KR20150143679A - Method for producing color filter, composition for forming base layer, and organic el display device - Google Patents

Abstract

An object of the present invention is to provide a method of manufacturing a color filter, a composition for forming a base layer, and an organic EL display device in which adhesion of colored layers to be formed is excellent and generation of a residue at the time of forming a colored layer is suppressed. The method for producing a color filter according to the present invention comprises 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 a support, And (C) a polymerizable compound, wherein the coloring layer is formed using a coloring and radiation sensitive composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for manufacturing a color filter, a composition for forming a base layer, and an organic EL display device.

The present invention relates to a method of manufacturing a color filter, and relates to a method of manufacturing a color filter using a ground layer (underlying layer) exhibiting a predetermined refractive index.

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

Patent Document 1: JP-A-2012-198408

On the other hand, in recent years, as the coloring layer is made finer, further improvement of the adhesion of the colored layer is required. At the same time, further suppression of the generation of residues during development processing at the time of coloring layer formation is required.

The inventors of the present invention have found that when the color filter is manufactured by using the foundation layer described in Patent Document 1, both the adhesion of the colored layer and the suppression of the residue can not be satisfied at the recently required level at the same time, .

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method of manufacturing a color filter in which adhesion of a colored layer to be formed is excellent in consideration of the above-described circumstances, and the generation of a residue at the time of forming the colored layer is suppressed.

Means for Solving the Problems The present inventors have intensively studied in order to achieve the above object, and as a result, they found that the above problems can be solved by using a base layer exhibiting a predetermined refractive index, thereby completing the present invention.

That is, the inventors of the present invention have found that the above problems can be solved by the following constitutions.

(1) 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 a support,

A colored layer forming step of forming a colored layer using a coloring and radiation sensitive composition comprising (A) a colorant (preferably a pigment), (B) a polymerization initiator, and (C)

Wherein the color filter comprises a plurality of color filters.

(2) The method for producing a color filter according to (1), wherein the coloring agent is a pigment and the content of the pigment is 45 mass% or more with respect to the total mass of the coloring and radiation-sensitive composition.

(3) The method for producing a color filter according to (1) or (2), wherein the base layer contains an organic compound having a refractive index of 1.60 or more at a wavelength of 633 nm.

(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 process for producing a color filter according to (4), wherein the triazine ring-containing polymer comprises at least one kind selected from the group consisting of repeating units represented by the following formulas (1A) to (4A).

(6) The method for producing a color filter according to (4) or (5), wherein the content of the triazine ring-containing polymer in the base layer is 40 mass% or more with respect to the total mass of the base layer.

(7) The process 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 metal particles or metal oxide particles are not substantially contained in the ground layer.

(9) A composition for forming a ground layer, which is used for forming a ground layer of a colored layer contained in a color filter, comprising a triazine ring-containing polymer.

(10) The composition for forming a foundation layer according to (9), further comprising a compound having a fluorene structure as a high refractive index low molecular weight compound.

(11) The composition for forming a foundation layer according to (9) or (10), further comprising NaCl.

(12) An organic EL display device having an organic EL element, a ground layer, and a colored layer,

Wherein the base layer is a ground layer 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 of manufacturing a color filter in which adhesion of a colored layer to be formed is excellent and generation of a residue at the time of forming the colored layer is suppressed.

1 is a cross-sectional view of a part of one embodiment of the organic EL display device of the present invention.

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

In the present specification, "" is used to mean that the numerical values described before and after the lower limit and the upper limit are included.

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

In the present specification, "(meth) acrylate" represents acrylate and methacrylate, "(meth) acryl" represents acryl and methacryl, "(meth) acryloyl" And methacryloyl. In the present specification, the terms "monomer" and "monomer" are synonyms. 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 involved in the polymerization reaction.

The "radiation" in the present invention means that it includes visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like. The "colored layer" in the present invention means a layer made of a pixel and / or a black matrix used for a color filter.

The characteristic feature of the method of producing a color filter of the present invention is that a base layer exhibiting a predetermined refractive index is used. The use of this undercoat layer minimizes irregular reflection at the time of exposure in the formation of the colored layer, reduces the amount of unexposed portions due to the leakage light, and improves the adhesion of the colored layer.

Among them, when the base layer contains a triazine ring-containing polymer as described later, since the triazine skeleton has a planar structure, the benzene ring structure in the colored layer, the planar structure in the coloring agent and the triazine skeleton are likely to interact with each other , The adhesion of the colored layer is further improved.

The method for manufacturing a color filter of the present invention includes at least a base layer forming step and a colored layer forming step.

Hereinafter, the materials and procedures used in each step will be described in detail.

≪ Lower layer forming step &

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 a support.

First, the support used in this step will be described in detail, and then the foundation layer will be described in detail.

(Support)

The support is not particularly limited as long as it is a substrate capable of supporting the base layer. For example, a photoelectric conversion element substrate (substrate for a solid-state imaging element) (for example, a silicon substrate, an oxide film, a silicon nitride, or the like) used for a solid-state imaging element or the like can be used. Further, other layers such as an intermediate layer may be provided between the support and the colored layer to be described later, so long as the effect of the present invention is not impaired.

Further, a colored layer to be described later may be formed on the imaging element formation surface side (surface) of the substrate for a solid-state imaging element, or on the imaging element formation surface side (back surface).

A light shielding film may be provided between each imaging element in the substrate for the solid-state imaging element or on the back surface of the substrate for the solid-state imaging element.

(Ground floor)

The underlayer 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 the residue is further suppressed (hereinafter also simply referred to as " ) Is preferably 1.65 or more, more preferably 1.70 or more. The upper limit is not particularly limited, but is usually 2.0 or less.

The refractive index can be measured by using an ellipsometer manufactured by JA Woollam Japan. The measurement conditions are set at 25 DEG C at 633 nm, and an average value of 5 points is adopted.

The thickness of the base 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 of more excellent effects of the present invention.

The component contained in the ground layer is not particularly limited as long as it is a material exhibiting the refractive index. However, an organic compound having a refractive index of 1.60 or more at a wavelength of 633 nm is preferable, and a triazine ring-containing polymer is preferable .

In addition, from the viewpoint of the effect of the present invention being more excellent, it is preferable that the ground layer contains substantially no metal particles or metal oxide particles. It is intended that the total content of the metal particles and the metal oxide particles in the ground layer is 0.01 mass% or less, preferably 100 ppm or less. Since the metal particles or the metal oxide particles are not substantially contained, the flatness of the surface of the ground layer is further improved, and as a result, the adhesion to the colored layer disposed on the ground layer is more excellent.

Hereinafter, the triazine ring-containing polymer will be described in detail.

(A triazine ring-containing polymer (hereinafter simply referred to as a polymer)

The triazine ring-containing polymer is a polymer containing a triazine ring in its structure, and has at least one kind selected from the group consisting of the repeating units represented by the following formulas (1A) to (4A) Triazine ring-containing polymer. In the formulas, * represents 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 from the viewpoint of the effect of the present invention being more excellent, , Preferably 50 to 100 mol%, and more preferably 80 to 100 mol%.

[Chemical Formula 1]

In the formula (1A) or in the formula (2A), R ^1A and R ^2A 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 of the alkyl group is preferably from 1 to 20, more preferably from 1 to 10, and still more preferably from 1 to 3, from the viewpoint of further improving the heat resistance of the polymer. Further, the structure may be any of chain, branched, and cyclic.

The number of carbon atoms of the alkoxy group is preferably from 1 to 20, more preferably from 1 to 10, and still more preferably from 1 to 3, from the viewpoint of further enhancing the heat resistance of the polymer. The structure of the alkyl moiety may be any of chain, branched, and cyclic.

The number of carbon atoms of the aryl group is preferably from 6 to 40, more preferably from 6 to 16, and even more preferably from 6 to 13, in view of further enhancing the heat resistance of the polymer.

The number of carbon atoms of the aralkyl group is preferably from 7 to 20, and the alkyl moiety thereof 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 of paragraphs 0020 to 002 of WO2010 / 128661 may be taken into consideration.

As the alkoxysilyl group-containing alkylamino group, any of a monoalkoxysilyl group-containing alkylamino group, a dialkoxysilyl group-containing alkylamino group and a trialkoxysilyl group-containing alkylamino group may be used, and specific examples thereof include those described in WO2010 / 128661 .

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. Examples of the heterocycle include a pyridine ring, pyrazole ring, triazole ring, thiazole ring, isothiazole ring, oxazole ring, thiadiazole ring, pyrrole ring, isoxazole ring, thiophen ring, quinoline ring, isoquinoline ring , Pyridazine ring, pyrimidine ring and the like. Also, Ar is other than an aromatic ring and a heterocyclic ring, a divalent aliphatic hydrocarbon (preferably having a carbon number of 1 ~ 8), -O-, -S- , -SO 2 -, -N (R) - (R: alkyl group) , -CO-, -NH-, -COO-, -CONH-, or a combination thereof (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, etc.).

Among them, Ar is preferably a group represented by the formulas (3) to (19). In particular, the groups represented by formulas (6) to (19) are preferable, and the groups represented by formulas (6), (8), (9), (12), (13) .

(2)

R ¹ to R ¹²⁸ independently represent a hydrogen atom, a halogen atom, a carboxyl group, a sulfonic group, an alkyl group which may have a branched structure of 1 to 10 carbon atoms, or an alkyl group which may have a branched structure of 1 to 10 carbon atoms Alkoxy group.

W ¹ , W ² and W ³ independently represent a single bond, CR ¹³⁰ R ¹³¹ (R ¹³⁰ and R ¹³¹ are each independently a hydrogen atom or an alkyl group which may have a branched structure of 1 to 10 carbon atoms , -O-, -S-, -SO-, -SO ₂ -, or -NR ¹²⁹ - (wherein R ¹²⁹ represents a hydrogen atom, , A hydrogen atom or an alkyl group which may have a branched structure of 1 to 10 carbon atoms).

Examples of the alkyl group and the alkoxy group include the same ones as 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 independently represent a single bond, an alkylene group which may have a branched structure of 1 to 10 carbon atoms, or a group represented by formula (20).

(3)

Each of R ¹³² to R ¹³⁵ independently represents a hydrogen atom, a halogen atom, a carboxyl group, a sulfonic group, an alkyl group which may have a branched structure of 1 to 10 carbon atoms, or an alkyl group which may have a branched structure of 1 to 10 carbon atoms Alkoxy group.

Y ¹ and Y ² independently represent an alkylene group which may have a single bond or a branched structure of 1 to 10 carbon atoms.

