KR101851547B1

KR101851547B1 - Coloring composition, cured film, color filter, pattern forming method, method for producing color filter, solid-state imaging element and image display device

Info

Publication number: KR101851547B1
Application number: KR1020167020562A
Authority: KR
Inventors: 토시히토 쿠게
Original assignee: 후지필름 가부시키가이샤
Priority date: 2014-02-14
Filing date: 2015-01-29
Publication date: 2018-04-24
Also published as: TW201531535A; JP6205288B2; TWI625365B; WO2015122285A1; KR20160103107A; JP2015151466A

Abstract

A coloring composition capable of forming a cured film which is less prone to color mixing of different colors. A cured film, a color filter, a pattern forming method, a color filter manufacturing method, a solid-state image pickup device, and an image display device using the coloring composition are also provided.
Wherein the coloring agent is at least one selected from the group consisting of a first phthalocyanine pigment which is a zinc phthalocyanine pigment and a second phthalocyanine pigment which is at least one selected from the group consisting of Al, Ti, Fe, Sn, Pb, Ga, V, And Nb as a central metal, and a halogenated phthalocyanine pigment not having a center metal, and a second phthalocyanine pigment selected from halogenated phthalocyanine pigments, , Wherein the content of the colorant relative to the total solid content in the coloring composition is 50% by mass or more, and the content of the first phthalocyanine pigment in the total colorant is 50% by mass or more.

Description

TECHNICAL FIELD [0001] The present invention relates to a color filter, a color filter, a color filter, a pattern forming method, a color filter manufacturing method, a solid-state image pickup device, IMAGING ELEMENT AND IMAGE DISPLAY DEVICE}

The present invention relates to a coloring composition. The present invention also relates to a cured film, a color filter, a pattern forming method, a color filter manufacturing method, a solid-state image pickup device, and an image display device using the colored composition.

In recent years, with the development of personal computers, particularly large-screen liquid crystal televisions, there is a tendency that the demand of liquid crystal displays (LCDs), especially color liquid crystal displays, increases. And the spread of organic EL displays is also demanded from the demand for further high image quality. On the other hand, demand for solid-state image pickup devices such as CCD image sensors has also been greatly increased due to the spread of digital cameras and mobile phones equipped with cameras.

Color filters are used as key devices for these displays and optical elements, and there is an increasing demand for cost reduction with the demand for further high image quality. Such a color filter usually has coloring patterns of three primary colors of red (R), green (G), and blue (B). In a display device or an imaging device, .

As the coloring agent for forming the green pixel portion of the color filter, for example, halogenated copper phthalocyanine pigments including bromine atoms such as C. I. Pigment Green 36 are well known. Recently, in order to secure a wider color gamut and to enhance the color reproducibility of a liquid crystal display, CI Pigment Green 58, a halogenated phthalocyanine pigment using zinc as a central metal, (zinc phthalocyanine pigment of halogens ) Has been proposed.

Patent Document 1 discloses an ink composition comprising a zinc phthalocyanine pigment having 8 to 16 halogen atoms in a phthalocyanine molecule, a pigment dispersant, a solvent, and an unsubstituted and / A green coloring composition for a color filter containing at least one halogenated metal phthalocyanine is disclosed. A metal selected from the group consisting of Al, Ti, Fe, Sn, Pb, Ga, V, Mo, Ta, and Nb is used as an unsubstituted and / or halogenated metal phthalocyanine having a square- Substituted and / or halogenated metal phthalocyanines having at least two heteroatoms as described above.

Patent Document 2 discloses a coloring material carrier comprising a transparent resin, a precursor thereof, or a mixture thereof, a halogenated copper phthalocyanine pigment dispersed in a coloring material carrier, and a coloring material selected from the group consisting of Mg, Al, Si, Ti, V, Mn, Fe , At least one halogenated heterometal phthalocyanine pigment selected from the group consisting of Co, Ni, Zn, Ge, and Sn, and further comprises a green coloring agent comprising a halogenated heterometal phthalocyanine pigment Based on the total amount of the green coloring material, in the range of 1 to 80 mol% based on the total amount of the green coloring material.

Patent Document 1: JP-A-2009-258415 Patent Document 2: JP-A-2002-250812

The inventors of the present invention have studied the properties and found that when a cured film such as a color filter is formed using a coloring composition containing a zinc phthalocyanine pigment, other colors remain on the surface, . In particular, it has been found that when the content of the coloring agent relative to the total solid content in the coloring composition exceeds 50% by mass, the color mixture tends to remarkably occur.

All of the coloring compositions disclosed in Patent Documents 1 and 2 have a pigment content of 50 mass% or less with respect to the total solid content in the coloring composition, and there is no description or suggestion about color mixing.

Accordingly, an object of the present invention is to provide a coloring composition comprising a zinc phthalocyanine pigment capable of forming a cured film which is less prone to color mixing of other colors. Another object of the present invention is to provide a cured film, a color filter, a pattern forming method, a color filter manufacturing method, a solid-state image pickup device, and an image display apparatus using the above-mentioned coloring composition.

As a result of a detailed investigation, the inventors of the present invention have found that when a first phthalocyanine pigment which is a zinc phthalocyanine pigment and a second phthalocyanine pigment which are composed of Al, Ti, Fe, Sn, Pb, Ga, V, Mo, Ta, And a halogenated phthalocyanine pigment having no central metal are used in combination with at least one second phthalocyanine pigment selected from the group consisting of halogenated phthalocyanine pigments having a central metal as a central metal and halogenated phthalocyanine pigments having no central metal , It has been found that even when the concentration of the colorant in the coloring composition is increased, it is difficult for other colors to remain on the surface of the formed cured film, and color mixing with other colors is improved. More specifically, the above-mentioned problem is solved by the following means <1>, preferably by <2> to <13>.

