency. Is preferable, and 0.5% by mass to 15% by mass is more preferable.
A sensitizer may be used individually by 1 type and may use 2 or more types together.

(Polymerizable compound)
The polymerizable compound may be a compound that is polymerized by the polymerization initiator, and a known polymerizable compound can be used.
Among these, from the viewpoint of polymerizability, an addition polymerizable compound having at least one ethylenically unsaturated double bond can also be used, and has at least one terminal ethylenically unsaturated bond, preferably two or more. Preference is given to using compounds.

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

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

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

Is preferred,

Is more preferable.
Specific examples of the radically polymerizable monomer represented by the above general formulas (MO-1) to (MO-6) include compounds described in paragraph numbers 0248 to 0251 of JP-A No. 2007-26979. Can also be suitably used in the present invention.

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

The polyfunctional monomer used in the present invention is particularly preferably at least one selected from a compound represented by the following general formula (i) and a compound represented by the general formula (ii).

In the general formulas (i) and (ii), E represents — ((CH ₂ ) _y CH ₂ O) — or — ((CH ₂ ) _y CH (CH ₃ ) O) —, respectively, Each represents an integer of 1 to 10, and X represents a hydrogen atom, an acryloyl group, a methacryloyl group, or a carboxyl group, respectively.
In the general formula (i), the total number of acryloyl groups and methacryloyl groups is 3 or 4, each m represents an integer of 0 to 10, and the total of each m is an integer of 1 to 40.
In general formula (ii), the total of acryloyl group and methacryloyl group is 5 or 6, n represents an integer of 0 to 10, respectively, and the total of n represents an integer of 1 to 60, respectively.

In the above formulae, E represents — ((CH ₂ ) _y CH ₂ O) — or — ((CH ₂ ) _y CH (CH ₃ ) O) —, and — ((CH ₂ ) _y CH ₂ O)-is preferred.
Each y represents an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably 1 to 3.
X represents a hydrogen atom, an acryloyl group, a methacryloyl group, or a carboxyl group, respectively.
In general formula (i), the total of the acryloyl group and the methacryloyl group is 3 or 4, and 4 is preferable.
Each m represents an integer of 0 to 10, and preferably 1 to 5. The total of each m is an integer of 1 to 40, preferably 4 to 20.
In general formula (ii), the sum total of an acryloyl group and a methacryloyl group is 5 or 6, and 6 is preferable.
n represents an integer of 0 to 10, respectively, and preferably 1 to 5. The total of n is an integer of 1 to 60, preferably 4 to 30.

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

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

About these polyfunctional monomers, the details of usage such as the structure, single use or combination, addition amount, etc. can be arbitrarily set according to the final performance design of the composition. In the present invention, there is also a method for adjusting both sensitivity and strength by using different functional numbers and / or different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). It is valid. Furthermore, it is preferable to use a polyfunctional monomer having an ethylene oxide chain length of 3 or more and 8 or less in that the developability of the composition can be adjusted and an excellent pattern forming ability can be obtained. In addition, the selection and use of polyfunctional monomers is important for compatibility and dispersibility with other components (for example, polymerization initiators, colorants (pigments), resins, etc.) contained in the composition. For example, compatibility may be improved by the use of a low-purity compound or a combination of two or more. In addition, a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a substrate.

The concentration (mixing ratio) of the polymerizable compound (especially the polyfunctional monomer) is preferably 15% by mass or more, more preferably 20% by mass or more, based on the total solid content in the composition, in that the effect of the present invention is more excellent. It is preferable that the content is 25% by mass or more. Although there is no restriction | limiting in particular about an upper limit, It is preferable that it is 50 mass% or less, and it is more preferable that it is 40 mass% or less.

(Other optional ingredients)
The above composition may contain components other than (A) a pigment, (B) a polymerization initiator, and (C) a polymerizable compound. For example, an alkali-soluble resin, an acrylic polymer having a polymerizable group, a dispersant, a solvent, a surfactant, a polymerization inhibitor, an adhesion improver, an ultraviolet absorber, and the like can be given.
Hereinafter, the optional components will be described in detail.

(Alkali-soluble resin)
The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having a group. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acryl / acrylamide copolymer resins are preferable. From the viewpoint of development control, acrylic resins and acrylamide resins are preferable. Resins and acrylic / acrylamide copolymer resins are preferred.
Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, but are soluble in a solvent and can be developed with a weak alkaline aqueous solution. Of these, (meth) acrylic acid is particularly preferred. These acid groups may be used alone or in combination of two or more.
Examples of the monomer that can give an acid group after polymerization include, for example, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an epoxy group such as glycidyl (meth) acrylate, and 2-isocyanatoethyl (meth). And monomers having an isocyanate group such as acrylate. These monomers for introducing an acid group may be only one type or two or more types. In order to introduce an acid group into an alkali-soluble resin, for example, a monomer having an acid group and / or a monomer capable of imparting an acid group after polymerization (hereinafter sometimes referred to as “monomer for introducing an acid group”) .) May be polymerized as a monomer component.
In addition, when introducing an acid group using a monomer capable of imparting an acid group after polymerization as a monomer component, for example, a treatment for imparting an acid group is required after the polymerization.

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

As the linear organic polymer used as the alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferable, such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, and a crotonic acid copolymer. , Maleic acid copolymers, partially esterified maleic acid copolymers, alkali-soluble phenolic resins such as novolak resins, etc., acid cellulose derivatives having a carboxylic acid in the side chain, and acid anhydrides added to polymers having a hydroxyl group. Can be mentioned. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Examples of alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and (iso) pentyl (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) ) Acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, etc., vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acryloni N-phenylmaleimide, N-phenylmaleimide, N-phenylmaleimide, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, etc. Examples thereof include cyclohexylmaleimide.
As another monomer copolymerizable with (meth) acrylic acid, it is also preferable that it is a monomer which gives the repeating unit represented by a following formula (X), for example.