Examples of the halogen atom, the alkyl group and the alkoxy group include the same ones as described above.

Examples of the alkylene group which may have a branched structure of 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 is a divalent organic group containing a fluorene ring, and for example, a divalent organic group represented by the following formula (21) or (22) is suitable.

[Chemical Formula 4]

Wherein, R ¹³⁶ ~ R ¹⁵⁹ are, independently of one another, a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, an alkyl group which may have a branched structure of 1 to 10 carbon atoms (however, R ¹⁵⁸ and R ¹⁵⁹ are one Or may form a ring), or an alkoxy group which may have a branched structure of 1 to 10 carbon atoms.

As the halogen atom, the same halogen atom can be mentioned.

Examples of the alkyl group which may have a branched structure of 1 to 10 carbon atoms include the same ones as described above.

Examples of the ring formed by R < ¹⁵⁸ > and R < ¹⁵⁹ > together are a cyclopentyl ring and a cyclohexyl ring.

Examples of the alkoxy group which may have a branched structure of 1 to 10 carbon atoms include the same ones as described above.

Among them, a hydrogen atom is preferable as R ¹³⁶ to R ¹⁵⁹ .

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

[Chemical Formula 5]

Of these, the groups represented by the following formulas are more preferable because a polymer having a higher refractive index can be obtained.

[Chemical Formula 6]

In addition, from the standpoint of expressing a high refractive index, the Ar portion is preferably a rigid structure having a cyclic skeleton such as a fluorene skeleton or a carbazole skeleton because the Ar portion tends to gather densely and the electron density improves, Since the benzene ring has a small structure, the Ar part is easy to gather densely and the electron density is improved.

As the linking group of the 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 preferably a hydrogen atom (when R ^1A and / or R ^2A is a hydrogen atom) And it is more preferable that the Ar portion is more likely to gather densely and the electron density is improved.

From the above viewpoint, the group represented by the following formula is preferable.

(7)

The aryl group represented by the following formula is more preferable in that it exhibits a higher refractive index.

[Chemical Formula 8]

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

[Chemical Formula 9]

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

[Chemical formula 10]

In the formula, R ^1A , R ^2A and R ⁷⁷ to R ⁸⁰ have the same meanings as defined above.

From this point of view, particularly suitable repeating unit structures include those represented by the following formula (26), and a hyper branched polymer (hyperbranched polymer) represented by the following formula (27) is the most suitable.

(11)

Wherein R &^lt; ^1A &^gt; and R &^lt; ^{2A >} have the same meanings as defined above.

[Chemical Formula 12]

The production method of the triazine ring-containing polymer having the repeating unit represented by the formula (1A) or the formula (2A) is not particularly limited, and includes the methods described in paragraphs 0051 to 0069 of WO2010 / 128661.

Next, Expression (3A) will be described.

[Chemical Formula 13]

Ar in formula (3A) is not particularly limited as long as it is a divalent organic group including at least one of an aromatic ring and a heterocyclic ring. In the present invention, the above-mentioned formulas (3) to (19) (10), (11), (13) and (14) is particularly preferable.

In the case of formulas (10) and (11), it is preferable that W ¹ and W ² are S (sulfur atom).

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

[Chemical Formula 14]

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

[Chemical Formula 15]

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

[Chemical Formula 16]

Suitable repeating unit structures include those represented by the following formulas, but are not limited thereto.

[Chemical Formula 17]

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 include the methods described in paragraphs 0036 to 0048 of Japanese Laid-Open Patent Publication No. 2012-97175.

Next, the equation (4A) will be described.

[Chemical Formula 18]

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, ≪ / RTI >

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 which may be substituted with W;

W represents an alkyl group of 1 to 10 carbon atoms, an alkoxy group of 1 to 10 carbon atoms, or a hydroxy group, and n represents 0 or an integer of 1 or more.

The number of carbon atoms of the alkyl group is from 1 to 10, but from the viewpoint of further enhancing the heat resistance of the polymer, the number of carbon atoms is more preferably from 1 to 5, and still more preferably from 1 to 3 carbon atoms.

The number of carbon atoms of the alkoxy group is from 1 to 10, more preferably from 1 to 5, and still more preferably from 1 to 3, from the viewpoint of further increasing the heat resistance of the polymer. The structure of the alkyl moiety may be any of chain, branched, and cyclic.

The structure of the alkyl group and the alkoxy group is not particularly limited, and the description of the alkyl group described in paragraph 0019, paragraph 0020 of Japanese Laid-Open Patent Publication No. 2012-097176 may be taken into consideration in the present specification.

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

Specific examples of the naphthyl group which may be substituted with W include an? -Naphthyl group and? -Naphthyl group.

The number of carbon atoms of the alkylene group is from 1 to 10, more preferably from 1 to 5, and still more preferably from 1 to 3, from the viewpoint of further improving the heat resistance of the polymer. Further, the structure may be any of chain, branched, and cyclic.

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.

As specific examples of the phenylene group which may be substituted with W, at least one of a p-phenylene group, a m-phenylene group, an o-phenylene group and hydrogen atoms contained in these phenylene groups is substituted with W, An alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a hydroxy group.

In the formula (4A), R ^4A to R ^9A are preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group 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.

When n is 0 or an integer of 1 or more, it is not particularly limited, but is preferably 0 or an integer of 1 to 8.

Suitable repeating unit structures in the present invention include those represented by the following formulas, but are not limited thereto.

In the formula, n is the same as described above.

[Chemical Formula 19]

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 include the methods described in paragraphs 0028 to 0044 of JP-A No. 2012-97176.

It is also preferable that the triazine ring-containing polymer contained in the ground layer is a polymer obtained by curing a polymerizable monomer containing at least a polymerizable monomer represented by the following formula (10A).

[Chemical Formula 20]

Type (10A) of, X ⁴ ~ 1 or 2 of X ^6, the formula (11A) or formula (12A) (formula (11A) of, R ¹⁴² is a hydrogen atom, an alkyl group or carbon number of 1 to 10 carbon atoms a group represented by represents an alkenyl group of ^{2 ~ 10), X 4 ~} X 6 of the other, the equation (13A) or formula (14A) (formula (13A) of, R ¹⁴³ and R ¹⁴⁴ are each independently a phenyl group Or a naphthyl group).

[Chemical Formula 21]

The weight average molecular weight of the polymer is not particularly limited, but is preferably 500 to 500,000, more preferably 1,000 to 100,000, more preferably 2,000 or more in view of improving the heat resistance and lowering the shrinkage rate, Is preferably 50,000 or less, more preferably 30,000 or less, and even more preferably 10,000 or less in view of increasing the viscosity of the obtained solution and lowering the viscosity of the obtained solution.

The weight average molecular weight in the present invention is an average molecular weight obtained by gel permeation chromatography (hereinafter referred to as GPC) analysis in terms of standard polystyrene.

In the present invention, a commercially available high refractive index resin can be suitably used. Open the product name (product number) below.

(1) Ultra high refractive index and high heat resistant coating materials: UR-108, UR-202, UR-501, HR-102 (manufactured by Nissan Kagaku Kogyo Co.,

(2) High refractive index coating material for thick film: UR-108, UR-204, HR-201 (manufactured by Nissan Kagaku Kogyo Co., Ltd.)

(3) Thioepoxy resin LPH1101 (manufactured by Mitsubishi Gas Kagaku Co., Ltd.)

(4) Episulfide resin MR-174 (manufactured by Mitsui Chemicals, Inc.)

(5) Thiourethane resin MR-7 (manufactured by Mitsui Chemicals, Inc.)

The content of the polymer in the base layer is not particularly limited, but is preferably 40% by mass or more, and more preferably 70 to 95% by mass, based on the total mass of the base layer, from the viewpoint of more excellent effects of the present invention.

The base layer may contain other components (for example, a surfactant, adhesion improver, etc.) other than the polymer. Examples of the surfactant and adhesion improver include the examples described in the surfactant and adhesion improver contained in the coloring and radiation-sensitive composition described later.

The base layer may further contain a high refractive index low molecular weight compound. The high refractive index low molecular weight compound may be a low molecular weight compound (high refractive index low molecular weight compound) having a structure capable of exhibiting a high refractive index, or may contain a polymerizable group. That is, the high refractive index low molecular weight compound may be a "polymerizable monomer" (a compound containing a polymerizable group) or a "low molecular weight compound" (a compound containing no polymerizable group), but a "low molecular weight compound" is preferable.

The molecular weight of the high refractive index low molecular weight compound is not particularly limited, but is preferably 3000 or less, more preferably 800 or less, still more preferably 600 or less.

The high-refractive-index low-molecular-weight compound also functions as a sensitivity adjusting agent in the base layer forming composition, and the yield can be improved in the film forming process by adjusting the content. The content of the high refractive index low molecular weight compound is not particularly limited, but is preferably 10 mass% or less, more preferably 7 mass% or less, and particularly preferably 5 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 weight compound, the refractive index can be further increased as compared with a triazine ring-containing polymer alone.

As the high refractive index low molecular weight compound, it is preferable that the high refractive index low molecular weight compound has the same structure as the structure which expresses the high refractive index of the triazine ring containing polymer. Specific examples of the high refractive index low molecular weight compound include a compound having a triazine ring structure (formula (A)) or a compound having a fluorene structure (formula (B)). 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 such as a (meth) acryloyl group or a vinyl group).

The high refractive index low molecular weight compound may be contained in a composition for forming a base layer to be described later, and the content thereof is preferably in the above range.

[Chemical Formula 22]

(Method of forming underlayer)

The method of forming the foundation layer is not particularly limited and a known method can be employed. For example, a composition for forming an undercoat layer containing a material for forming a base layer such as the polymer described above is applied on a support, and a curing treatment (for example, a heat treatment and / or an exposure treatment) May 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.

More specifically, when a base layer having a thickness of 1.0 탆 is formed by the composition, the light transmittance of the base layer in the thickness direction is preferably from 400 to 700 nm Is not less than 90% over the whole wavelength region of the wavelength region of the visible light.

That is, the base layer is preferably a film having a light transmittance of 90% or more over the entire wavelength range of 400 to 700 nm in the film thickness direction of 1.0 占 퐉.

The light transmittance is preferably 95% or more, more preferably 99% or more, and most preferably 100%, over the entire wavelength range of 400 to 700 nm.

It is preferable that the composition for forming the foundation layer substantially contains no coloring agent described later. More specifically, the content of the colorant is preferably 0 mass% with respect to the total solid content of the composition.

The base layer 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, surfactant and adhesion improver include the examples described in the solvent, surfactant, and adhesion improver included in the coloring and radiation-sensitive composition described later.