1. A coloring composition comprising a colorant and a resin, wherein the colorant comprises a first phthalocyanine pigment which is a zinc phthalocyanine pigment and at least one phthalocyanine pigment selected from the group consisting of Al, Ti, Fe, Sn, Pb, Ga, V, Mo , Ta, and Nb as a central metal, and halogenated phthalocyanine pigments having no central metal, and at least one second phosphor selected from halogenated phthalocyanine pigments having no central metal. Wherein the content of the first phthalocyanine pigment in the total amount of the colorant is 50% by mass or more, and the content of the colorant relative to the total solid content in the colorant composition is 50% by mass or more.

<2> The coloring composition according to <1>, wherein the content of the second phthalocyanine pigment in the total amount of the coloring agent is 0.01% by mass or more and 1.00% by mass or less.

&Lt; 3 > a second phthalocyanine pigment, wherein the second phthalocyanine pigment is a halogenated phthalocyanine pigment having Fe as a central metal, and / or a halogenated phthalocyanine pigment having no center metal, 2 >.

<4> The coloring composition according to any one of <1> to <3>, further comprising a compound having an epoxy group.

<5> The coloring composition according to <4>, wherein the compound having an epoxy group has a structure in which at least two benzene rings are connected by hydrocarbon groups.

<6> The coloring composition according to <4> or <5>, wherein the compound having an epoxy group is represented by the following general formula (1)

[Chemical Formula 1]

In the general formula (1), R ¹ to R ¹³ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, and L ¹ represents a single bond or a divalent linking group.

<7> The coloring composition according to any one of <1> to <6>, which is used for forming a coloring layer of a color filter.

<8> A cured film obtained by curing a colored composition according to any one of <1> to <7>.

<9> A color filter having a cured film according to <8>.

&Lt; 10 > A process for producing a color filter comprising the steps of applying a coloring composition according to any one of < 1 > to < 7 > onto a support to form a coloring composition layer and curing to form a coloring layer; A step of patterning the photoresist layer by exposure and development to obtain a resist pattern; and a step of dry-etching the colored layer using the resist pattern as an etching mask.

&Lt; 11 > A method of manufacturing a color filter, comprising the pattern formation method according to < 9 > or < 10 >.

&Lt; 12 > A solid-state imaging device having a color filter obtained by the method of manufacturing a color filter according to < 9 > or a color filter according to < 11 >.

&Lt; 13 > An image display device having a color filter obtained by a method of manufacturing a color filter according to < 9 > or a color filter according to < 11 >.

According to the present invention, it becomes possible to provide a coloring composition comprising a zinc phthalocyanine pigment capable of forming a cured film which is less likely to be mixed with other colors. It is also possible to provide a cured film, a color filter, a pattern forming method, a color filter manufacturing method, a solid-state image pickup device, and an image display device using the colored composition.

1 is a schematic cross-sectional view of a first colored layer.
2 is a schematic cross-sectional view showing a state where a photoresist layer is formed on the first colored layer.
3 is a schematic cross-sectional view showing a state in which a resist pattern is formed on the first colored layer.
4 is a schematic cross-sectional view showing a state in which a first coloring pattern is formed by providing a through-air group in the first coloring layer by etching.
5 is a schematic cross-sectional view showing a state in which the resist pattern in Fig. 4 is removed.
6 is a schematic sectional view showing a state in which a second coloring pattern and a second coloring and radiation-sensitive layer are formed.
7 is a schematic cross-sectional view showing a state in which a part of the second colored pixels constituting the second colored pattern is removed, in the second colored radiation sensitive layer in Fig.
8 is a schematic sectional view showing a state in which a third coloring pattern and a third coloring and radiation-sensitive layer are formed.
9 is a schematic sectional view showing a state in which the third coloring and radiation-sensitive layers in Fig. 8 are removed.

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. The organic EL element in the present invention refers to an organic electroluminescence element.

In the present specification, the total solid content refers to the total mass of the components excluding the solvent from the total composition of the coloring composition. The solid content refers to the solid content at 25 占 폚.

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).

The term "radiation " in the present specification means, for example, a line spectrum of a mercury lamp, far ultraviolet ray, extreme ultraviolet ray (EUV light) represented by an excimer laser, X-ray or electron ray. In the present invention, light means an actinic ray or radiation. The term "exposure" in this specification refers to not only exposure by deep ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, etc., but also imaging by particle beams such as electron beams and ion beams, .

In the present specification, the term " (meth) acrylate "refers to both or either acrylate and methacrylate, and" (meth) acrylate " refers to both acrylate and methacrylate, The term "(meth) acryloyl" refers to both acryloyl and methacryloyl.

In the present specification, the terms "monomer" and "monomer" are synonyms. Monomers in the present specification are distinguished from oligomers and polymers and refer to compounds 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.

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

In the present specification, the term " process "is included in this term, not only in the independent process but also in the case where the desired action of the process is achieved even if it can not be clearly distinguished from other processes.

In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene reduced values by GPC measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by TOSOH CORPORATION) and TSKgel Super AWM-H , 6.0 mm ID x 15 cm) can be obtained by using 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.

The pigment used in the present invention means an insoluble dye compound which is hardly soluble in a solvent. Typically, it refers to a pigment compound present as dispersed as particles in a composition. Here, examples of the solvent include any solvent, and examples thereof include solvents exemplified in the column of the solvent to be described later. The pigment used in the present invention preferably has a solubility of 0.1 g / 100 g Solvent or less at 25 DEG C, for example, propylene glycol monomethyl ether acetate and water.

The coloring composition of the present invention is a coloring composition containing a coloring agent and a resin, wherein the coloring agent is at least one selected from the group consisting of a first phthalocyanine pigment which is a zinc phthalocyanine pigment and at least one phthalocyanine pigment selected from Al, Ti, Fe, Sn, Pb, Ga , A halogenated phthalocyanine pigment having one kind selected from the group consisting of V, Mo, Ta, and Nb as a central metal, and a halogenated phthalocyanine pigment not having a center metal Wherein the content of the first phthalocyanine pigment in the total amount of the coloring agent is 50% by mass or more, and the content of the coloring agent in the total solid content in the coloring composition is 50% by mass or more .