In the above formula (X), R ^1X represents a hydrogen atom or a methyl group, R ^2X represents an alkylene group having 2 or 3 carbon atoms, R ^3X represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, n Represents an integer of 1 to 15. The repeating unit represented by the above formula (X) has good adsorption and / or orientation on the colorant (particularly pigment) surface due to the effect of π electrons of the benzene ring present in the side chain. In particular, when this side chain portion has an ethylene oxide or propylene oxide structure of paracumylphenol, its steric effect is added, and a better adsorption and / or orientation surface for a colorant (particularly a pigment). Is more effective and preferable. R ^3X represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms. In addition, when R ^3X is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. This is because, when R ^3X is an alkyl group having 1 to 10 carbon atoms, this alkyl group becomes an obstacle and suppresses the approach between the resins and promotes adsorption and / or orientation to the colorant (particularly pigment). This is because if the number of carbon atoms exceeds 10, the steric hindrance effect of the alkyl group is increased, and the adsorption and / or orientation of the benzene ring on the colorant (particularly pigment) surface may be hindered. This phenomenon becomes more prominent as the chain length of the alkyl group of R ^3X becomes longer. When the carbon number exceeds 20, the adsorption and / or orientation of the benzene ring is extremely lowered. Therefore, the alkyl group represented by R ^3X has a carbon number in the range of 1-20. The alkyl group represented by R ^3X is preferably an unsubstituted alkyl group or an alkyl group substituted with a phenyl group.

R ^2X in formula (X) is preferably an alkylene group having 2 carbon atoms from the viewpoint of developability.
Further, n in the formula (X) is preferably in the range of 1 to 12 from the viewpoint of developability.
The repeating unit represented by the formula (X) in the present invention is introduced into the alkali-soluble resin using an ethylenically unsaturated monomer represented by the following formula (Y).

In the formula ^{^{(Y), R 1X, R}} 2X, R 3X, and n are the same as ^{^{^{R 1X, R 2X, R 3X}}} , and n in the formula (X), and preferred examples are also the same.
Examples of the ethylenically unsaturated monomer represented by the formula (Y) include phenol ethylene oxide-modified (meth) acrylate, paracumylphenol ethylene oxide-modified (meth) acrylate, nonylphenol ethylene oxide-modified (meth) acrylate, and nonylphenol propylene oxide. Examples thereof include modified (meth) acrylate.
In addition, only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acids, and 2 or more types may be sufficient as it.

As the alkali-soluble resin, a resin obtained by polymerizing a monomer component essentially containing a compound represented by the following general formula (ED) is also preferable.

In formula (ED), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
By using a resin obtained by polymerizing a monomer component essentially comprising a compound represented by the formula (ED) (hereinafter sometimes referred to as “ether dimer”), it is extremely excellent in heat resistance and transparency. A cured coating film can be formed.
In the general formula (ED) showing an 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, but for example, methyl Linear or branched groups such as a group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, t-amyl group, stearyl group, lauryl group, 2-ethylhexyl group, etc. Alkyl group; aryl group such as phenyl; fat such as cyclohexyl group, t-butyl group, cyclohexyl group, dicyclopentadienyl group, tricyclodecanyl group, isobornyl group, adamantyl group, 2-methyl-2-adamantyl group, etc. A cyclic group; an alkyl group substituted with an alkoxy group such as a 1-methoxyethyl group or a 1-ethoxyethyl group; an alkyl group substituted with an aryl group such as benzyl; Can be mentioned. Among these, a primary or secondary carbon substituent which is difficult to be removed by an acid or heat, such as a methyl group, an ethyl group, a cyclohexyl group, or a benzyl group, is particularly preferable in terms of heat resistance.

As specific examples of the ether dimer, the description of the ether dimer described in paragraph 0565 of JP2012-208494A (corresponding to US Patent Application Publication No. 2012/235099, [0694]) can be referred to. It is incorporated herein.
Among these, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2′- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be only one kind or two or more kinds. The structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.

As the alkali-soluble resin, a benzyl (meth) acrylate / (meth) acrylic acid copolymer and a multi-component copolymer consisting of benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl methacrylate are particularly suitable. . Other monomers in this case include 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl described in JP-A-7-140654. 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 / A methacrylic acid copolymer etc. are mentioned.

The acid value of the alkali-soluble resin is preferably 30 to 200 mgKOH / g, more preferably 50 to 150 mgKOH / g, still more preferably 70 to 120 mgKOH / g. By setting it as such a range, the image development residue of an unexposed part can be reduced effectively.
The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and particularly preferably 7,000 to 20,000.
The content of the alkali-soluble resin in the composition of the present invention is preferably 10 to 50% by mass, more preferably 15 to 40% by mass, particularly preferably 20 to 20% by mass with respect to the total solid content of the composition. 35% by mass.

<Solvent>
In general, the composition of the present invention can be constituted using a solvent. The solvent is basically not particularly limited as long as the solubility of each component and the coating property of the composition are satisfied.
Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, Alkyl oxyacetates (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), 3-oxypropionic acid alkyl esters (Eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)) ), 2-Oki Alkyl propionates (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionate) Propyl acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg 2-methoxy-2-methyl Methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. As ethers, For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc. Preferred examples of the aromatic hydrocarbon include xylene.

It is also preferable to mix two or more of these solvents from the viewpoints of solubility of the alkali-soluble resin, improvement of the coated surface, and the like. In this case, particularly preferably, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol It is a mixed solution composed of two or more selected from acetate, butyl carbitol acetate, ethylene glycol monobutyl ether acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.
The content of the solvent in the composition is preferably such that the total solid content of the composition is 5 to 80% by mass, more preferably 5 to 60% by mass, from the viewpoint of applicability. Mass% is particularly preferred.