The crosslinking agent is not particularly limited as long as it is a compound having a substituent capable of reacting with the above-mentioned polymer.

As such a compound, a compound containing a crosslinking forming substituent such as a melamine compound having a crosslinking forming substituent such as a methylol group or a methoxymethyl group, a substituted urea compound, an epoxy group or an oxetane group, a compound containing a blocked isocyanate , A compound having an acid anhydride, a compound having a (meth) acryl group, and a phenoplast compound. From the viewpoint of heat resistance and storage stability, a compound having an epoxy group, a block isocyanate group and a (meth) desirable.

The composition for forming the undercoat layer preferably has a low content of salts such as NaCl, preferably 100 mass ppm or less, more preferably 50 mass ppm or less. 1 mass ppm or more is preferable, and 5 mass ppm or more is more preferable. When the salt content is not more than the predetermined value, occurrence of defects of the film is further suppressed. In addition, by adding a small amount of salt, it functions as a pattern shape adjuster, and when a pattern is formed by photolithography, a desired pattern can be easily formed. The salt content can be adjusted by filtration.

≪ Coloring layer forming step &

The coloring layer forming step is a step of forming a colored layer on the base layer described above by using a coloring and radiation sensitive composition comprising (A) a colorant (preferably a pigment), (B) a polymerization initiator, and (C) Thereby forming a colored layer. The color of the coloring layer is not particularly limited and can be appropriately adjusted according to the type of the coloring agent to be used. Examples of the coloring layer include a red coloring layer, a green coloring layer, and a blue coloring layer. You can.

Hereinafter, the coloring and radiation-sensitive composition used in the present step will be described in detail first, and the sequence of steps thereafter will be described in detail.

(Hereinafter, simply referred to as "composition" "composition of the present invention"),

The coloring and 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 pigments or dyes of a rape color system (red, magenta, yellow, blue, cyan, and green), black pigments or dyes are used.

As the pigments of the raindrop series, various conventionally known inorganic pigments or organic pigments can be used. In view of the fact that the inorganic pigment or the organic pigment is preferably a high transmittance, it is preferable to use as fine as possible, and considering the handling property, the average primary particle diameter of the pigment is preferably from 0.01 mu m to 0.1 mu m , And more preferably 0.01 mu m to 0.05 mu m.

Examples of the inorganic pigments include metallic compounds represented by metal oxides and metal complex salts and specifically include metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, Oxides and complex oxides of metals. Nitrides of titanium, silver tin compounds, silver compounds, and the like can also be used.

Examples of pigments that can be preferably used in the present invention include the following pigments. However, the present invention is not limited thereto.

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

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

CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 81: 2, 81: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 175, 176, 177, 178, 179, 170, 176, 168, 169, 170, 171, 172, 175, 176, 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

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 singly or in various combinations in order to enhance color purity.

As the pigment, an inorganic pigment may be used as described above. Examples of the inorganic pigment include metal pigments, metal-containing inorganic pigments such as metal compounds and metal oxides, and carbon black.

The composition may be used not only for forming a coloring region (pixel) of a color filter but also for forming a black matrix. Examples of the black pigment used for the black matrix forming composition include carbon black, titanium black, iron oxide, Tin, silver and the like, a metal mixture containing a metal oxide such as titanium oxide, or the like can be used. Examples of commercially available products of titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N manufactured by Mitsubishi Materials Corporation and Tilack D manufactured by Ako Kasei Co.,

As the pigment, a pigment which satisfies an average particle diameter (r) of 20 nm? R? 300 nm, preferably 125 nm? R? 250 nm, particularly preferably 30 nm? R? 200 nm is preferable. By using such a pigment having an average particle diameter, a pixel having a high contrast ratio and a high light transmittance can be obtained. The "average particle diameter" as used herein means an average particle diameter of secondary particles in which primary particles (single crystals) of a pigment are aggregated. The average primary particle size can be obtained by observing with SEM or TEM, measuring 100 particle sizes at the portion where particles are not aggregated, and calculating an average value.

The particle size distribution (hereinafter simply referred to as "particle size distribution") of the secondary particles of the pigment that can be used in the present invention is such that the secondary particles reaching the (average particle diameter ± 100) nm are not less than 70% It is preferably at least 80% by mass. In the present invention, the particle size distribution was measured using the scattering intensity distribution.

The above-mentioned pigment having an average particle diameter and a particle diameter distribution is a pigment mixture in which commercially available pigments are mixed with other pigments (average particle diameter is usually more than 300 nm) used as occasion demands, preferably with a dispersant and a solvent, For example, by pulverizing using a pulverizer such as a bead mill or a roll mill. The pigment thus obtained usually takes the form of a pigment dispersion.

The content (concentration) of the pigment contained in the composition is preferably 40% by mass or more, more preferably 45% by mass or more, and more preferably 50% by mass or more of the total solid content of the composition, desirable. The upper limit is not particularly limited, but is preferably 75% by mass or less.

The dye is not particularly limited, and a known dye can be appropriately selected and used. For example, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, JP-A-2592207 , U.S. Patent No. 4,808,501, U.S. Patent No. 5,667,920, U.S. Patent No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-211599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283 Japanese Patent Application Laid-Open Nos. 7-286107, 2001-4823, 8-15522, 8-29771, and 8-146215 , Japanese Unexamined Patent Application Publication No. 11-343437, Japanese Unexamined Patent Application, First Publication No. Hei 8-62416, Japanese Unexamined Patent Application, First Publication No. 2002-14220, Japanese Patent Application Laid-Open Nos. 2002-14221, 2002-14222, 2002-14223, 8-302224, 8-73758, 8-179120, and 8-151531.

Examples of the chemical structure include a pyrazolone group, anilino group, triphenylmethane group, anthraquinone group, anthrapyridone group, benzilidene group, oxolin group, pyrazolotriazole group, pyridazo group, , Pyrrolopyrazole azo methain, zanthene, phthalocyanine, benzopyran, indigo and the like can be used. These dyes may be multimers.

(Dispersant)

Further, in the composition of the present invention, it is preferable to add a dispersant in order to further improve the dispersibility of the pigment.

Examples of the dispersant (hereinafter also referred to as "pigment dispersant") include polymer dispersants (for example, polyamide amines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethane, (Meth) acrylic copolymer, naphthalenesulfonic acid-formalin condensate) and polyoxyethylene alkylphosphoric acid ester, polyoxyethylene alkylamine, alkanolamine, pigment derivative and the like .

The polymer dispersant can be classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer from the structure.

The polymer dispersant adsorbs on the surface of the pigment and acts to prevent re-aggregation. Accordingly, a terminal modified polymer, graft-type polymer, and block-type polymer having an anchor site to the pigment surface are preferable 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 the pigment dispersant usable in the present invention include Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide), 161, BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), BYK2001 ", manufactured by EFKA" EFKA 4047, 4050, 4010, 4165 (polyurethane copolymer) (Modified polyacrylate), 5010 (polyester amide), 5765 (high molecular weight polycarboxylic acid salt), 6220 (fatty acid polyester), 6745 (phthalate), EFKA 4330, 4340 (block copolymer), 4400, 6750 (azo pigment derivative) "manufactured by Ajinomoto Fine Techno Co., Ltd." Ajisper PB821, PB822 "manufactured by Ajinomoto Fine Techno Co., Ltd.," Floren TG-710 (uretene oligomer) "manufactured by Kyoeisha Chemical Co., 50E, No.300 (acrylic copolymer) ", Dysparon KS-860, 873SN, 874, # 2150 (aliphatic polyvalent carboxylic acid) manufactured by Kusumoto Chemical Co., N (naphthalene sulfonic acid-formaldehyde polycondensate), MS, C, SN-B (aromatic polyester), "# 7004 (polyetherester), DA-703-50, DA-705, DA- (Polyoxyethylene nonylphenyl ether) ", "acetamin 86 (stearyl polyoxyethylene nonylphenyl ether) ", " Homogenol L-18 (polymeric polycarboxylic acid) "," Emulgen 920, 930, 935, 985 Amine acetate) ", manufactured by Lubrizol Corporation," Sol Spurs 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 17000, 27000 , 28000, 32000 and 38500 (graft polymer), NIKKOL T106 (polyoxyethylene sorbitan monooleate) and MYS-IEX (polyoxyethylene monostearate) manufactured by Nikko Chemical Co.,

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 polymeric dispersing agent.

The content of the dispersant in the composition of the present invention is preferably from 1 to 100% by mass, more preferably from 3 to 100% by mass, and still more preferably from 5 to 80% by mass, based on the pigment. Further, it is preferably 10 to 30% by mass relative to the total solid content of the composition.

<Polymerization Initiator>

The composition of the present invention includes a polymerization initiator. The polymerization initiator may be used alone or in combination of two or more, and in the case of two or more types, the total amount is in 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 still more preferably 0.1 to 15% by mass, based on the solid content of the composition of the present invention. 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 the polymerizable compound by either or both of light and heat, and can be appropriately selected in accordance with the purpose, but is preferably a photopolymerization initiator. In the case of initiating polymerization by light, it is preferable to have photosensitivity to visible light from the ultraviolet region.

When heat polymerization is initiated, a polymerization initiator which decomposes at 150 to 250 캜 is preferable.

The polymerization initiator usable in the present invention is preferably a compound having at least an aromatic group, and examples thereof include an acylphosphine compound, an acetophenone compound, an? -Amino ketone compound, a benzophenone compound, a benzoin ether compound, The present invention relates to a process for producing a compound represented by the general formula (I), a thiazonone compound, an oxime compound, a hexaarylbaimidazole compound, a trihalomethyl compound, an azo compound, an organic peroxide, a diazonium compound, an iodonium compound, An onium salt compound such as a ketal derivative compound and a metallocene compound, an organic boron salt compound, and a disulfone compound.

From the viewpoint of sensitivity, oxime compounds, acetophenone compounds,? -Amino ketone compounds, trihalomethyl compounds, hexaarylbaiimidazole compounds and thiol compounds are preferable.

Specific examples of the acetophenone compound, the trihalomethyl compound, the hexaaryl bimidazole compound and the oxime compound are described in Japanese Laid-Open Patent Publication No. 2012-208494, paragraphs 0506 to 0510 (corresponding US Patent Application Publication No. 2012/0235099 [0622 to 0628]), which are incorporated herein by reference.

As the photopolymerization initiator, compounds selected from the group consisting of oxime compounds, acetophenone compounds and acylphosphine compounds are more preferred. More specifically, for example, an aminoacetophenone-based initiator disclosed in Japanese Patent Application Laid-Open No. 10-291969, an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898, a oxime-based initiator described above, The compounds described in JP 2001-233842 A can also be used.