The cured film obtained by the coloring composition containing the zirconated phthalocyanine pigment of the present invention was easy to cause color mixing due to residual color on the surface thereof. However, by using the coloring composition of the present invention, a cured film Can be obtained. The reason for obtaining such an effect of the present invention is that by blending the above-mentioned second halogenated phthalocyanine pigment into the zinc phthalocyanine pigment, it is possible to obtain a pigment having a crystal structure (in particular, the outermost surface of the pigment) It is presumed that the hydrophobicity is originally caused and the hydrophobic pigment is slightly hydrophilized, so that the affinity with the developer or the like is improved and the residue is reduced.

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

<< First phthalocyanine pigment >>

In the coloring composition of the present invention, as the first phthalocyanine pigment, a halogenated phthalocyanine pigment is used.

The zinc phthalocyanine pigment of halogens has a planar structure in which zinc of the central metal is located in a region surrounded by four nitrogen atoms of an isoindole ring, as shown by the following general formula (A1).

(2)

In the general formula (A1), it is preferable that any of 8 to ¹⁶ of X ¹ to X ¹⁶ represents a halogen atom, and the remainder represents a hydrogen atom or a substituent. Of X ¹ to X ¹⁶ , the halogen atom is preferably 8 to 12. It is preferable that X ¹ to X ¹⁶ contain one or more of a chlorine atom, a bromine atom and a hydrogen atom. It is also preferred that the chlorine atom is 0-4, the bromine atom is 8-12, and the hydrogen atom is 0-4.

The same halogen atoms as the halogen atoms in X ¹ to X ¹⁶ may be used.

Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom, and in particular, a bromine atom and a chlorine atom are preferred.

As the substituent, reference can be made to the description of paragraphs 0025 to 0027 of JP-A-2013-209623, the contents of which are incorporated herein by reference.

The halogenated phthalocyanine pigments can be referred to, for example, in Japanese Laid-Open Patent Publication No. 2007-284592, paragraphs 0013 to 0039, 0084 to 0085, the content of which is incorporated herein by reference.

The halogenated phthalocyanine pigments are compounds classified as pigments in, for example, the Color Index (CI) (published by The Society of Dyers and Colourists), and include CI Pigment Green 58 . The average composition of CI Pigment Green 58 is 9.8 of bromine atoms out of X ¹ to X ¹⁶ , 3.1 are chlorine atoms, and 3.1 are hydrogen atoms.

In the coloring composition of the present invention, the content of the first phthalocyanine pigment in the total amount of the colorant is 50% by mass or more, preferably 55% by mass or more, and more preferably 60 to 95% by mass. According to the present invention, it is possible to form a cured film hardly causing color mixing even if the content of the zinc phthalocyanine pigment as the first phthalocyanine pigment is increased, so that the content of the first phthalocyanine pigment is increased In one case, the effect of the present invention is more remarkable.

The content of the first phthalocyanine pigment relative to the total solid content in the coloring composition is preferably 20% by mass or more, more preferably 25 to 60% by mass, and particularly preferably 30 to 50% by mass.

One kind of the first phthalocyanine pigment may be used. In addition, X ¹ to X ^{16 in} the general formula (A1) may contain two or more different combinations of compounds. When two or more kinds are included, the total amount is in the above range.

<< Second phthalocyanine pigment >>

In the coloring composition of the present invention, as the second phthalocyanine pigment, one kind selected from the group consisting of Al, Ti, Fe, Sn, Pb, Ga, V, Mo, Ta, Halogenated phthalocyanine pigments, halogenated phthalocyanine pigments having no central metal, and the like. Preferably, a halogenated phthalocyanine pigment having Fe as a central metal, a halogenated phthalocyanine pigment having Al as a central metal, and a halogenated phthalocyanine pigment having no central metal are selected Or more. More preferably, it is a halogenated phthalocyanine pigment having Fe as a central metal and / or a halogenated phthalocyanine pigment having no central metal. Particularly preferred is a halogenated phthalocyanine pigment having Fe as a central metal.

Examples of the halogenated phthalocyanine pigment having a central metal selected from the group consisting of Al, Ti, Fe, Sn, Pb, Ga, V, Mo, Ta, Is a preferable example.

(3)

In the general formula (A2), M represents Al, Ti, Fe, Sn, Pb, Ga, V, Mo, Ta or Nb, and any of 8 to 16 of X ¹ to X ¹⁶ represents a halogen atom And the remainder represents a hydrogen atom or a substituent. All the halogen atoms represented by X ¹ to X ¹⁶ may be the same halogen atom or different halogen atoms.

X ¹ ~ of the formula (A2) is X ^16, and X ¹ ~ X ¹⁶ and consent of the (A1), the preferable range is also the same. X ¹ to X ¹⁶ in formula (A2) are preferably the same as X ¹ to X ^{16 in} formula (A1). According to this, since the first phthalocyanine pigment and the second phthalocyanine pigment have a similar structure, the second phthalocyanine pigment becomes easy to approach the first phthalocyanine pigment, It is easy to cause non-uniformity in the crystal structure of the talrosocyanic pigment, and the effect of the present invention is more easily obtained.

As a halogenated phthalocyanine pigment having no central metal, a compound having a structure represented by the following general formula (A3) is a preferable example.

[Chemical Formula 4]

In formula (A3), any of 8 to 16 of X ¹ to X ¹⁶ represents a halogen atom, and the remainder represents a hydrogen atom or a substituent. All the halogen atoms represented by X ¹ to X ¹⁶ may be the same halogen atom or different halogen atoms.

X ¹ ~ of the formula (A3) X ¹⁶ is an X ¹ ~ X ¹⁶ and consent of the (A1), the preferable range is also the same. In addition, from the above reason, X ¹ ~ X ¹⁶ in the formula (A3) is that the same combination is preferable as X ¹ ~ X ¹⁶ in the formula (A1).