<Surfactant>
Various surfactants may be added to the composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
In particular, since the composition of the present invention contains a fluorosurfactant, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved. Sex can be improved more.
That is, when a film is formed using a coating liquid to which a composition containing a fluorosurfactant is applied, the wettability to the coated surface is reduced by reducing the interfacial tension between the coated surface and the coating liquid. Is improved, and the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.
The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. A fluorosurfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the composition.

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

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

Only one type of surfactant may be used, or two or more types may be combined.
When added, the addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass and more preferably 0.005% by mass to 1.0% by mass with respect to the total mass of the composition. .

<Polymerization inhibitor>
In the composition of the present invention, it is desirable to add a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polyfunctional monomer during the production or storage of the composition.
Polymerization inhibitors that can be used in the present invention include hydroquinone, p-methoxyphenol, o-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3 -Methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.

Furthermore, the composition may contain a co-sensitizer for the purpose of further improving the sensitivity of the sensitizing dye or initiator to actinic radiation or suppressing the polymerization inhibition of the polyfunctional monomer by oxygen. Moreover, in order to improve the physical property of a cured film, you may add well-known additives, such as a diluent, a plasticizer, a fat-sensitizing agent, as needed.

When the polymerization inhibitor is used, the addition amount is preferably in the range of 0.001% by mass to 0.015% by mass, and 0.03% by mass to 0.09% by mass in the total solid content in the composition. % Is more preferable.

<Adhesion improver (adhesion promoter)>
An adhesion improver can be added to the composition of the present invention in order to improve adhesion to a hard surface such as a substrate.
Examples of the adhesion improver include a silane coupling agent and a titanium coupling agent.
The silane coupling agent preferably has an alkoxysilyl group as a hydrolyzable group that can be chemically bonded to an inorganic material. In addition, it preferably has a group that interacts or forms a bond with an organic resin and exhibits an affinity, and such a group has a (meth) acryloyl group, a phenyl group, a mercapto group, a glycidyl group, or an oxetanyl group. Among them, those having a (meth) acryloyl group or a glycidyl group are preferable.
That is, the silane coupling agent used in the present invention is preferably a compound having an alkoxysilyl group and a (meth) acryloyl group or an epoxy group, and specifically, a (meth) acryloyl-tri having the following structure. Examples include methoxysilane compounds and glycidyl-trimethoxysilane compounds.

In addition, the silane coupling agent in the present invention is also preferably a silane compound having at least two functional groups having different reactivity in one molecule, and particularly preferably having an amino group and an alkoxy group as the functional group. Examples of such silane coupling agents include N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-602), N-β-aminoethyl-γ- Aminopropyl-trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-603), N-β-aminoethyl-γ-aminopropyl-triethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-602), γ -Aminopropyl-trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-903), γ-aminopropyl-triethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-903).

When the silane coupling agent is used, the addition amount is preferably in the range of 0.1% by mass to 5.0% by mass, and 0.2% by mass to 3.0% by mass in the total solid content in the composition. The mass% is more preferable.

<Acrylic polymer having a polymerizable group>
The composition of the present invention may contain an acrylic polymer having a polymerizable group. Examples of the polymerizable group that the acrylic polymer having a polymerizable group has include an ethylenically unsaturated bond group, a (meth) acryloyl group or a vinyl group is preferable, and a (meth) acryloyl group is more preferable.
The acrylic polymer having a polymerizable group used in the present invention usually contains a structural unit having a polymerizable group and other structural units.
The acrylic polymer in the present invention refers to a vinyl polymer having a repeating unit derived from one or more of (meth) acrylic acid, (meth) acrylic acid ester, and (meth) acrylamide.

The ratio of the polymerizable group contained in the acrylic polymer having a polymerizable group is preferably 5 to 50, and more preferably 10 to 40. By setting it as such a range, coexistence of hardening, property, and developability is achieved more effectively. Here, the ratio of a polymerizable group means a molar copolymerization ratio.

As another structural unit, the structural unit containing an acid group is illustrated, for example. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group, and the like, and a carboxyl group is preferable.
The acid value of the acrylic polymer having a polymerizable group used in the present invention is preferably 10 to 200 mgKOH / g, and more preferably 20 to 150 mgKOH / g. By setting it as such a range, it becomes possible to improve the solubility of the unexposed part at the time of pattern formation. The acid value in the present invention refers to a value obtained by neutralization titration with a potassium hydroxide solution.

Examples of the acrylic polymer having a polymerizable group include carboxyl group-containing resins such as glycidyl group-containing unsaturated compounds such as glycidyl (meth) acrylate and allyl glycidyl ether, allyl alcohol, 2-hydroxy acrylate, and 2-hydroxy methacrylate. Resins reacted with unsaturated alcohol, carboxyl group-containing resins having hydroxyl groups, free isocyanate group-containing unsaturated compounds, resins reacted with unsaturated acid anhydrides, and addition reaction products of epoxy resins and unsaturated carboxylic acids. Resin in which basic acid anhydride is reacted, resin in which hydroxyl group-containing polyfunctional monomer is reacted with addition reaction product of conjugated diene copolymer and unsaturated dicarboxylic acid anhydride, and elimination reaction is caused by base treatment to cause unsaturated reaction A resin having a specific functional group that gives a group is synthesized, and the resin is subjected to base treatment. Resin or the like to produce an unsaturated group at Succoth can be cited as typical resins.
Regarding the acrylic polymer having a polymerizable group, the description in paragraphs 0043 to 0067 of JP-A-2009-79150 can be referred to, and the contents thereof are incorporated in the present specification. Further, description of polymer compounds 1 to 22 in paragraphs 0063 to 0067 of JP-A-2009-79150 can be referred to, and the contents thereof are incorporated in the present specification.