As the oxime type initiator, commercially available IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) can be used. As the acetophenone-based initiator, commercially available IRGACURE-907, IRGACURE-369 and IRGACURE-379 (all trade names, all manufactured by BASF Japan) can be used. As the acylphosphine-based initiator, commercial products IRGACURE-819 and DAROCUR-TPO (all trade names, all manufactured by BASF Japan) can be used.

Examples of the oxime-based initiator (oxime-based polymerization initiator) include compounds represented by the following formulas (OX-1), (OX- 2) or (OX-3), the contents of which are incorporated herein by reference.

As the oxime type initiator, commercial products such as TRONLY TR-PBG-304, TRONLY TR-PBG-309 and TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD. Can also be used. Also, the description of the polymerization initiator described in paragraph 0096 of paragraph [0092] of Japanese Laid-Open Patent Publication No. 2012-113104 may be taken into consideration, and the contents thereof are incorporated herein by reference. By using such a oxime-based initiator, a resin composition having high curability and high developability can be provided. The oxime-based initiator is a compound described in JP-A-2012-113104, column &quot; 0030 &quot; The general formula is represented by the general formula (I) described in claim 1 of the method of Japanese Laid-Open Patent Publication No. 2012-113104, more preferably represented by the general formula (IA) described in claim 3, , The contents of which are incorporated herein by reference.

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 wavelength of the photosensitive wavelength. As the sensitizer usable in the present invention, it is preferable to increase or decrease the amount of the polymerization initiator by an electron transfer mechanism or an energy transfer mechanism.

As the sensitizer, for example, compounds described in paragraphs 0101 to 0154 of JP-A No. 2008-32803 can be mentioned.

The content of the sensitizer in the composition of the present invention is preferably from 0.1% by mass to 20% by mass, more preferably from 0.5% by mass to 20% by mass, in terms of solid content, To 15% by mass is more preferable.

The sensitizer may be used alone, or two or more may be used in combination.

(Polymerizable compound)

As the polymerizable compound, any compound that is polymerized by the polymerization initiator may be used, and a known polymerizable compound may be used.

Among them, from the viewpoint of polymerizability, an addition polymerizable compound having at least one ethylenic unsaturated double bond may be used, or a compound having at least one, preferably two or more, terminal ethylenic unsaturated bonds is preferably used .

Of these, a polymerizable compound having three or more ethylenically unsaturated double bonds (hereinafter sometimes referred to as a "multifunctional monomer") is preferable as the polymerizable compound from the viewpoint of better adhesion of the colored layer. These compounds are well known in the art and can be used in the present invention without particular limitation. The multifunctional monomers in the present invention may be used singly or in combination of two or more. The multifunctional monomer used in the present invention is preferably a (meth) acrylate monomer.

As specific compounds of these compounds, compounds described in paragraphs 0095 to 0108 of JP-A-2009-288705 can be suitably used in the present invention.

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

(23)

Wherein n is 0 to 14 and m is 1 to 8, respectively. The 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's are polymerizable groups.

n is preferably 0 to 5, more preferably 1 to 3.

m is preferably from 1 to 5, more preferably from 1 to 3.

R &lt;

&Lt; EMI ID =

Lt; / RTI &gt;

(25)

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 paragraphs 0248 to 0251 of JP-A No. 2007-269779 And can be suitably used.

Among them, dipentaerythritol triacrylate (KAYARAD D-330 manufactured by Nippon Kayaku K.K.) and dipentaerythritol tetraacrylate (KAYARAD D-320 manufactured by Nippon Kayaku Co., Ltd.) (Trade name: KAYARAD D-310, manufactured by Nippon Kayaku K.K.), dipentaerythritol hexa (meth) acrylate (KAYARAD DPHA; Nippon Kayaku Co., Ltd.) and a structure in which these (meth) acryloyl groups interpose ethylene glycol and propylene glycol residues are preferable. These oligomer types can also be used.

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

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

(26)

In the general formulas (i) and (ii), E represents - ((CH ₂ ) _y CH ₂ O) - or - ((CH ₂ ) _y CH (CH ₃ ) , 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 sum of the acryloyl group and the methacryloyl group is 3 or 4, m is an integer of 0 to 10, and the sum of m is an integer of 1 to 40 .

In the general formula (ii), the sum of the acryloyl group and the methacryloyl group is 5 or 6, and n is an integer of 0 to 10, and the sum of n is an integer of 1 to 60.

In the formula, E, _{respectively, - ((CH 2) y} CH 2 O) -, or _{- ((CH 2) y CH} (CH 3) O) - represents _{the, - ((CH 2) y} CH 2 O) - is preferred.

y each represent an integer of 1 to 10, preferably an integer of 1 to 5, more preferably 1 to 3.

X represents a hydrogen atom, an acryloyl group, a methacryloyl group or a carboxyl group, respectively.

In the general formula (i), the total of the acryloyl group and the methacryloyl group is 3 or 4, preferably 4.

m each represents an integer of 0 to 10, preferably 1 to 5; The sum of each m is an integer of 1 to 40, preferably 4 to 20.

In the general formula (ii), the total of the acryloyl group and the methacryloyl group is 5 or 6, preferably 6.

n each represent an integer of 0 to 10, preferably 1 to 5; The sum of n is an integer of 1 to 60, preferably 4 to 30.

The multifunctional monomer may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Thus, if the ethylenic compound has an unreacted carboxyl group as in the case of the mixture as described above, it can be used as it is. If necessary, the nonylic carboxylic acid anhydride is reacted with the hydroxyl group of the ethylenic compound described above An acid group may be introduced. In this case, specific examples of the non-aromatic carboxylic acid anhydrides to be used include anhydrous tetrahydrophthalic acid, alkylated anhydrous tetrahydrophthalic acid, anhydrous hexahydrophthalic acid, alkylated anhydrous hexahydrophthalic acid, succinic anhydride, and maleic anhydride.

In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, which is obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a nonaromatic carboxylic acid anhydride to give an acid group, Monomers are preferred, and particularly preferred in this ester is aliphatic polyhydroxy compound pentaerythritol and / or dipentaerythritol. Commercially available products include, for example, M-305, M-510, and M-520 of Aronix series as a polybasic acid-modified acrylic oligomer made by Toagosei Co.,

The preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg KOH / g, particularly preferably 5 to 30 mg KOH / g.

For these polyfunctional monomers, the details of the structure, the single use, the combination use, the amount of addition, and the like can be arbitrarily set in accordance with the final performance design of the composition. In the present invention, a method of controlling both sensitivity and strength by using other functional water and / or other polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound) Do. Further, it is preferable to use other multifunctional monomers having three or more functional groups and less than eight functional groups on the chain of ethylene oxide from the viewpoint that the developability of the composition can be controlled and excellent pattern forming ability can be obtained. The compatibility and dispersibility with other components (for example, a polymerization initiator, a coloring agent (pigment), a resin, etc.) contained in the composition is also an important factor for selecting and using the polyfunctional monomer. For example, The compatibility may be improved by the use of the compound or by the combined use of two or more compounds. In addition, a specific structure may be selected from the viewpoint of improving adhesion with a hard surface such as a substrate.

The concentration (mixing ratio) of the polymerizable compound (in particular, the multifunctional monomer) is preferably 15% by mass or more, more preferably 20% by mass or more, and more preferably 25% by mass or more based on the total solid content in the composition, % Or more. The upper limit is not particularly limited, but is preferably 50 mass% or less, and more preferably 40 mass% or less.

(Other optional components)

The composition may contain components other than the pigment (A), the polymerization initiator (B), and the polymerizable compound (C). Examples thereof include an alkali-soluble resin, an acrylic polymer having a polymerizable group, a dispersant, a solvent, a surfactant, a polymerization inhibitor, an adhesion improver, and an ultraviolet absorber.

Hereinafter, the optional components will be described in detail.

(Alkali-soluble resin)

As the alkali-soluble resin, a linear organic polymer can be appropriately selected from an alkali-soluble resin having at least one group capable of promoting alkali solubility in a molecule (preferably an acrylic copolymer, a styrene-based copolymer as a main chain) . From the viewpoint of heat resistance, a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin and an acryl / acrylamide copolymer resin are preferable. From the viewpoint of development control, an acrylic resin, an acrylamide resin , An acrylic / acrylamide copolymer resin is preferable.

Examples of the group capable of promoting alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group and the like, but they are preferably soluble in a solvent and developable by a weakly alkaline aqueous solution, (Meth) acrylic acid is particularly preferable. These acid groups may be only one kind, or two or more kinds.

Examples of the monomer capable of giving an acid group after polymerization include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, monomers having an epoxy group such as glycidyl (meth) acrylate, And an isocyanate group-containing monomer such as an ethyl (meth) acrylate. The monomers for introducing these acid groups may be one kind or two or more kinds. In order to introduce an acid group into the alkali-soluble resin, for example, a monomer having an acid group and / or a monomer capable of giving an acid group after polymerization (hereinafter sometimes referred to as " monomer for introducing an acid group ") is used as a monomer component The polymerization may be carried out.

When an acid group is introduced as a monomer component capable of imparting an acid group after polymerization, a treatment for giving an acid group, for example, is required after polymerization.

For the production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as the temperature, pressure, kind and amount of the radical initiator and the type of the solvent when the alkali-soluble resin is produced by the radical polymerization method can be easily set by those skilled in the art, have.

As the linear organic polymer used as an alkali-soluble resin, a polymer having a carboxylic acid in its side chain is preferable, and a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, Maleic acid copolymer, novolac-type resin and the like, acidic cellulose derivatives having a carboxylic acid in the side chain, and acid anhydrides added to the polymer having a hydroxyl group. Particularly, a copolymer of (meth) acrylic acid and other monomers copolymerizable therewith is suitable as an alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compounds. Examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hexyl (meth) (Meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. Examples of the vinyl compound include styrene, Vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate As above, N-substituted maleimide monomers such as the monomer described in Black, Japanese Laid-Open Patent Publication No. Hei 10-300922, and the like can be mentioned N- phenyl maleimide, N- cyclohexyl maleimide.

As the other monomer copolymerizable with (meth) acrylic acid, for example, it is also preferable to be a monomer which gives a repeating unit represented by the following formula (X).