In the coloring composition of the present invention, the content of the second phthalocyanine pigment in the total amount of the colorant is preferably 0.01 to 1.00 mass%, more preferably 0.02 to 0.90 mass%, and more preferably 0.02 to 0.05 mass% Is particularly preferable. When the content of the second phthalocyanine pigment is within the above range, the color mixture can be suppressed more effectively.

The second phthalocyanine pigment is preferably contained in an amount of 0.01 to 5.00 parts by mass, more preferably 0.01 to 2.00 parts by mass, per 100 parts by mass of the first phthalocyanine pigment.

The second phthalocyanine pigment may be contained singly or in combination of two or more. When two or more kinds are included, the total amount is in the above range.

<< Other coloring agents >>

In addition to the first phthalocyanine pigment and the second phthalocyanine pigment described above, the coloring composition of the present invention may contain other coloring agents, and preferably contains other coloring agents. As the other coloring agent, a yellow coloring agent is preferably used. The other coloring agent may be either a dye or a pigment, or both of them may be used in combination.

As the pigment, various conventionally known inorganic pigments or organic pigments can be mentioned. Considering that it is preferable that an inorganic pigment or an organic pigment is high in transmittance, it is preferable to use a pigment having an average particle size as small as possible, and considering the handling property, the average particle size of the pigment is preferably 0.01 to 0.1 mu m , And more preferably 0.01 to 0.05 mu m.

Specific examples of the inorganic pigments include black pigments such as carbon black and titanium black; pigments such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium , Metal oxides such as zinc and antimony, and complex oxides of the above metals.

Examples of organic 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, 73,

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

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

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.

Among these, C. I. Pigment Yellow 150 and 185 are preferable, and C. I. Pigment Yellow 185 is particularly preferable.

Examples of the dye that can be used in the coloring composition of the present invention include those disclosed in Japanese Laid-Open Patent Publication No. 64-90403, Japanese Laid-Open Patent Publication No. 64-91102, Japanese Laid-Open Patent Publication No. 1-94301, 6-11614, 2592207, 4808501, 5667920, 505950, 5667920, 5333207, and 660169, which are incorporated herein by reference. -35183, JP-A-6-51115, JP-A-6-194828, and the like can be used. As a chemical structure, it is possible to use a pyrazole compound, a pyromethene compound, an anilino compound, a triphenylmethane compound, an anthraquinone compound, a benzilidene compound, an oxolin compound, a pyrazolotriazoazo compound, A cyanine compound, a phenothiazine compound, a pyrrolopyrazolequamethane compound, and the like can be used. As the dye, a dye multimer may be used. Examples of the pigment multimer include the compounds described in JP-A-2011-213925 and JP-A-2013-041097.

When the coloring composition of the present invention contains a different coloring agent, the content of the other coloring agent is preferably 10 to 100 parts by mass, more preferably 30 to 90 parts by mass relative to 100 parts by mass of the first phthalocyanine pigment desirable. Within this range, preferable spectral characteristics on the color reproducibility can be obtained.

When CI Pigment Yellow 150 and / or CI Pigment Yellow 185 are contained as other colorants, the amount is preferably 10 to 100 parts by mass relative to 100 parts by mass of the first phthalocyanine pigment, To 90 parts by mass is more preferable. Within this range, preferable spectral characteristics on the color reproducibility can be obtained.

In the coloring composition of the present invention, the content of the coloring agent relative to the total solid content in the coloring composition is 50% by mass or more, preferably 50 to 80% by mass, and particularly preferably 55 to 70% by mass.

That is, when the above-mentioned other coloring agent is not used in the coloring composition of the present invention, the total amount of the first phthalocyanine pigment and the second phthalocyanine pigment described above relative to the total solid content in the coloring composition Is 50 mass% or more, preferably 50 to 80 mass%, and particularly preferably 55 to 70 mass%. When a different colorant is used, the total amount of the first phthalocyanine pigment and the second phthalocyanine pigment described above relative to the total solid content in the coloring composition is 50% by mass or more, , More preferably 50 to 80 mass%, and particularly preferably 55 to 70 mass%.

When the content of the coloring agent is 50 mass% or more, the concentration of the coloring agent in the solid content becomes high, and the crosstalk (light mixing) when the color filter is thinned can be reduced. In addition, when dry etching is performed using the coloring composition of the present invention, the etching rate at the time of pattern formation by dry etching is slowed down. As a result, the difference in etching rate between the upper and lower portions of the pattern becomes smaller, so that the perpendicularity of the pattern with respect to the substrate is enhanced, and the rectangularity is improved. This also increases the uniformity of the film thickness of the colored pattern formed by etching, thereby suppressing the surface roughness during the planarization process. Also, the higher the colorant concentration, the higher the strength of the colored layer, and the surface roughness caused by the planarization treatment by the polishing treatment such as the CMP treatment can be reduced. Therefore, it can be suitably used as a coloring composition for dry etching.

<< Resin >>

The coloring composition of the present invention comprises a resin. The resin usually functions as a dispersing agent for dispersing the pigment in the coloring composition.

It is preferable that the resin serving as the dispersing agent is composed substantially of acid-forming resin or base-forming resin. Since the resin serving as the dispersing agent is composed only of the acid forming resin or the base molding resin, the dispersibility of the pigment can be further improved. Among them, it is particularly preferable that the resin serving as the dispersing agent is substantially composed of only the acid-forming resin. Further, the phrase "substantially composed of the acid-forming resin only" means that the content of the resin other than the acid-forming resin in the resin is preferably 5 mass% or less, more preferably 3 mass% or less, and 1 mass% More preferable, and it is particularly preferable that it is not contained. Also, the phrase "consisting essentially of only the base molding resin" means that the content of the resin other than the base molding resin in the resin is preferably 5 mass% or less, more preferably 3 mass% or less, and 1 mass% More preferable, and it is particularly preferable that it is not contained.