<Other ingredients>
In the composition of the present invention, other components may be appropriately selected and used according to the purpose as long as the effects of the present invention are not impaired in addition to the essential components and the optional additives.
Examples of other components that can be used in combination include a binder polymer, a dispersant, a sensitizer, a crosslinking agent, a curing accelerator, a filler, a thermosetting accelerator, a thermal polymerization inhibitor, a plasticizer, and an ultraviolet absorber. Furthermore, adhesion promoters to the substrate surface and other auxiliary agents (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers. , Chain transfer agent, etc.) may be used in combination.
By appropriately containing these components, properties such as stability of the film to be formed and film physical properties can be adjusted.
These components are described, for example, in paragraph No. 0183 of JP 2012-003225 A or later (corresponding to [0237] or later of US Patent Application Publication No. 2013/0034812) or JP 2008-250074. The description of paragraph numbers 0101 to 0102, paragraph numbers 0103 to 0104, paragraph numbers 0107 to 0109, and the like can be taken into consideration, and the contents thereof are incorporated in the present specification.

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

In filter filtration, two or more filters may be used in combination.
For example, the filtration can be performed first using a first filter and then using a second filter having a pore diameter different from that of the first filter.
At that time, the filtering by the first filter and the filtering by the second filter may be performed only once or may be performed twice or more, respectively.
As the second filter, a filter formed of the same material as the first filter described above can be used.

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

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

<Process procedure>
The manufacturing method in particular of the colored layer formed using the composition of this invention is not restrict | limited, A well-known method is employable. Among them, a step of forming a colored radiation-sensitive composition layer by applying a colored radiation-sensitive composition on an underlayer (hereinafter also referred to as “colored radiation-sensitive composition layer forming step”), and a mask Through the process of pattern exposure of the colored radiation-sensitive composition layer (hereinafter also referred to as “exposure process”), and developing the colored radiation-sensitive composition layer after exposure to develop a colored layer (hereinafter referred to as “colored pattern” and “ A step of forming a color pixel ”(hereinafter also referred to as a“ development step ”).
Hereinafter, the procedure of each step of the preferred embodiment will be described in detail.

(Colored radiation-sensitive composition layer forming step)
In the colored radiation-sensitive composition layer forming step, the colored radiation-sensitive composition layer is formed by applying the above composition on the underlayer.
As a method for applying the composition of the present invention on the underlayer, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like can be applied.
The thickness of the colored radiation-sensitive composition layer is preferably from 0.1 μm to 10 μm, more preferably from 0.2 μm to 5 μm, and even more preferably from 0.2 μm to 3 μm.
The colored radiation-sensitive composition layer coated on the support may be dried (pre-baked) as necessary. The drying is performed at a temperature of 50 ° C. to 140 ° C. for 10 seconds to 300 seconds using a hot plate, oven or the like. It can be carried out.
(Exposure process)
In the exposure step, the colored radiation-sensitive composition layer formed in the colored radiation-sensitive composition layer forming step is subjected to pattern exposure through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper, for example.
As radiation (light) that can be used for exposure, ultraviolet rays such as g-line and i-line are particularly preferable (particularly preferably i-line). Irradiation dose (exposure dose) is preferably 30 ~ 1500mJ / cm ^2, more preferably 50 ~ 1000mJ / cm ^2, and most preferably 80 ~ 500mJ / cm ^2.

(Development process)
Subsequently, by performing development such as alkali development treatment, the colored radiation-sensitive composition layer in the light unirradiated portion in the exposure step is eluted in the developer, and only the photocured portion remains.
The developer is preferably an organic alkali developer that does not cause damage to the underlying image sensor or circuit. The development temperature is usually 20 ° C. to 30 ° C., and the development time is, for example, 20 seconds to 90 seconds. In order to remove the residue more, in recent years, it may be carried out for 120 seconds to 180 seconds. Furthermore, in order to further improve residue removability, the process of shaking off the developer every 60 seconds and further supplying a new developer may be repeated several times.
Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5, 4, 0] -7-undecene and the like, and an alkaline aqueous solution obtained by diluting these alkaline agents with pure water so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. Is preferably used as a developer.
In addition, an inorganic alkali may be used for the developer, and as the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metaoxalate and the like are preferable.
In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

Next, it is preferable to perform heat treatment (post-bake) after drying. If a multicolored colored layer (colored pattern) is formed, a cured film can be produced by sequentially repeating the above steps for each color. Thereby, a color filter is obtained.
The post-baking is a heat treatment after development for complete curing, and a heat curing treatment is usually performed at 100 ° C. to 240 ° C., preferably 200 ° C. to 240 ° C.
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above-described condition. be able to.
In addition, the manufacturing method of this invention may have a well-known process as a manufacturing method of a color filter as a process other than the above as needed. For example, after performing the above-mentioned colored radiation-sensitive composition layer forming step, exposing step, and developing step, if necessary, a curing step of curing the formed colored layer (colored pattern) by heating and / or exposure. May be included.

The film thickness of the colored layer (colored pixel) in the color filter is preferably 2.0 μm or less, and more preferably 1.0 μm or less.
In addition, the size (pattern width) of the colored layer (colored pixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.7 μm or less.
The color filter can be used for a liquid crystal display device, a solid-state imaging device, or an organic EL display device, and is particularly suitable for a solid-state imaging application or an organic EL display device. When used in a liquid crystal display device, there are few alignment defects of liquid crystal molecules due to a decrease in specific resistance, the color of a display image is good, and the display characteristics are excellent.

Since the color filter of the present invention has colored pixels that are excellent in hue and excellent in light resistance, it is particularly suitable as a color filter for liquid crystal display devices. A liquid crystal display device provided with such a color filter can display a high-quality image having a good display image color tone and excellent display characteristics.
When the color filter of the present invention is used in a liquid crystal display device, a high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube. By using as a backlight, a liquid crystal display device having high luminance and high color purity and good color reproducibility can be provided.