(27)

Wherein 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, and n represents an integer of 1 to 15 Lt; / RTI &gt; The repeating unit represented by the formula (X) has good adsorption and / or orientation to the surface of the colorant (particularly, pigment) due to the effect of the pi electrons of the benzene ring present in the side chain. Particularly, when the side chain moiety has the ethylene oxide or propylene oxide structure of para-cumylphenol, the stereosubstance is also added, so that a better adsorption and / or orientation plane can be formed with respect to the colorant (in particular, the pigment) , It is more effective and preferable. R ^3X represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, but is preferably an alkyl group having 1 to 20 carbon atoms. When R ^3X is an alkyl group, an alkyl group having 1 to 10 carbon atoms is particularly preferable. When R ^3X is an alkyl group having 1 to 10 carbon atoms, the alkyl group is impaired to inhibit the approach of resins to each other to promote adsorption and / or orientation to a colorant (in particular, a pigment). When the number of carbon atoms exceeds 10, And the adsorption and / or orientation to the surface of the benzene ring coloring agent (particularly, pigment) may be disturbed. This phenomenon becomes remarkable as the chain length of the alkyl group of R ^3X becomes longer. When the number of carbon atoms exceeds 20, the adsorption and / or orientation of the benzene ring is extremely lowered. As a result, the alkyl group represented by R ^3X has a carbon number of 1 to 20. As the alkyl group represented by R ^3X , an unsubstituted alkyl group or an alkyl group substituted with a phenyl group is preferable.

In addition, R ^2X in the 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).

(28)

The formula (Y), and ^{of, R 1X, R 2X, R} 3X and n, R ^1X, R ^2X, and R ^3X n and copper in the formula (X), preferred examples are the same.

Examples of the ethylenic unsaturated monomer represented by the formula (Y) include phenol ethylene oxide modified (meth) acrylate, para-cumylphenol ethylene oxide modified (meth) acrylate, nonylphenol ethylene oxide modified (meth) acrylate, nonylphenol propylene oxide modified (Meth) acrylate, and the like.

In addition, these monomers copolymerizable with (meth) acrylic acid may be either one type alone or two or more types.

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

[Chemical Formula 29]

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

It is possible to form a cured coating film having excellent heat resistance as well as transparency by using a resin obtained by polymerizing a monomer component containing a compound represented by formula (ED) (hereinafter sometimes referred to as "ether dimer ").

In the general formula (ED) representing the ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited and includes, for example, methyl, ethyl, A linear or branched alkyl group such as methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl or 2-ethylhexyl; An aryl group such as phenyl; An alicyclic group such as a cyclohexyl group, a t-butyl group, a cyclohexyl group, a dicyclopentadienyl group, a tricyclodecanyl group, an isobornyl group, an adamantyl group and a 2-methyl-2-adamantyl group; An alkyl group substituted by an alkoxy such as a 1-methoxyethyl group or a 1-ethoxyethyl group; An alkyl group substituted with an aryl group such as benzyl; And the like. Among these, an acid such as a methyl group, an ethyl group, a cyclohexyl group, a benzyl group and the like, or a substituent of a primary or secondary carbon which is difficult to be removed by heat, is preferable from the viewpoint of heat resistance.

As concrete examples of the ether dimer, the description of the ether dimmer of Japanese Patent Laid-Open Publication No. 2012-208494, Publication No. 0565 (corresponding to United States Patent Application Publication No. 2012/235099 [0694]), .

Among these, dimethyl-2,2'- [oxybis (methylene)] bis-2-propenoate, diethyl-2,2 '- [oxybis (methylene)] bis- Propylene glycol dicyclohexyl-2,2 '- [oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2' - [oxybis (methylene)] bis-2-propenoate. These ether dimers may be either one kind or two or more kinds. The structure derived from the compound represented by the formula (ED) may be copolymerized with another monomer.

As the alkali-soluble resin, a multi-component copolymer comprising benzyl (meth) acrylate / (meth) acrylic acid copolymer and benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl methacrylate is particularly suitable. Examples of other monomers in this case include 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy- 3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer , 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, and the like.

The acid value of the alkali-soluble resin is preferably 30 to 200 mgKOH / g, more preferably 50 to 150 mgKOH / g, and even more preferably 70 to 120 mgKOH / g. Such a range makes it possible to effectively reduce the development residue of the unexposed portion.

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 from 10 to 50 mass%, more preferably from 15 to 40 mass%, and particularly preferably from 20 to 35 mass%, based on the total solid content of the composition. to be.

<Solvent>

The composition of the present invention can be generally constituted by using a solvent. The solvent is not particularly limited if it satisfies the solubility of each component and the coating property of the composition.

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, , Methyl lactate, ethyl lactate, alkyloxyacetate (such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, Ethoxyacetic acid ethyl, etc.), 3-oxypropionic acid alkyl esters (e.g., methyl 3-oxypropionate, ethyl 3-oxypropionate (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Ethoxypropionate, ethyl 3-ethoxypropionate), 2-oxypropionic acid alkyl esters (e.g., methyl 2-oxypropionate, 2-oxypropionate Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate) Methyl 2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy- , Ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like, and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, Diethylene glycol Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono Propylene glycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol monobutyl ether, propyl ether acetate and the like, and ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone and aromatic hydrocarbons such as xylene have.

From the viewpoints of the solubility of the alkali-soluble resin, the improvement on the coated surface, etc., it is also preferable to mix two or more of these solvents. In this case, particularly preferable examples include methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate , 2-heptanone, cyclohexanone, ethylcarbitol acetate, butylcarbitol acetate, ethylene glycol monobutyl ether acetate, propylene glycol methyl ether and propylene glycol methyl ether acetate. It is a mixed solution composed of more than species.

The content of the solvent in the composition is preferably 5 to 80% by mass, more preferably 5 to 60% by mass, and more preferably 10 to 50% by mass, in terms of the total solids concentration of the composition, Particularly preferred.

<Surfactant>

Various surfactants may be added to the composition of the present invention from the viewpoint of further improving the applicability. As the surfactant, various surfactants such as a fluorine surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.

Particularly, since the composition of the present invention contains a fluorine-containing surfactant, the uniformity of liquid coating thickness and the liquid-repellency (liquid-repellency) can be improved by improving the liquid property Can be improved.

That is, in the case of forming a film using a coating liquid to which a composition containing a fluorine-containing surfactant is applied, wettability to the surface to be coated is improved by lowering the interfacial tension between the surface to be coated and the coating liquid, . Therefore, even when a thin film of about several micrometers is formed in a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with a small thickness deviation.

The fluorine content in the fluorine surfactant 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. The fluorine-containing surfactant having a fluorine content within this range is effective from the viewpoint of the uniformity of the thickness of the coating film and the lyophobic property, and the solubility in the composition is also good.

Examples of the fluorine-based surfactant include Megapak F171, Dong F172, Dong F173, Dong F176, Dong F177, Dong F141, Dong F142, Dong F143, Dong F144, Dong R30, Dong F437, Dong F475, Dong F479, Dong F482 (Manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, and SC-101 (manufactured by Sumitomo 3M Limited), F554, F780, and F781 (manufactured by DIC Corporation), Fluorad FC430, (Manufactured by Asahi Glass Co., Ltd.), PF636, PF656 (manufactured by Asahi Glass Co., Ltd.), SC-103, SC-104, SC-105, SC1068, SC-381, SC- , PF6320, PF6520, PF7002 (manufactured by OMNOVA), and the like.

Specific examples of the nonionic surfactant include glycerol, trimethylol propane, trimethylol ethane and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerine ethoxylate and the like), polyoxyethylene Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol diallylate, polyethylene glycol Diestearate and consumptive fatty acid ester (pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Pionin D- (Manufactured by Takemoto Yushi Co., Ltd.) and Solspers 20000 (manufactured by Nihon Lubrizol Corporation)).

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.) Acrylic acid type (co) polymer Polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.).

Specific examples of the anionic surfactant include W004, W005 and W017 (manufactured by YUHO Co., Ltd.).

Examples of silicon based surfactants include fluororesins such as "TORAY Silicon DC3PA", "TORAY Silicone SH7PA", "TORAY Silicon DC11PA", "TORAY Silicone SH21PA", "TORAY Silicone SH28PA", "DORAY Silicone SH29PA TSF-4440 "," TSF-4445 "," TSF-4460 "," TSF-4452 "," Tory Silicone SH8400 "and" TSF-4440 "manufactured by Momentive Performance Materials "KF341", "KF6001", and "KF6002" manufactured by Shin-Etsu Silicones Co., Ltd., "BYK307", "BYK323", and "BYK330" manufactured by Big Chemie.

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

The amount of the surfactant to be added is preferably from 0.001 mass% to 2.0 mass%, more preferably from 0.005 mass% to 1.0 mass%, based on the total mass of the composition.

<Polymerization inhibitor>

In the composition of the present invention, it is preferable to add a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polyfunctional monomer during or during the preparation of the composition.

Examples of the polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, o-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl- Salts and the like.

Further, the composition may contain a notarization sensitizer for the purpose of further improving the sensitivity to the active radiation of the sensitizing dye or the initiator, or inhibiting the polymerization inhibition of the polyfunctional monomer by oxygen. In order to improve the physical properties of the cured coating, known additives such as a diluting agent, a plasticizer, and a sensitizing agent may be added as needed.

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

&Lt; Adhesion improving agent (adhesion promoter) >

In the composition of the present invention, an adhesion improver may be added in order to improve the adhesion with a hard surface such as a substrate.

Examples of the adhesion improver include a silane-based coupling agent and a titanium coupling agent.

The silane coupling agent preferably has an alkoxysilyl group as a hydrolyzable group chemically bondable to an inorganic material. (Meth) acryloyl group, a phenyl group, a mercapto group, a glycidyl group, and an oxetanyl group are preferable as the group having a group capable of interacting or forming a bond with an organic resin and exhibiting affinity , And among them, a (meth) acryloyl group or glycidyl group is 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 more specifically, a (meth) acryloyl-trimethoxysilane Compounds, glycidyl-trimethoxysilane compounds, and the like.

(30)

The silane coupling agent in the present invention is also preferably a silane compound having at least two functional groups different in reactivity from each other in one molecule, particularly preferably having an amino group and an alkoxy group as a functional group. Examples of such a silane coupling agent include N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (trade name: KBM-602 available from Shin-Etsu Chemical Co., -Aminopropyl-trimethoxysilane (trade name: KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.), N -? - aminoethyl -? - aminopropyltriethoxysilane -602),? -Aminopropyltrimethoxysilane (trade name: KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.),? -Aminopropyltriethoxysilane (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, more preferably 0.2% by mass to 3.0% by mass, in the total solid content in the composition.