Here, the acid form resin means that the amount of acid groups is larger than the amount of basic groups. It is preferable that the amount of the acid group occupies 70 mol% or more when the total amount of the acid group amount and the basic group amount in the resin is 100 mol%, and it is more preferable that the acid forming resin consists substantially only of the acid group. The acid group of the acid-forming resin is preferably a carboxyl group. The acid value of the acid forming resin is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and even more preferably 60 to 105 mgKOH / g.

Further, the term "base-molding resin" means that the amount of the basic group is larger than that of the acid group. It is preferable that the amount of the basic group accounts for 50 mol% or more when the total amount of the acid group amount and the basic group amount in the resin is 100 mol%. The basic group of the base forming resin is preferably an amine.

Examples of the resin that can be used in the present invention include polymer dispersants such as polyamide amines and salts thereof, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethane, modified polyester, modified poly (meth) Acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid-formalin condensate], and polyoxyethylene alkylphosphoric ester, polyoxyethylene alkylamine, alkanolamine, pigment derivative and the like.

The polymer dispersant can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer based on 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.

Examples of the end-modified polymer having an anchor site on the surface of the pigment include polymers having a phosphate group at the terminals described in JP-A-3-112992, JP-A-2003-533455, JP- 273191 and the like, polymers having a partial skeleton of an organic dye described in JP-A No. 9-77994 and the like, and polymers having a heterocyclic ring, and the like. Further, a polymer in which an anchor site (an acid group, a basic group, a partial structure of an organic dye, a heterocycle, etc.) is introduced into two or more pigment surfaces on the polymer terminal end as disclosed in Japanese Patent Application Laid-Open No. 2007-277514 is also excellent in dispersion stability desirable.

Examples of the graft polymer having an anchor portion to the surface of the pigment include a polyester dispersant and the like. Specific examples thereof include those disclosed in JP-A-54-37082, JP-A-8-507960, Reaction products of poly (lower alkyleneimine) and polyester described in JP-A-2009-258668 and the like, reaction products of polyallylamine and polyester described in JP-A-9-169821 and the like, 10-339949, JP-A-2004-37986, WO2010 / 110491 and the like, copolymers of nitrogen atom monomers, JP-A-2003-238837, JP-A-2008-9426 , A graft polymer having a partial skeleton of an organic dye or a heterocycle described in JP-A-2008-81732 and the like, a macromonomer described in JP-A-2010-106268 And copolymers of acid group-containing monomers. Particularly, the amphoteric dispersing resin having a basic group and an acidic group described in JP-A-2009-203462 is particularly preferable from the viewpoints of the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the coloring composition using the pigment dispersion Do.

A known macromonomer can be used as the macromonomer used when the graft polymer having an anchor site to the pigment surface is produced by radical polymerization. Macromonomer AA-6 (a macromonomer having a terminal group of methacryloyl AS-6 (polystyrene having a terminal group of methacryloyl group), AN-6S (copolymer of styrene and acrylonitrile having a terminal group of methacryloyl group), AB-6 (methyl methacrylate) Polylactic acid butyl ester whose terminal group is methacryloyl group), Flaccel FM5 (5-molar equivalent of 2-hydroxyethyl methacrylate-epsilon -caprolactone) manufactured by Daicel Chemical Industries, Ltd., FA10L (acrylic acid 2 - 10-molar equivalent of ε-caprolactone of hydroxyethyl), and polyester-based macromonomers described in JP-A-2-272009. Of these, polyester-based macromonomers having particularly good flexibility and good solvent-solubility are particularly preferred from the viewpoints of dispersibility of the pigment dispersion, dispersion stability, and developability exhibited by the coloring composition using the pigment dispersion, A polyester-based macromonomer represented by the polyester-based macromonomer described in JP-A No. 2-272009 is most preferable.

As block type polymers having anchor sites to the pigment surface, block type polymers described in JP-A-2003-49110 and JP-A-2009-52010 are preferable.

DA-7301 "manufactured by Gusumoto Kasei Co., Ltd.," Disperbyk-101 "(polyamide amine phosphate), 107 (carboxylic acid ester) manufactured by BYK Chemie, etc. are used as the resin which can be used in the present invention, , 110 (copolymer containing an acid group), 111 (phosphoric acid dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymeric copolymer) "," BYK-P104, P105 (High molecular weight unsaturated polycarboxylic acid) ", EFKA 4047, 4050 to 4010 to 4165 (polyurethane resin), EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 6750 (azo pigment derivative) "manufactured by Ajinomoto Fine Techno Co., Ltd.," Ajisper PB821, PB822, PB880, PB881 "manufactured by Ajinomoto Fine Techno Co., Quot; Fluorene TG-710 (uretene oligomer) ", "Polyflow No. 50E ", No. 300 873, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725 ", "Demol RN, N (naphthalene sulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "," Homogenol L- , "Acetamine 86 (Stearylamine Acetate)", "Nippon Lubrizol Co., Ltd.", "Solpres 5000" (manufactured by Nippon Polyurethane Industry Co., Ltd.), "Emulsion 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) (Graft polymer) ", 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 17000, 27000 (polymer having functional group at the terminal), 24000, 28000, 32000, 38500 (Polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) "manufactured by Kawaken Fine Chemicals Co., Ltd.," Hinoact T-8000E "manufactured by Kawaken Fine Chemicals Co., High school ( Quot; Organosiloxane Polymer KP341 ")," W001: Cationic Surfactant ", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, poly Quot; W004, W005, W017 "such as oxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, (EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401 and EFKA Polymer 450 "manufactured by Morishita Sangyo Co., L38, L42, L44, L61, L64, F68, L68, L68, L68, L68, L68, , L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 "manufactured by Sanyo Chemical Industries, ), And the S-20 "or the like.

As the resin, an acrylic base FFS-6752, an acrylic base FFS-187, an acrylic luster RD-F8, and a cyclamer P may be used. The following resins may also be used.