Further, the color filter of the present invention can be suitably used for a solid-state imaging device.
The configuration of the solid-state image sensor is not particularly limited as long as it is a configuration provided with the color filter of the present invention and functions as a solid-state image sensor, and examples thereof include the following configurations.
On the support, there are a plurality of photodiodes constituting a light receiving area of a solid-state imaging device (CCD, CMOS, etc.) and a transfer electrode made of polysilicon, etc., and only the light receiving part of the photodiode is opened on the photodiode and the transfer electrode. And a device protective film made of silicon nitride or the like formed on the light shielding film so as to cover the entire surface of the light shielding film and the photodiode light-receiving portion. A configuration having a color filter.
Further, there are a configuration having a light condensing means (for example, a micro lens) on the device protective film and under the color filter (on the side close to the support), or a structure having the light condensing means on the color filter. May be.

The present invention also relates to an organic EL display device having the above-described underlayer.
An embodiment of the organic EL display device of the present invention will be described below with reference to the drawings.
FIG. 1 is a cross-sectional view of a part of one embodiment of an organic EL display device 100 including a base layer 40 and a colored layer 50. Each pixel generates light of one of the three primary colors (red, green, and blue) by combining a plurality of organic EL elements 20 that generate white light and the colored layer 50 (50R, 50G, 50B), for example. It is. The pitch (inter-center distance) P of the plurality of organic EL elements 20 is, for example, 30 μm or less, more preferably 10 μm or less, and specifically, for example, about 2 μm to 3 μm. The pitch p is preferably 0.5 μm or more, and more preferably 1 μm or more. That is, this display device is a so-called micro display in which the size of the organic EL element 20 is extremely small. Note that an eyepiece lens (not shown) is provided on the display device, and the user views an image displayed on the display device in an enlarged manner through the eyepiece lens. Therefore, the user can see only a portion of the image displayed on the display device within the range of the eyepiece lens capture angle.

The organic EL elements 20 are arranged in a matrix on the substrate 10 and are covered with a protective film 30. A sealing substrate 60 made of glass or the like is bonded to the entire surface of the protective film 30 with an adhesive layer (not shown) therebetween. A colored layer 50 is provided on the surface of the sealing substrate 60 on the substrate 10 side.
As the substrate 10, a glass substrate or the like is used.
The configuration of the organic EL element 20 is not particularly limited, and the configuration can be adopted. Usually, the light emitting layer taught between the electrodes is often included.

For example, the protective film 30 has a thickness of 0.5 μm to 10 μm and is made of silicon nitride (SiN). The adhesive layer (not shown) is made of, for example, an ultraviolet curable resin or a thermosetting resin. The sealing substrate 60 seals the organic EL element 20 together with an adhesive layer (not shown). The sealing substrate 60 is made of, for example, a material such as glass that is transparent to the light generated by the organic EL element 20.
The colored layer 50 is for extracting white light generated in the organic EL element 20 as red, green, or blue color light. The red colored layer 50R and the green colored layer 50G that face the plurality of organic EL elements 20 respectively. And a blue colored layer 50B. The red colored layer 50 </ b> R, the green colored layer 50 </ b> G, and the blue colored layer 50 </ b> B are sequentially arranged corresponding to the organic EL element 20. The red colored layer 50R, the green colored layer 50G, and the blue colored layer 50B are layers formed from a colored radiation-sensitive composition containing the above-described colorant and the like. The light transmittance is adjusted to be high in the green or blue wavelength region and low in other wavelength regions.
The colored layer 50 may be provided with a semi-transmissive region in a part of the colored layer 50. Thereby, in this display device, even when the dimension of the organic EL element 20 is small, it is possible to further suppress color mixing due to diffraction of light that has passed through the adjacent colored layer. The semi-transmissive region is obtained by varying the transmittance of a part of the colored layer by providing a semi-permeable film on a part of the colored layer.
Under the colored layer 50, the above-described underlayer 40 having a refractive index of 1.60 or more at a wavelength of 633 nm is provided. By disposing the underlayer 40, the adhesion of the colored layer 50 is further improved.

As described above, in the micro display, the size of the organic EL element is extremely small. Therefore, since the size of the colored layer provided corresponding to the organic EL element is extremely small, further adhesion is required for the colored layer. In the present invention, it is possible to arrange a colored layer having a very small size with good adhesion by arranging the colored layer on the above-described underlayer.
In addition, as described above, when the base layer is substantially free of metal particles or metal oxide particles, the flatness of the base layer is improved, and the adhesion of the colored layer disposed on the base layer is improved. It can be suitably applied to a micro display.

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

(Production Example 1: Preparation of Red pigment dispersion)
A mixed solution having the following composition was mixed and dispersed for 3 hours using a zirconia bead having a diameter of 0.3 mm in a bead mill (high pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon BEE Co., Ltd.)). A Red pigment dispersion was prepared.
・ C. I. Pigment Red 254 12.4 parts C.I. I. Pigment Red 139 5.6 parts, dispersing agent: BYK-2001 BYK-2001 3.6 parts, alkali-soluble resin 1: benzyl methacrylate / methacrylic acid copolymer (= 70/30 molar ratio, Mw: 30000, acid value: 110 mg KOH / g) 3.6 parts Solvent: 74.8 parts propylene glycol methyl ether acetate

(Production Example 2: Preparation of Green pigment dispersion)
The mixed solution having the following composition was mixed and dispersed for 3 hours using a zirconia bead having a diameter of 0.3 mm in a bead mill (high pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon BEE Co., Ltd.)). A Green pigment dispersion was prepared.
・ C. I. Pigment green 36 10.8 parts C.I. I. Pigment Yellow 150 7.2 parts, Dispersant: BYK-2001 3.6 parts BYK, alkali-soluble resin 1 3.6 parts, solvent: propylene glycol methyl ether acetate 74.8 parts