&Lt; Acrylic polymer having polymerizable group >

The composition of the present invention may contain an acrylic polymer having a polymerizable group. As the polymerizable group of the acrylic polymer having a polymerizable group, an ethylenically unsaturated bonding group is exemplified, and 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 constituent unit having a polymerizable group and another constituent unit.

The acrylic polymer in the present invention refers to a vinyl polymer having a repeating unit derived from at least one of (meth) acrylic acid, (meth) acrylic acid ester and (meth) acrylamide.

The proportion of the polymerizable group contained in the acrylic polymer having a polymerizable group is preferably from 5 to 50, and more preferably from 10 to 40. By setting this range, compatibility between hardenability and developability can be more effectively achieved. Here, the ratio of the polymerizable group means a molar copolymerization ratio.

As another structural unit, for example, a structural unit containing an acid group is exemplified. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, 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 this range, it becomes possible to enhance the solubility of the unexposed portion 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 a glycidyl group-containing unsaturated compound such as glycidyl (meth) acrylate and allyl glycidyl ether, allyl alcohol, 2-hydroxyacrylate, A resin obtained by reacting an unsaturated compound containing a free (isocyanate group) or an unsaturated acid anhydride with a resin containing a carboxyl group having a hydroxyl group, a resin obtained by reacting an epoxy resin with an unsaturated carboxylic acid , A resin obtained by reacting an addition reaction product of a conjugated diene copolymer and an unsaturated dicarboxylic acid anhydride with a polyfunctional monomer containing a hydroxyl group, a resin obtained by reacting a polyfunctional monomer with an addition reaction product of a conjugated diene copolymer with an unsaturated dicarboxylic anhydride, A resin having a specific functional group is synthesized, and the resin is subjected to a base treatment A resin obtained by forming an unsaturated group as a typical resin.

As the acrylic polymer having a polymerizable group, the description of paragraphs 0043 to 0067 of Japanese Laid-Open Patent Publication No. 2009-79150 may be taken into consideration and the contents thereof are incorporated herein by reference. Further, the description of Polymer Compounds 1 to 22 in paragraphs 0063 to 0067 of Japanese Patent Laid-Open Publication No. 2009-79150 may be taken into consideration and the contents thereof are incorporated herein by reference.

<Other components>

The composition of the present invention may be appropriately selected and used in addition to the essential components and the optional additives as long as the effects of the present invention are not impaired.

Examples of other components that can be used in combination include a binder polymer, a dispersant, a sensitizer, a crosslinking agent, a curing accelerator, a filler, a thermosetting accelerator, a thermal polymerization inhibitor, a plasticizer and an ultraviolet absorber. Adhesion promoters and other additives (for example, conductive particles, fillers, defoamers, flame retardants, leveling agents, release promoters, antioxidants, fragrances, surface tension regulators, chain transfer agents and the like) may be used in combination.

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

These components are described, for example, in Japanese Patent Laid-Open Publication No. 2012-003225, paragraphs 0183 and 2013 (corresponding to [0237] of U.S. Patent Application Publication No. 2013/0034812), Japanese Patent Application Publication No. 2008-250074 0101 to 0102, paragraph numbers 0103 to 0104, and paragraph numbers 0107 to 0109 can be taken into consideration, and these contents are incorporated herein by reference.

&Lt; Preparation of composition >

The preparation of the composition of the present invention is not particularly limited, but it may be prepared by mixing, for example, the essential components of the present invention and various additives used in combination according to the purpose.

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

The filter used for the filter filtration is not particularly limited as long as it is a filter that has been conventionally used for filtration.

Examples of the filter material include fluororesins such as PTFE (polytetrafluoroethylene); Polyamide based resins such as nylon-6, nylon-6,6 and the like; Polyolefin resins (including high density, ultra high molecular weight) such as polyethylene and polypropylene (PP); And the like. Of these materials, polypropylene (including high-density polypropylene) is preferable.

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

By setting the pore diameter of the filter within the above-mentioned range, fine particles can be removed more effectively, and turbidity can be further reduced.

Here, the hole diameter of the filter can refer to the nominal value of the filter manufacturer. As a commercially available filter, there may be selected, for example, various filters provided by Nippon Oil Corporation, Advantech Toyokawa Co., Ltd., Nippon Integrity Corporation (formerly Nihon Micro-Roller Corporation) or Kitsch Microfilter .

In filter filtration, two or more kinds of filters may be used in combination.

For example, first, filtration is performed using a first filter, and then filtration can be performed using a second filter having a different pore diameter from the first filter.

At this time, the filtering in the first filter and the filtering in the second filter may be performed only once or two or more times, respectively.

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

The composition of the present invention is preferably applied by inkjet, and preferably has 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 a discharging temperature is preferably 100 mPa · s or less, more preferably 50 mPa · s or less, It is preferable to adjust the composition ratio as appropriate.

The viscosity of the composition at 25 ° C (room temperature) is preferably 0.5 mPa · s or more and 200 mPa · s or less, more preferably 1 mPa · s or more and 100 mPa · s or less, more preferably 2 mPa · s or more and 50 mPa S or less. By setting the viscosity at room temperature high, it is possible to prevent the composition from being dripped even when applied to a substrate having unevenness, and as a result, a uniform light-shielding film can be formed. When the viscosity at 25 占 폚 is more than 200 mPa 占 퐏, problems may occur in the conveyance of the composition (the conveying 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, and more preferably 23 mN / m to 35 mN / m. When it is applied to the surface of a silicon substrate or metal wiring, it is preferably 20 mN / m or more from the viewpoint of suppressing the dropping, and is preferably 35 mN / m or less from the viewpoint of adhesiveness with the substrate or the like and affinity.

&Lt; Sequence of process >

The method for producing the colored layer formed using the composition of the present invention is not particularly limited and a known method can be employed. Among them, the step of imparting a coloring and radiation-sensitive composition onto a base layer to form a coloring and radiation-sensitive composition layer (hereinafter also referred to as a "step of forming a coloring and radiation-sensitive composition layer"), (Hereinafter also referred to as " coloring pattern ") is formed by developing the patterned radiation-sensitive composition layer after exposure (hereinafter also referred to as " coloring pattern " (Hereinafter, also referred to as "development step").

Hereinafter, the order of each step of the preferred embodiment will be described in detail.

(Coloring and radiation-sensitive composition layer forming step)

In the step of forming the coloring and radiation-sensitive composition layer, the composition is applied to the base layer to form a coloring and radiation-sensitive composition layer.

As a method of applying the composition of the present invention to the base layer, various coating methods such as slit coating, inkjet coating, spin coating, flex coating, roll coating, screen printing and the like can be applied.

The film thickness of the coloring and radiation-sensitive composition layer is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and further preferably 0.2 to 3 μm.

The coloring and radiation-sensitive composition layer applied on the support may be dried (pre-baked) if necessary, and the drying can be performed in a hot plate, an oven or the like at a temperature of 50 ° C to 140 ° C for 10 seconds to 300 seconds.

(Exposure step)

In the exposure step, the coloring and radiation-sensitive composition layer formed in the coloring and radiation-sensitive composition layer forming step is pattern-exposed through a mask having a predetermined mask pattern by using an exposure apparatus such as a stepper.

As the radiation (light) usable at the time of exposure, ultraviolet rays such as g line and i line are preferably used (particularly preferably i line). Irradiation dose (exposure dose) is 30 ~ 1500mJ / cm ² are preferred, and 50 ~ 1000mJ / cm ² is more preferably, 80 ~ 500mJ / cm ² is most preferred.

(Developing step)

Subsequently, development such as alkali developing treatment is carried out, whereby the coloring and radiation-sensitive composition layer of the light-irradiated portion in the exposure step is eluted into the developer, leaving only the light-cured portion.

As the developer, an organic alkali developing solution which does not cause damage to the underlying imaging element or circuit is preferable. 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 residues, it is sometimes carried out 120 to 180 seconds in recent years. Further, in order to further improve the removability of the residue, the step of removing the developing solution every 60 seconds and further supplying the developing solution may be repeated several times.

Examples of the alkaline agent to be used in the developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8- And organic alkali compounds such as Javancyclo- [5,4,0] -7-undecene. These alkaline agents are diluted with pure water to a concentration of 0.001 to 10 mass%, preferably 0.01 to 1 mass% An alkaline aqueous solution is preferably used as the developer.

As the developing solution, an inorganic alkali may be used. As the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, sodium metasilicate and the like are preferable.

When a developer comprising such an alkaline aqueous solution is used, it is generally cleaned (rinsed) with pure water after development.

Next, it is preferable to carry out a heat treatment (post-baking) after drying. If a multicolored coloring layer (coloring pattern) is formed, the above process can be repeated for each color in order to produce a cured coating. As a result, a color filter is obtained.

The post-baking is a post-development heat treatment for making the curing to be complete, and is generally subjected to a heat curing treatment at 100 캜 to 240 캜, preferably at 200 캜 to 240 캜.

The post-baking treatment can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot-air circulation type drier), a high-frequency heater or the like so as to achieve the above-

Further, the production method of the present invention may have a known process as a production method of a color filter as a process other than the above, if necessary. For example, it includes a curing step of curing the above-described colored layer (coloring pattern) by heating and / or exposure, if necessary, after the coloring and radiation-sensitive composition layer forming step, the exposure step and the developing step, .

The thickness of the colored layer (colored pixel) in the color filter is preferably 2.0 占 퐉 or less, more preferably 1.0 占 퐉 or less.

The size (pattern width) of the colored layer (coloring pixel) is preferably 2.5 占 퐉 or less, more preferably 2.0 占 퐉 or less, and particularly preferably 1.7 占 퐉 or less.

The color filter can be used for a liquid crystal display device, a solid-state imaging device, and an organic EL display device, and is particularly suitable for use in a solid-state imaging device or an organic EL display device. When used in a liquid crystal display device, the alignment defect of the liquid crystal molecules accompanying the lowering of the resistivity is small, the display image has a good color tone, and the display characteristics are excellent.

The color filter of the present invention is particularly suitable as a color filter for a liquid crystal display device because it has coloring pixels excellent in color and excellent in light resistance. A liquid crystal display device provided with such a color filter can display a high-quality image with good display characteristics and excellent display characteristics.

When the color filter of the present invention is used in a liquid crystal display device, high contrast can be realized when combined with a conventional three-wavelength tube of a cold cathode tube, and LED light sources (RGB-LEDs) of red, As the light, it is possible to provide a liquid crystal display device having high luminance and high color purity and good color reproducibility.

Further, the color filter of the present invention can be suitably used for a solid-state image pickup device.

The configuration of the solid-state image pickup device is not particularly limited as long as it has the color filter of the present invention and functions as a solid-state image pickup device.