[Chemical Formula 5]

Further, a block copolymer obtained by radical-polymerizing a polymerizable unsaturated compound in the presence of a reversible addition-fragmentation chain transfer (RAFT agent) such as a dithiocarbonyl compound or the like and a radical initiator, or a block copolymer having a narrow molecular weight distribution The coalescence may be used as a dispersing agent. Specific examples of such resins include resins described in Japanese Patent Laid-Open Publication No. 2008-242081, paragraphs 0053 to 0129 and Japanese Patent Laid-Open No. 2008-176218, paragraphs 0049 to 0117, do. Such a block copolymer or a copolymer having a narrow molecular weight distribution may be used as an alkali-soluble resin.

These resins may be used alone, or two or more resins may be used in combination. 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 resin in the coloring composition of the present invention is preferably from 10 to 40 mass%, more preferably from 20 to 40 mass%, and still more preferably from 25 to 40 mass%, based on the total solid content of the coloring composition of the present invention. 35% by mass.

The content of the resin is preferably 20 to 100 parts by mass, more preferably 30 to 85 parts by mass, and particularly preferably 40 to 70 parts by mass, based on 100 parts by mass of the pigment.

The resin may be contained in only one kind or two or more kinds in the coloring composition of the present invention. When two or more kinds are included, the total amount is preferably in the above range.

The resin may be the same or different for each pigment to be used, and the same is preferable for each pigment to be used.

<< Pigment Derivatives >>

The coloring composition of the present invention preferably contains a pigment derivative. The pigment derivative is a compound having a structure in which a part of the organic pigment is substituted with an acidic group, a basic group or a phthalimide methyl group. As the pigment derivative, a pigment derivative having an acidic group or a basic group is preferable from the viewpoints of dispersibility and dispersion stability. Particularly preferably, it is a pigment derivative having a basic group. The combination of the resin (dispersant) and the pigment derivative described above is preferably an acid-forming resin having an acid group and a pigment derivative having a basic group.

Examples of the organic pigments for constituting the pigment derivative include pigments such as diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perynone pigments, , Thioindigo pigments, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, trene pigments, metal complex pigments, and the like.

The acid group of the pigment derivative is preferably a sulfonic acid group, a carboxylic acid group or a quaternary ammonium salt group thereof, more preferably a carboxylic acid group or a sulfonic acid group, and particularly preferably a sulfonic acid group. As the basic group of the pigment derivative, an amino group is preferable, and a tertiary amino group is particularly preferable.

As the pigment derivative, a quinoline-based, benzimidazolone-based, and isoindoline-based pigment derivative is particularly preferable, and a quinoline-based and benzimidazolone-based pigment derivative is more preferable. Particularly, a pigment derivative having the following structure is preferable.

[Chemical Formula 6]

In the general formula (P), A represents a partial structure selected from the following general formulas (PA-1) to (PA-3). B represents a single bond, or a (t + 1) -configured linking group. C represents a single bond, -NH-, -CONH-, -CO ₂ -, -SO ₂ NH-, -O-, -S- or -SO ₂ -. D represents a single bond, an alkylene group, a cycloalkylene group or an arylene group. E represents -SO ₃ H, -SO ₃ M (M represents an alkali metal atom), -CO ₂ H or N (Rpa) (Rpb). Rpa and Rpb each independently represent an alkyl group or an aryl group, and Rpa and Rpb may be connected to each other to form a ring. t represents an integer of 1 to 5;

(7)

In the general formulas (PA-1) and (PA-2), Rp ₁ represents an alkyl group or an aryl group having 1 to 5 carbon atoms. In formula (PA-3), Rp ₂ represent a hydrogen atom, a halogen atom, an alkyl group, or a hydroxyl group. s represents an integer of 1 to 4; When s is 2 or more, plural Rp ₂ may be the same or different. In formula (PA-1) and the general formula _(PA-3), Rp 3 is a single _{bond, -NH-, -CONH-, -CO 2 -} , -SO 2 NH-, -O-, -S- Or SO ₂ -. * Denotes the connection with B

In the general formula (P), Rp ₁ is preferably a methyl group or a phenyl group, and most preferably a methyl group. In the general formula (PA-3), Rp ₂ is preferably a hydrogen atom or a halogen atom, and most preferably a hydrogen atom or a chlorine atom.

In the general formula (P), the linking group of (t + 1) represented by B includes, for example, an alkylene group, a cycloalkylene group, an arylene group and a heteroarylene group. Among them, a linking group represented by the following structural formulas (PA-4) to (PA-9) is particularly preferable.

[Chemical Formula 8]

Among the structural formulas (PA-4) to (PA-9), a pigment derivative having a linking group represented by the structural formula (PA-5) or (PA-8) as B is preferable because of better dispersibility.

Examples of the alkylene group, cycloalkylene group and arylene group represented by D in the general formula (P) include methylene, ethylene, propylene, butylene, pentylene, hexylene, decylene, cyclopropylene, cyclobutylene, Pentylene, cyclohexylene, cyclooctylene, cyclodecylene, phenylene, naphthylene and the like. Among them, D is preferably an alkylene group, more preferably an alkylene group having 1 to 5 carbon atoms.

In the general formula (P), when E represents -N (Rpa) (Rpb), examples of the alkyl group and the aryl group in Rpa and Rpb include a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group, an octyl group, a decyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group , A cyclodecyl group, a phenyl group, and a naphthyl group. As Rpa and Rpb, an alkyl group is particularly preferable, and an alkyl group having 1 to 5 carbon atoms is most preferable. T is preferably 1 or 2.

Specific examples of the pigment derivative are shown below, but the present invention is not limited thereto.

In addition, as the pigment derivative, reference can be made to paragraphs 0162 to 0183 of Japanese Laid-Open Patent Publication No. 2011-252065, which disclosure is incorporated herein by reference.

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

The content of the pigment derivative in the coloring composition of the present invention is preferably from 1 to 30 mass%, more preferably from 3 to 20 mass%, based on the total mass of the pigment. The pigment derivative may be used alone or in combination of two or more.