(Production Example 3: Preparation of Blue pigment dispersion)
The mixed solution having the following composition was mixed and dispersed for 3 hours using a zirconia bead having a diameter of 0.3 mm in a bead mill (high pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon BEE Co., Ltd.)). A Blue pigment dispersion was prepared.
・ C. I. Pigment Blue 15: 6 14.4 parts C.I. I. Pigment Violet 23 3.6 parts, dispersant: BYK-2001 BYK-2001 3.6 parts, alkali-soluble resin 1 3.6 parts, solvent: propylene glycol methyl ether acetate 74.8 parts

(Production Example 4: Preparation of red radiation-sensitive composition)
The following components were mixed to prepare a red radiation sensitive composition.
Red pigment dispersion 70.0 parts Alkaline-soluble resin 1 1.9 parts Polymerizable compound 1: Dipentaerythritol hexaacrylate (trade name Kayarad DPHA manufactured by Nippon Kayaku Co., Ltd.) 3.0 parts Polymerizable compound 2 : Pentaerythritol ethylene oxide-modified tetraacrylate (trade name RP-1040, manufactured by Nippon Kayaku Co., Ltd.) 1.3 parts ・ Polymerization initiator 1: The following structure (IRGACURE-OXE01, manufactured by BASF) 1.3 parts ・ Solvent: Propylene 22.4 parts of glycol methyl ether acetate

(Production Example 5: Preparation of green radiation-sensitive composition)
A green radiation-sensitive composition was prepared using the same components as in Example 1 except that the Red pigment dispersion in Example 1 was replaced with the Green pigment dispersion.
(Production Example 6: Preparation of blue radiation-sensitive composition)
A blue radiation-sensitive composition was prepared using the same components as in Example 1 except that the Red pigment dispersion in Example 1 was replaced with a Blue pigment dispersion.

(Production Example 7: Base material A)
With reference to WO2010 / 128661, m-phenylenediamine (28.94 g, 0.27 mol, manufactured by Aldrich), 2,4,6-trichloro-1,3,5-triazine (36.91 g, 0.20 mol, Tokyo) Synthesis was performed using Kasei Kogyo Co., Ltd.) and aniline (56.53 g, 0.6 mol, manufactured by Junsei Kagaku Co., Ltd.) to obtain 46.12 g of the target polymer compound A. The obtained polymer compound A is a compound having the following structural units. The weight average molecular weight Mw measured in terms of polystyrene by GPC of the polymer compound A was 4,900, and the polydispersity Mw / Mn was 2.21.

Under air, 2.0 g of the polymer compound A obtained above was added to a 10 mL eggplant flask, and 8.0 g of cyclohexanone was added as a solvent, and completely dissolved at room temperature, and a 20 mass% cyclohexanone solution of the polymer compound A was added. Prepared.
Next, 0.94 g of cyclohexanone was added to 1.0 g of this 20% by mass cyclohexanone solution, and then 10% by mass cyclohexanone of Epolide GT-401 (manufactured by Daicel Chemical Industries), which is a compound containing an epoxy group as a crosslinking agent. 0.20 g of the solution (10.0 parts by mass with respect to 100 parts by mass of the solid content of the polymer) was added. Further, 0.040 g of a 5 mass% cyclohexanone solution of 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion promoter (1 mass relative to 100 mass parts of the solid content of the polymer) Part), and as a surfactant, 0.040 g of a 0.5 wt% cyclohexanone solution of the trade name Megafac R-30 (manufactured by DIC Corporation) (the solid content of the polymer was 100 parts by weight) 0.1 parts by mass) was added and stirred for 3 hours until the solution became homogeneous. After stirring, the solute was completely dissolved, and a polymer varnish (base material A) having a total mass% of solid content of 10 mass% was obtained as a pale yellow transparent solution.

(Production Example 8: Base material B)
With reference to WO2010 / 128661, 9,9-bis (4-aminophenyl) fluorene [2] (6.48 g, 0.018 mol), 2,4,6-trichloro-1,3,5-triazine [1] (4.06 g, 0.022 mol) and aniline (5.64 g, 0.06 mol) were used for synthesis to obtain 10.1 g of polymer compound B. The polymer compound B is a compound having the following structural unit. The weight average molecular weight Mw measured by GPC of the high molecular compound B in terms of polystyrene was 2,200, and the polydispersity Mw / Mn was 1.51.

Under air, 2.0 g of the polymer compound B obtained above is added to a 10 mL eggplant flask, and 8.0 g of cyclohexanone is added as a solvent, and completely dissolved at room temperature to prepare a 20 mass% cyclohexanone solution of the polymer compound B. did.
Next, 0.72 g of cyclohexanone was added to 1.0 g of this 20% by mass cyclohexanone solution, and then 10% by mass of Epolide GT-401 (produced by Daicel Chemical Industries, Ltd.), which is a compound containing an epoxy group as a crosslinking agent. 0.15 g of cyclohexanone solution (7.5 parts by mass with respect to 100 parts by mass of the solid content of the polymer) was added. Further, 0.10 g of a 2% by mass cyclohexanone solution of 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion promoter (1 mass relative to 100 mass parts of the solid content of the polymer) Parts) and 0.20 g of a 0.1% by weight cyclohexanone solution of the trade name Megafac R-30 (manufactured by DIC Corporation) as a surfactant (the solid content of the polymer was 100 parts by weight) 0.1 parts by mass) was added and stirred for 3 hours until the solution became homogeneous. After stirring, the solute was completely dissolved to obtain a polymer varnish (base material B) having a total mass% of solid content of 10 mass% as a colorless light yellow solution.