A plurality of photodiodes constituting a light receiving area of a solid-state image pickup device (CCD, CMOS, or the like), a transfer electrode made of polysilicon or the like, and a photodiode and a tungsten And a device protective film made of silicon nitride or the like formed on the entire surface of the light shielding film and the photodiode light receiving portion so as to cover the light shielding film and has the color filter of the present invention on the device protective film.

Further, the device protective film may be a structure having condensing means (for example, a microlens or the like) under the color filter (near the support) or a structure having the condensing means on the color filter.

The present invention also relates to an organic EL display device having the base layer described above.

Hereinafter, one embodiment of the organic EL display device of the present invention will be described with reference to the drawings.

1 is a cross-sectional view of a part of an embodiment of an organic EL display device 100 including a base layer 40 and a colored layer 50. Fig. Each pixel is formed by combining any one of the three primary colors (red, green, and blue), for example, by combining a plurality of organic EL elements 20 that generate white light and the colored layers 50 (50R, 50G, . The pitch (center-to-center distance) P of the plurality of organic EL elements 20 is, for example, 30 占 퐉 or less, more preferably 10 占 퐉 or less, and specifically about 2 占 퐉 to 3 占 퐉. The pitch (p) is preferably 0.5 mu m or more, more preferably 1 mu m or more. That is, this display device is what is called a so-called micro display in which the size of the organic EL element 20 is very small. An eyepiece lens (not shown) is provided on the display device, and the user views the image displayed on the display device through the eyepiece lens in an enlarged manner. Therefore, only the portion of the image displayed on the display device within the range of the light receiving angle of the eyepiece can be seen by the user.

The organic EL elements 20 are arranged in a matrix on the substrate 10 and are covered with a protective film 30. On the protective film 30, a sealing substrate 60 made of glass or the like is bonded over the entire surface with an adhesive layer (not shown) interposed 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 constitution of the organic EL element 20 is not particularly limited, and a configuration can be employed, and in many cases, a light emitting layer taught between electrodes is often included.

The protective film 30 is, for example, 0.5 탆 to 10 탆 in thickness and is made of silicon nitride (SiN). The adhesive layer (not shown) is made of, for example, an ultraviolet curing 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 a material such as glass which is transparent to the light emitted from the organic EL element 20, for example.

The coloring layer 50 is for extracting white light generated from the organic EL element 20 as red, green or blue color light and includes a red coloring layer 50R and a red coloring layer 50R opposed to the plurality of organic EL elements 20, A green coloring layer 50G, and a blue coloring layer 50B. The red coloring layer 50R, the green coloring layer 50G and the blue coloring layer 50B are arranged in order corresponding to the organic EL element 20. [ The red coloring layer 50R, the green coloring layer 50G and the blue coloring layer 50B are layers formed of a coloring and radiation-sensitive composition including the above-mentioned coloring agent and the like. Depending on the choice of the coloring agent, , The light transmittance in the green or blue wavelength range is high and the light transmittance in the other wavelength range is low.

The coloring layer 50 may be provided with a semi-transmissive region in a part of the coloring layer 50. Thus, in this display apparatus, even when the size of the organic EL element 20 is small, color mixing due to diffraction of light passing through the adjacent coloring layers can be further suppressed. The semitransmissive region is obtained by changing the transmittance of a part of the colored layer by providing a semi-transparent film on a part of the colored layer.

Below the colored layer 50, the above-described base layer 40 having a refractive index of 1.60 or more at a wavelength of 633 nm is provided. Since the underlayer 40 is disposed, the adhesion of the colored layer 50 is more excellent.

As described above, in the microdisplay, the dimensions of the organic EL element are very small. Because of this, the size of the colored layer provided corresponding to the organic EL element is also very small, and further additional adhesion is required for the colored layer. In the present invention, by arranging the coloring layer on the base layer, it is possible to arrange the coloring layer having a very small dimension with good adhesion.

In the case where metal particles or metal oxide particles are not substantially contained in the ground layer as described above, the flatness of the ground layer is improved, and the adhesion of the colored layer disposed on the ground layer is improved. .

Example

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

(Preparation Example 1: Preparation of Red pigment dispersion)

The mixed liquid of the following composition was mixed and dispersed for 3 hours in a bead mill (high pressure disperser NANO-3000-10 (manufactured by Nippon Express Co., Ltd.) equipped with a decompression apparatus) using zirconia beads having a diameter of 0.3 mm, To prepare a pigment dispersion.

C. I. Pigment Red 254 12.4 part

C. I. Pigment Red 139 5.6 part

· Dispersing agent: BYK-2001 manufactured by BYK 3.6 part

Alkali-soluble resin 1: Benzyl methacrylate / methacrylic acid copolymer

(= 70/30 molar ratio, Mw: 30000, acid value: 110 mgKOH / g) 3.6 part

Solvent: propylene glycol methyl ether acetate 74.8 parts

(Preparation Example 2: Preparation of Green Pigment Dispersion)

The mixed liquid of the following composition was mixed and dispersed for 3 hours in a bead mill (high-pressure disperser NANO-3000-10 (manufactured by Nihon Baii K.K.) equipped with a pressure reducing mechanism) using 0.3 mm diameter zirconia beads, To prepare a pigment dispersion.

C. I. Pigment Green 36 10.8 part

C. I. Pigment Yellow 150 7.2

· Dispersing agent: BYK-2001 manufactured by BYK 3.6 part

The alkali-soluble resin 1 3.6 part

Solvent: propylene glycol methyl ether acetate 74.8 parts

(Preparation Example 3: Preparation of Blue Pigment Dispersion)

The mixed liquid of the following composition was mixed and dispersed for 3 hours in a bead mill (high-pressure disperser NANO-3000-10 (manufactured by Nippon Express Co., Ltd.) equipped with a pressure reducing mechanism) using zirconia beads having a diameter of 0.3 mm, To prepare a pigment dispersion.

C. I. Pigment Blue 15: 6 14.4 part

C. I. PIGMENT Violet 23 3.6 part

· Dispersing agent: BYK-2001 manufactured by BYK 3.6 part

The alkali-soluble resin 1 3.6 part

Solvent: propylene glycol methyl ether acetate 74.8 parts

(Preparation 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

The alkali-soluble resin 1 1.9 part

Polymerizable compound 1: Dipentaerythritol hexaacrylate (Kayadard DPHA available from Nippon Kayaku Co., Ltd.) 3.0 parts

Polymerizable compound 2: pentaerythritol ethylene oxide-modified tetraacrylate (RP-1040 available from Nippon Kayaku Co., Ltd.) 1.3 part

Polymerization initiator 1: The following structure (IRGACURE-OXE01, manufactured by BASF) 1.3 part

Solvent: propylene glycol methyl ether acetate 22.4 parts

(31)

(Preparation Example 5: preparation of green-sensitive radiation-sensitive composition)

A green radiation-sensitive composition was prepared using the same components as in Example 1 except that the Red pigment dispersion of Example 1 was replaced by a Green pigment dispersion.

(Preparation Example 6: Preparation of blue sensitive radiation-sensitive composition)

A blue radiation-sensitive composition was prepared using the same components as in Example 1, except that the Red pigment dispersion of Example 1 was replaced by a Blue pigment dispersion.

(Production Example 7: Base material A)

M-phenylene diamine (28.94 g, 0.27 mol, manufactured by Aldrich), 2,4,6-trichloro-1,3,5-triazine (36.91 g, 0.20 mol, Tokyo Kasei Co., (56.53 g, 0.6 mol, manufactured by Junsei Kagaku) to obtain 46.12 g of the desired polymeric compound A. The obtained polymeric compound A is a compound having a structural unit below. The polymer A had a weight average molecular weight Mw of 4,900 and a polydispersity Mw / Mn of 2.21 as measured by GPC in terms of polystyrene.

(32)

2.0 g of the polymeric compound A obtained above was added to a 10 mL eggplant-shaped flask, 8.0 g of cyclohexanone was added as a solvent, and the solution was completely dissolved at room temperature to obtain a 20% by mass cyclohexanone solution of Polymer Compound A It was prepared.

Next, 0.94 g of cyclohexanone was added to 1.0 g of this 20 mass% cyclohexanone solution, and then Epolide GT-401 (manufactured by Daicel Chemical Industries, Ltd.) which is an epoxy group-containing compound as a crosslinking agent, (10.0 parts by mass relative to 100 parts by mass of the solid content of the polymer) of 10 mass% cyclohexanone solution of 10 mass%. Further, 0.040 g of a 5 mass% cyclohexanone solution of 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion promoter (100 parts by mass of the solid content of the polymer was 1 And 0.040 g of a 0.5 mass% cyclohexanone solution (trade name: Megapak R-30, manufactured by DIC Corporation) (0.1 mass part based on 100 mass parts of polymer solid content) was added as a surfactant And the mixture was stirred for 3 hours until the solution became homogeneous. After stirring, the solute was completely dissolved to obtain a polymer varnish (foundation material A) having a total mass% of solid content of 10% by mass as a pale yellow transparent solution.

(Production Example 8: Foundation material B)

(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) to obtain 10.1 g of the polymer compound B. [ Polymer Compound B is a compound having the following structural unit. Polymer Compound B had a weight average molecular weight Mw of 2,200 and a polydispersity Mw / Mn of 1.51 as measured by GPC in terms of polystyrene.

(33)

2.0 g of the polymer compound B obtained above was added to a 10 mL eggplant-shaped flask, 8.0 g of cyclohexanone as a solvent was added, and the solution was completely dissolved at room temperature to obtain a 20% by mass cyclohexanone solution of Polymer Compound B It was prepared.

Next, 0.72 g of cyclohexanone was added to 1.0 g of the 20% by mass cyclohexanone solution, and thereafter, a mixture of Epolide GT-401 (manufactured by Daicel Chemical Industries, Ltd.), which is an epoxy group- ) Of cyclohexanone solution (7.5 parts by mass relative to 100 parts by mass of the solid content of the polymer) was added. Further, 0.10 g of a 2 mass% cyclohexanone solution of 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion promoter (the solid content of the polymer was adjusted to 1 , And 0.20 g of a 0.1 mass% cyclohexanone solution (trade name: Megapak R-30, manufactured by DIC Corporation) of 0.1 mass part based on 100 mass parts of the solid content of the polymer) was added as a surfactant And the mixture was stirred for 3 hours until the solution became homogeneous. After stirring, the solute was completely dissolved to obtain a polymer varnish (foundation material B) having a total mass% of solid content of 10 mass% as a colorless pale yellow solution.