<< Curing compound >>

The coloring composition of the present invention preferably contains a curable compound. As the curable compound, known polymerizable compounds capable of crosslinking by radicals, acids, and heat can be used. Examples thereof include polymerizable compounds including ethylenically unsaturated bonds, cyclic ethers (epoxy, oxetane), methylol, and the like. When a pattern is formed by a dry etching method, a compound having an epoxy group is preferably used.

<<< Compound having an epoxy group >>>

As the compound having an epoxy group, it is preferable to have two or more epoxy groups in one molecule. By using a compound having two or more epoxy groups in one molecule, the effect of the present invention can be more effectively achieved. The epoxy group is preferably 2 to 10, more preferably 2 to 5, and most preferably 3 in one molecule.

The compound having an epoxy group in the present invention is preferably a compound having a structure in which two benzene rings are connected to each other through hydrocarbon groups. The hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms.

The epoxy group is preferably connected through a linking group. Examples of the linking group include a structure represented by an alkylene group, an arylene group, -O-, -NR'- (wherein R 'represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent and preferably a hydrogen atom) -SO ₂ -, -CO-, -O-, and -S-.

The compound having such a structure is likely to exist in the vicinity of the halogenated zinc phthalimide pigment due to the interaction between the compound having the halogenated zinc phthalimide pigment and the epoxy group. This makes it easy for the compound having an epoxy group to react in the vicinity of the zinc phthalimide pigment to effectively suppress the sublimation and heat transfer of the zinc phthalimide pigment.

The compound having an epoxy group preferably has an epoxy equivalent (= molecular weight of a compound having an epoxy group / number of epoxy groups) of 500 g / eq or less, more preferably 100 to 400 g / eq, further preferably 100 to 300 g / eq Do. The above effect can be obtained by setting the upper limit of the epoxy equivalent of the epoxy group-containing compound to 500 g / eq or less. It is preferable from the standpoint of practical stability that the lower limit of the epoxy equivalent of the compound having an epoxy group is set to 100 g / eq or more.

The compound having an epoxy group may be a low molecular weight compound (for example, having a molecular weight of less than 2,000, and further having a molecular weight of less than 1000), and a macromolecule (for example, a molecular weight of 1000 or more, Or more). The weight average molecular weight of the compound having an epoxy group is preferably from 200 to 100,000, more preferably from 500 to 10000.

As the compound having an epoxy group in the structure in which two benzene rings are connected to each other through a hydrocarbon group, a compound represented by the following general formula (1) is preferably used.

[Chemical Formula 14]

R ¹ to R ¹³ in the general formula (1) each independently represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom.

The alkyl group for R ¹ to R ¹³ is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms.

The alkyl group is not limited to any of linear, branched and cyclic, but is preferably straight-chain or branched, and particularly preferably straight-chain.

The alkyl group may have a substituent or may be unsubstituted. Non-substitution is preferred.