(Production Example 9: Base material C)
Under air, 2.0 g of the polymer compound B obtained above is added to a 10 mL eggplant flask, and 8.0 g of cyclohexanone is added as a solvent, and completely dissolved at room temperature to prepare a 20 mass% cyclohexanone solution of the polymer compound B. did.
Subsequently, 0.72 g of cyclohexanone was added to 1.0 g of this 20% by mass cyclohexanone solution, and then 0.1% of a 10% by mass cyclohexanone solution of VESTAGON B 1065 (manufactured by Degussa AG), which is a compound containing a blocked isocyanate as a crosslinking agent. 10 g (5 parts by mass with respect to 100 parts by mass of the solid content of the polymer) was added. Furthermore, 0.10 g of a 2% by weight cyclohexanone solution of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion promoter (the solid content of the polymer was 100 parts by mass). 0.20 g of a 0.1% by weight cyclohexanone solution of the trade name Megafac R-30 (manufactured by DIC Corporation) as a surfactant (100 parts by weight of the solid content of the polymer). Was added for 0.1 hour, and the mixture was stirred for 3 hours until the solution became homogeneous. After stirring, the solute was completely dissolved, and a polymer varnish (underlying material C) having a total mass% of solid content of 10 mass% was obtained as a colorless light yellow solution.

<Examples 1 to 9, Comparative Examples 1 to 3>
A base film A to C or CT-2010 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) is uniformly applied by spin coating on an 8-inch silicon wafer to form a coating film, and the formed coating film is 150 ° C. For 2 minutes, and further for 5 minutes on a 300 ° C. hot plate. The spin coating speed was adjusted so that the thickness of the coating film after the heat treatment was about 0.4 μm.
A silicon wafer with a base layer was obtained as described above.

Next, the colored radiation-sensitive composition (red radiation-sensitive composition, blue radiation-sensitive composition, or green radiation-sensitive composition) produced above is under the silicon wafer with the underlayer obtained above. It applied using a spin coater so that the film thickness after drying might be set to 0.6 micrometer on a base layer, and the heat processing (prebaking) were performed for 120 second using a 100 degreeC hotplate.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), pattern exposure was performed at a total of 399 locations in a pattern arranged in a matrix of 21 rows × 19 columns. At this time, the above-mentioned 21 rows in the matrix are under the condition that the minimum exposure amount is 500 J / m ² and the exposure amount is increased for each row at intervals of 500 J / m ^2. The focal length is changed at intervals of 0.1 μm around the optimum focal length (Focus 0.0 μm). That is, the photo is formed so that a square pixel pattern of 1.1 μm square is arranged within a range of 4 mm × 3 mm under the condition that the focal length is optimal for the central row and the focal length is changed for each row. A mask was used.
Thereafter, the silicon wafer on which the exposed coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2060 (Fuji Film Electronics Co., Ltd.). Paddle development was performed at 23 ° C. for 60 seconds using Materials Co., Ltd. to form a colored layer (colored pattern) on the silicon wafer.
The silicon wafer on which the colored layer was formed was rinsed with pure water and then spray-dried.
Further, a heat treatment (post-bake) was performed for 300 seconds using a 200 ° C. hot plate to obtain a silicon wafer (color filter) having colored pixels corresponding to the colorant.
The combinations of the underlayer material and the colored radiation-sensitive composition used in each example and comparative example are collectively shown in Table 1 described later. Further, the refractive index of the underlayer was measured by the method (apparatus) described above.

<Evaluation>
(Pattern formability)
The colored pattern formed on the wafer obtained above was measured using a length measuring SEM (S-9260 scanning electron microscope, manufactured by Hitachi, Ltd.), and the size of the colored pattern in the exposed portion and the unexposed portion. The degree of development remaining was evaluated by SEM images. It is desirable that there is a difference in developer solubility between the exposed part and the unexposed part, the exposed part is imaged with the dimensions of the mask design, and there is no dissolved residue in the unexposed part. The results are shown in the table below. Although the evaluation criteria are shown below, A and B are practical levels.
(Evaluation criteria)
A: In the exposed portion, the image was formed at a ratio of 1: 1 with respect to the mask size. There was no dissolved residue in the unexposed portion, and the pattern shape was a good rectangle.
B: In the exposed area, the image was formed at a ratio of 1: 1 with respect to the mask size, and no dissolved residue was observed in the unexposed area, but the pattern shape was somewhat disturbed.
C: A pattern was formed in the exposed area, but it was not formed at a ratio of 1: 1 with respect to the mask size, or development failure was observed in the unexposed area.
D: The unexposed portion was hardly dissolved, and the exposed portion was not formed at 1: 1 with respect to the mask size.

(Pattern adhesion)
The colored pattern formed on the wafer was observed using a length measuring SEM (S-9260 scanning electron microscope manufactured by Hitachi, Ltd.), and the adhesion of the exposed portion was evaluated with an optical microscopic image. It is desirable that there is no pattern peeling at an exposure amount at which the same pattern size as the mask size is obtained. The results are shown in the table below. Although the evaluation criteria are shown below, A and B are practical levels.
<Evaluation criteria>
A: Pattern peeling is not seen at all.
B: 1 to 5 pixels of pattern peeling is observed.
C: Pattern peeling is observed in 6 to 100 pixels.
D: 101 pixels or more of pattern peeling is observed.

The evaluation results of each example and comparative example are summarized in Table 1.
In Table 1, “Red” means “red radiation-sensitive composition”, “Green” means “green radiation-sensitive composition”, and “Blue” means “blue radiation-sensitive composition”.

As shown in Table 1, in the method for producing a color filter of the present invention, the adhesion of the colored layer was excellent and the generation of residues was also suppressed.
On the other hand, as shown in the comparative example, when an underlayer that does not exhibit a predetermined refractive index is used, a desired effect cannot be obtained.