(Production Example 9: Foundation material C)

2.0 g of the polymer compound B obtained above was added to a 10 mL eggplant-shaped flask, 8.0 g of cyclohexanone as a solvent was added, and the solution was completely dissolved at room temperature to obtain a 20% by mass cyclohexanone solution of Polymer Compound B It was prepared.

Next, 0.72 g of cyclohexanone was added to 1.0 g of the 20 mass% cyclohexanone solution, and then 10 mass parts of VESTAGON B 1065 (manufactured by Degussa AG), which is a compound containing blocked isocyanate, as a crosslinking agent % Cyclohexanone solution (5 parts by mass relative 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 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion promoter (solid content of the polymer was 100 1 part by mass with respect to the mass part) was added and 0.20 g of a 0.1% by mass cyclohexanone solution of a trade name Megapak R-30 (manufactured by DIC Corporation) (the solid content of the polymer was changed to 100 parts by mass 0.1 part by mass), and the mixture was stirred for 3 hours until the solution became homogeneous. After stirring, the solute was completely dissolved to obtain a polymer varnish (foundation material C) having a total mass% of solid content of 10 mass% as a colorless pale yellow solution.

&Lt; Examples 1 to 9 and Comparative Examples 1 to 3 >

The substrate A to C or CT-2010 (manufactured by FUJIFILM ELECTRONICS MATERIALS CO., LTD.) Was evenly coated on an 8-inch silicon wafer by spin coating to form a coating film. Minute, and then further heat-treated for 5 minutes on a hot plate at 300 ° C. The spinning speed of the spin coat was adjusted so that the film thickness of the coating film after the heat treatment was about 0.4 mu m.

Thus, a silicon wafer with a base layer was obtained.

Next, the coloring and radiation-sensitive composition (red radiation-sensitive composition, blue radiation-sensitive composition or green radiation-sensitive composition) prepared above was applied onto the base layer of the base layer- (Thickness: 0.6 mu m) using a spin coater, and subjected to heat treatment (prebaking) using a hot plate at 100 DEG C for 120 seconds.

Next, using i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), pattern exposure was performed at 399 locations in total of patterns arranged in a matrix of 21 rows x 19 columns. In this case, the 21 rows of the matrix, which is in that condition to increase the exposure amount for each and the minimum exposure dose to 500J / m ^2, 500J / m in ^two intervals row, the 19th column of the one side, the focal length optimum value ( Foucus 0.0 mu m) at the center of the focal length of 0.1 mu m. That is, a photomask was used in which a square pixel pattern with four sides of 1.1 m was formed so as to be arranged in a range of 4 mm x 3 mm with the center one row being a focal length optimum value and the focal length being changed for each row .

Thereafter, the silicon wafer on which the exposed coated film was formed was placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by KEMITRONICS Co., Ltd.), and a CD-2060 (manufactured by Fuji Film Electronics Materials Co., ) For 60 seconds at 23 deg. C to form a colored layer (colored pattern) on a silicon wafer.

The silicon wafer on which the colored layer was formed was rinsed with pure water, and then spray-dried.

Further, heat treatment (post-baking) was performed for 300 seconds using a hot plate at 200 占 폚 to obtain a silicon wafer (color filter) having colored pixels corresponding to the coloring agent.

The combination of the base layer material and the coloring and radiation-sensitive composition used in each of the Examples and Comparative Examples is summarized in Table 1 described later. The refractive index of the ground layer was measured by the above-described method (apparatus).

<Evaluation>

(Pattern forming property)

The coloring pattern formed on the wafer thus obtained was measured using a measuring SEM (S-9260 Scanning Electron Microscope, Hitachi SEISAKUSHO CO., LTD.), And the dimension of the coloring pattern of the exposed portion and the degree of the remaining unexposed portion of the unexposed portion Was evaluated on a SEM. It is preferable that there is a difference in solubility of the developing solution between the exposed portion and the unexposed portion, that the exposed portion is image-formed with a dimension according to the mask design, and that there is no dissolved residue in the unexposed portion. The results are shown in the following table. The evaluation criteria are shown below, where A and B are practical levels.

(Evaluation standard)

A: The exposed portion of the image was formed at a ratio of 1: 1 with respect to the mask size, the unexposed portion had no dissolved residue, and the pattern had a good rectangular shape.

B: The exposed portion of the image was formed at a ratio of 1: 1 with respect to the mask size, and no residue remained in the unexposed portion, but the pattern was slightly disordered.

C: The pattern was formed in the exposed portion, but the pattern was not formed at a ratio of 1: 1 with respect to the mask size, or the development failure was observed in the unexposed portion.

D: The unexposed portion was hardly dissolved, and the exposed portion was not formed at a ratio of 1: 1 with respect to the mask size.

(Pattern adhesion)

The coloring pattern formed on the wafer was observed using a measurement SEM (S-9260 Scanning Electron Microscope, Hitachi Seisakusho Co., Ltd.), and the adhesion of the exposed portion was evaluated in terms of optical microscope. It is preferable that there is no pattern peeling at an exposure amount at which a pattern size equal to the mask size is obtained. The results are shown in the following table. The evaluation criteria are shown below, where A and B are practical levels.

<Evaluation Criteria>

A: Pattern peeling is not seen at all.

B: The pattern peeling is 1 to 5 pixels.

C: The pattern peeling is 6 ~ 100 pixels.

D: Pattern peeling is visible at 101 pixels or more.

The evaluation results of the examples and the comparative examples are summarized in Table 1.

In Table 1, "Red ", " Red radiation sensitive composition "," Green ", and "Blue radiation sensitive composition"

[Table 1]

As shown in Table 1, in the production method of the color filter of the present invention, the adhesion of the colored layer was excellent, and the occurrence of residue was also suppressed.

On the other hand, as shown in the comparative example, when a ground layer not showing a predetermined refractive index was used, a desired effect was not obtained.

The above-described organic EL display device (micro OLED) of the embodiment of Fig. 1 was fabricated by using the ground layer formed of the ground materials A to C described above. More specifically, a plurality of organic EL devices each comprising a first electrode, a light emitting layer and a second electrode were formed on a substrate (glass substrate) by a vacuum evaporation method. In addition, the pitch P between the organic EL elements shown in Fig. 1 was 2 m. Next, a protective layer was disposed, and a ground layer was formed on the protective layer using the ground material A described above in the same manner as in the above example. Further, by using the red radiation sensitive composition, the green radiation sensitive composition and the blue radiation sensitive composition described above, a red coloring layer, a green coloring layer and a blue coloring layer Size 2 占 퐉 占 2 占 퐉), and further, a sealing substrate was disposed thereon.

In each of the resulting organic EL display devices, each coloring layer exhibited excellent adhesion and excellent pattern formation properties.

Also, instead of the above-mentioned foundation material A, desired effects can be similarly obtained by using the foundation materials B and C.

The base materials A-1, A-2 and A-3 were prepared by adding 50 mass ppm, 30 mass ppm, or 5 mass ppm of NaCl to the base material A, respectively.

The base materials B-1, B-2, and B-3 were prepared by adding 50 mass ppm, 30 mass ppm, or 5 mass ppm of NaCl in the foundation material B, respectively.

The materials C-1, C-2 and C-3 were prepared by adding 50 mass ppm, 30 mass ppm, or 5 mass ppm of NaCl to ground material C, respectively.

A ground layer and a color filter were formed in the same manner as in Examples 1 to 9 except that these ground materials were used. As a result, it was confirmed that the occurrence of defects in the ground layer was reduced.

(10% by mass, 7% by mass or 5% by mass) of the high refractive index low molecular weight compound (low molecular weight compound having fluorene structure (formula (B) 4, A-5, and A-6, respectively.

10 mass%, 7 mass%, or 5 mass% of the high refractive index low molecular weight compound (the low molecular weight compound having fluorene structure (formula (B))) is further added 4, B-5, and B-6, respectively.

, 10 mass%, 7 mass%, or 5 mass% of the high refractive index low molecular weight compound (a low molecular weight compound having a fluorene structure (the above formula (B))) C-4, C-5, and C-6, respectively.

A ground layer and a color filter were formed in the same manner as in Examples 1 to 9 except that these ground materials were used. As a result, it was confirmed that the refractive index of the base layer was improved.

10 substrate
20 organic EL device
30 Shield
40 base layer
50 colored layer
50R red coloring layer
50G green colored layer
50B blue coloring layer
60 sealing substrate
100 organic EL display device (micro OLED)

Claims (12)

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 a support,
A coloring layer forming step of forming a coloring layer on the base layer by using a coloring and radiation sensitive composition comprising (A) a colorant, (B) a polymerization initiator, and (C)
Wherein the color filter comprises a plurality of color filters. The method according to claim 1,
Wherein the coloring agent is a pigment and the content thereof is 45 mass% or more with respect to the total mass of the coloring and radiation-sensitive composition. The method according to claim 1 or 2,
Wherein the base layer contains an organic compound having a refractive index of 1.60 or more at a wavelength of 633 nm. The method according to any one of claims 1 to 3,
Wherein the base layer contains a triazine ring-containing polymer. The method of claim 4,
Wherein the triazine ring-containing polymer comprises at least one kind selected from the group consisting of repeating units represented by formulas (1A) to (4A).
[Chemical Formula 1]

(In the formula (1A), R ^1A and R ^2A independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group, Ar represents an aromatic ring and / or a heterocyclic ring, And * indicates a bonding position.
In formula (2A), R ^1A and R ^2A 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 the binding position.
In the formula (3A), Ar represents a divalent organic group containing at least one of an aromatic ring and a heterocyclic ring. * Indicates the binding position.
In 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, Naphthyl group. 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 which may be substituted with W; W represents an alkyl group of 1 to 10 carbon atoms, an alkoxy group of 1 to 10 carbon atoms, or a hydroxy group, and n represents 0 or an integer of 1 or more. * Indicates the binding position.) The method according to claim 4 or 5,
Wherein the content of the triazine ring-containing polymer in the ground layer is 40 mass% or more with respect to the total mass of the ground layer. The method 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 according to any one of claims 1 to 7,
Wherein the base layer is substantially free of metal particles or metal oxide particles. A composition for forming a ground layer, which is used for forming a ground layer of a colored layer contained in a color filter, comprising a triazine ring-containing polymer. The method of claim 9,
Further, the composition for forming a ground layer contains a compound having a fluorene structure as a high refractive index low molecular compound. The method according to claim 9 or 10,
Further, the composition for forming the ground layer contains NaCl. An organic EL display device having an organic EL element, a ground layer, and a colored layer,
Wherein the base layer is a ground layer having a refractive index of 1.60 or more at a wavelength of 633 nm.

Images