Using the base layer formed from the base materials A to C described above, the organic EL display device (micro OLED) of the above-described embodiment of FIG. 1 was produced. More specifically, a plurality of organic EL elements composed of a first electrode, a light emitting layer, and a second electrode were produced on a substrate (glass substrate) by vacuum deposition. Note that the pitch P between the organic EL elements shown in FIG. 1 was 2 μm. Next, a protective layer was disposed, and a base layer was produced using the base material A described above on the protective layer according to the same procedure as in the above example. Furthermore, using the above-mentioned red radiation-sensitive composition, green radiation-sensitive composition, and blue radiation-sensitive composition, a red colored layer, a green colored layer, and a blue color are provided at positions facing each organic EL element. A colored layer (size of each colored layer: 2 μm × 2 μm) was formed, and a sealing substrate was further disposed thereon.
In the obtained organic EL display device, each colored layer exhibited excellent adhesion and was excellent in pattern formability.
In addition, even if it used base material B and C instead of the said base material A, the desired effect was acquired similarly.

Base materials A to which NaCl was added at 50 mass ppm, 30 mass ppm, or 5 mass ppm were designated as base materials A-1, A-2, and A-3, respectively.
Base materials B to which NaCl was added at 50 mass ppm, 30 mass ppm, or 5 mass ppm were designated as base materials B-1, B-2, and B-3, respectively.
Base materials C to which NaCl was added at 50 ppm by mass, 30 ppm by mass, or 5 ppm by mass were designated as base materials C-1, C-2, and C-3, respectively.
A base layer and a color filter were formed in the same manner as in Examples 1 to 9 except that these base materials were used. As a result, it was confirmed that the occurrence of defects in the underlayer was reduced.

In the base material A, the high-refractive-index low-molecular compound (low-molecular compound having a fluorene structure (the above formula (B))) is 10% by mass, 7% by mass, or 5% by mass with respect to the total mass of the polymer compound A. Further, they were added to make base materials A-4, A-5, and A-6, respectively.
In the base material B, the high-refractive-index low-molecular compound (low-molecular compound having a fluorene structure (the above formula (B))) is 10% by mass, 7% by mass, or 5% by mass with respect to the total mass of the polymer compound A. Further, they were added as base materials B-4, B-5, and B-6, respectively.
In the base material C, the high-refractive-index low-molecular compound (low-molecular compound having a fluorene structure (the above formula (B))) is 10% by mass, 7% by mass, or 5% by mass with respect to the total mass of the polymer compound A. Further, the base materials C-4, C-5, and C-6 were added, respectively.
A base layer and a color filter were formed in the same manner as in Examples 1 to 9 except that these base materials were used. As a result, it was confirmed that the refractive index of the underlayer was improved.

DESCRIPTION OF SYMBOLS 10 Substrate 20 Organic EL element 30 Protective film 40 Underlayer 50 Colored layer 50R Red colored layer 50G Green colored layer 50B Blue colored layer 60 Substrate for sealing 100 Organic EL display device (micro OLED)

Claims

An underlayer forming step of forming an underlayer having a refractive index of 1.60 or more at a wavelength of 633 nm on a support;
A colored layer forming step of forming a colored layer on the underlayer using a colored radiation-sensitive composition containing (A) a colorant, (B) a polymerization initiator, and (C) a polymerizable compound;
A method for producing a color filter, comprising:
The method for producing a color filter according to claim 1, wherein the colorant is a pigment, and the content thereof is 45% by mass or more based on the total mass of the colored radiation-sensitive composition.
The method for producing a color filter according to claim 1 or 2, wherein the underlayer contains an organic compound having a refractive index of 1.60 or more at a wavelength of 633 nm.
The method for producing a color filter according to claim 1, wherein the underlayer contains a triazine ring-containing polymer.
The method for producing a color filter according to claim 4, wherein the triazine ring-containing polymer contains at least one selected from the group consisting of repeating units represented by formulas (1A) to (4A).

(In Formula (1A), R 1A and R 2A each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group. Ar represents one of an aromatic ring and a heterocyclic ring, or Represents a divalent organic group containing both, * indicates a bonding position.
In formula (2A), R 1A and R 2A each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group. Ar represents a divalent organic group containing one or both of an aromatic ring and a heterocyclic ring. R 3A represents an alkyl group, an aralkyl group, an aryl group, an alkylamino group, an alkoxysilyl group-containing alkylamino group, an aralkylamino group, an arylamino group, an alkoxy group, an aralkyloxy group, or an aryloxy group. * Indicates a binding position.
In formula (3A), Ar represents a divalent organic group containing one or both of an aromatic ring and a heterocyclic ring. * Indicates a binding position.
In the formula (4A), R 4A to R 9A each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a phenyl group optionally substituted with W, Alternatively, it represents a naphthyl group which may be substituted with W. Y 1 and Y 2 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Z 1 and Z 2 each independently represents an alkylene group having 1 to 10 carbon atoms or a phenylene group optionally substituted with W. W represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxy group, and n represents 0 or an integer of 1 or more. * Indicates a binding position. )
The method for producing a color filter according to claim 4 or 5, wherein the content of the triazine ring-containing polymer in the underlayer is 40% by mass or more based on the total mass of the underlayer.
The method for producing a color filter according to any one of claims 4 to 6, wherein the triazine ring-containing polymer has a weight average molecular weight of 1,000 to 100,000.
The method for producing a color filter according to any one of claims 1 to 7, wherein the underlayer is substantially free of metal particles or metal oxide particles.
An underlayer forming composition used for forming an underlayer of a colored layer contained in a color filter, the underlayer forming composition containing a triazine ring-containing polymer.
Furthermore, the composition for base layer formation of Claim 9 containing the compound which has a fluorene structure as a high refractive index low molecular weight compound.
Furthermore, the composition for base layer formation of Claim 9 or 10 containing NaCl.
An organic EL display device having an organic EL element, a base layer, and a colored layer,
An organic EL display device, wherein the base layer is a base layer having a refractive index of 1.60 or more at a wavelength of 633 nm.