Examples of the substituent that the alkyl group may have include an alkyl group (preferably a linear, branched, or cyclic alkyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methyl, ethyl, Isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, (Preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms, such as vinyl, allyl, 3-butene-1-yl), an alkynyl group (Preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms, such as propargyl and 3-pentanyl) 48, more preferably an aryl group having 6 to 24 carbon atoms, such as phenyl or naphthyl), a heterocyclic group Is a heterocyclic group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, and examples thereof include 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, A silyl group (preferably a silyl group having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a propyl group, Butylsilyl, tert-butyldimethylsilyl, tert-hexyldimethylsilyl), a hydroxyl group, a cyano group, a nitro group, an alkoxy group (preferably having 1 to 48 carbon atoms , More preferably an alkoxy group having 1 to 24 carbon atoms, still more preferably an alkoxy group having 1 to 3 carbon atoms, and examples thereof include methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, tert -Butoxy, dodecyloxy, cycloalkyloxy groups such as cyclopentyloxy, cyclohexyloxy), aryloxy groups (preferably having from 6 to 48 carbon atoms , More preferably an aryloxy group having 6 to 24 carbon atoms, such as phenoxy, 1-naphthoxy), a heterocyclic oxy group (preferably having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms (Preferably 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as silyloxy having 1 to 18 carbon atoms, such as 1-phenyltetrazole-5-oxy and 2-tetrahydropyranyloxy) (For example, trimethylsilyloxy, tert-butyldimethylsilyloxy, diphenylmethylsilyloxy), an acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms, more preferably an acyloxy group having 2 to 24 carbon atoms Ethylhexanoyloxy group, 2-methylpropanyloxyl group, octanoyloxyl group, butaneyloxyl group, 2-methylbutanyloxyl group, benzoyloxy group, dodecaneyloxy group), for example, , An alkoxycarbonyloxy group (preferably having 2 to 48 carbon atoms, more preferably An alkoxycarbonyloxy group having 2 to 24 carbon atoms, such as ethoxycarbonyloxy, tert-butoxycarbonyloxy or cycloalkyloxycarbonyloxy group, for example, cyclohexyloxycarbonyloxy), aryloxycarbonyl (Preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as phenoxycarbonyloxy), a carbamoyloxy group (preferably having 1 to 48 carbon atoms, Preferably a carbamoyloxy group having 1 to 24 carbon atoms, such as N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N-ethyl- ), A sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy) A sulfonyloxy group (preferably having 1 to 38 carbon atoms, more preferably 1 to 3 carbon atoms (Preferably having from 6 to 32 carbon atoms, more preferably from 6 to 24 carbon atoms, more preferably from 6 to 32 carbon atoms, and most preferably from 6 to 24 carbon atoms). Examples of the alkylsulfonyloxy group include alkylsulfonyloxy groups having 1 to 24 carbon atoms, such as methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy, An arylsulfonyloxy group having 1 to 24 carbon atoms such as phenylsulfonyloxy), an acyl group (preferably an acyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as formyl, acetyl, (Preferably an alkoxycarbonyl group having 2 to 48 carbon atoms, more preferably a carbon number of 2 to 24, such as methoxycarbonyl, ethoxycarbonyl, etc.), an alkoxycarbonyl group Cyclohexyloxycarbonyl, cyclohexyloxycarbonyl, 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl), an aryloxycarbonyl group (preferably having 7 to 32 carbon atoms, more preferably Is an aryloxycarbonyl group having 7 to 24 carbon atoms, for example, phenox (Preferably a carbamoyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as carbamoyl, N, N-diethylcarbamoyl, N-ethyl-N N, N-dicyclohexylcarbamoyl), an amino group (preferably an amino group), an amino group (preferably an amino group) Is an amino group having not more than 32 carbon atoms, more preferably not more than 24 carbon atoms, such as amino, methylamino, N, N-dibutylamino, tetradecylamino, 2-ethylhexylamino, cyclohexylamino) (Preferably an anilino group having 6 to 32 carbon atoms, and more preferably 6 to 24 carbon atoms, such as anilino, N-methylanilino), a heterocyclic amino group (preferably having 1 to 32 carbon atoms, Is a heterocyclic amino group having 1 to 18 carbon atoms, for example, 4-pyridylamino), a carbonamido group The sugar is a carbonyl group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as acetamide, benzamide, tetradecaneamide, pivaloylamide, cyclohexane amide, Is an ethylidene group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as an ureido group, an N, N-dimethyl ureido group, an N-phenyl ureido group, (Preferably N-succinimide, N-phthalimide), an alkoxycarbonylamino group (preferably having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, Alkoxycarbonylamino group of 1 to 24 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyloxycarbonylamino), aryloxycarbonyl (Preferably An aryloxycarbonylamino group having 7 to 32 carbon atoms, and more preferably 7 to 24 carbon atoms, such as phenoxycarbonylamino), a sulfonamido group (preferably having 1 to 48 carbon atoms, more preferably 1 to 48 carbon atoms, (Preferably having 1 to 48 carbon atoms, such as methanesulfonamide, butanesulfonamide, benzenesulfonamide, hexadecane sulfonamide, cyclohexanesulfonamide), a sulfamoylamino group Preferably a C 1-24 sulfamoylamino group, such as N, N-dipropylsulfamoylamino, N-ethyl-N-dodecylsulfamoylamino), an azo group (preferably having 1 to 32 carbon atoms Preferably an alkylthio group having 1 to 48 carbon atoms, more preferably an alkylthio group having 1 to 24 carbon atoms, preferably an alkylthio group having 1 to 24 carbon atoms, such as phenyl azo, 3-pyrazolylthio) For example, methylthio, (Preferably an arylthio group having from 6 to 48 carbon atoms, more preferably from 6 to 24 carbon atoms, such as phenylthio), a heterocyclic group (for example, benzylthio group, (Preferably a heterocyclic thio group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as 2-benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolyl (Preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably a 1 to 24 carbon atoms, such as dodecane sulfinyl), an arylsulfinyl group (preferably having 6 to 32 carbon atoms) , More preferably an arylsulfinyl group having 6 to 24 carbon atoms, such as phenylsulfinyl), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably a carbon number 1 to 24, and examples For example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, iso Ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl, cyclohexylsulfonyl), an arylsulfonyl group (preferably having 6 to 48 carbon atoms, more preferably an arylsulfonyl group having 6 to 24 carbon atoms (Preferably phenyl sulfone, 1-naphthylsulfonyl), a sulfamoyl group (preferably a sulfamoyl group having not more than 32 carbon atoms, more preferably not more than 24 carbon atoms, such as sulfamoyl, N, N- Ethyl-N-dodecylsulfamoyl, N-ethyl-N-phenylsulfamoyl, N-cyclohexylsulfamoyl), sulfo group, phosphonyl group (preferably having 1 to 32 carbon atoms (Preferably 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, more preferably 1 to 20 carbon atoms, and more preferably 1 to 20 carbon atoms), preferably 1 to 24 carbon atoms, such as phenoxyphosphonyl, octyloxyphosphonyl and phenylphosphonyl. To 24 phosphinoylamino groups, such as diethoxyphosphinoylamino, di Butyl-oxy and the like phosphino-ylamino). These substituents may be further substituted. When two or more substituents are present, they may be the same or different. If possible, they may be connected to form a ring.

The alkoxy group in R ¹ to R ¹³ is preferably an alkoxy group having 1 to 30 carbon atoms, particularly preferably an alkoxy group having 1 to 12 carbon atoms.

The alkoxy group may have a substituent or may be unsubstituted. Non-substitution is preferred. Specific examples of the substituent include the same ones as the substituent which the alkyl group may have.

Examples of the halogen atom in R ¹ to R ¹³ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

R ¹ to R ¹³ are each independently preferably a hydrogen atom, a methyl group, an ethyl group or a methoxy group. R ¹³ is preferably a methyl group. R ¹ to R ¹² are preferably hydrogen atoms.

L ¹ in the general formula (1) represents a single bond or a divalent linking group. And is preferably a divalent linking group.

Examples of the divalent linking group include a group represented by an alkylene group, an arylene group, -O-, -NR'- (wherein R 'represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, Structure, -SO ₂ -, -CO-, -O-, and -S-. These may have a substituent. Examples of the substituent include those described above for the substituent which the alkyl group in R ¹ to R ¹³ may have.

The number of carbon atoms of the alkylene group is preferably from 1 to 30, more preferably from 1 to 12.

The carbon number of the arylene group is preferably from 6 to 30, more preferably from 6 to 12.

The compound represented by the above general formula (1) is more preferably a compound represented by the following general formula (1a).

[Chemical Formula 15]

In formula (1a), R ¹ to R ¹⁹ each independently represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom.

R ¹ to R ¹⁹ in the general formula (1a) are synonymous with R ¹ to R ^{13 in} the general formula (1).

In particular, each of R ¹ to R ¹⁹ is preferably independently a hydrogen atom, a methyl group, an ethyl group or a methoxy group. More preferably, at least one group selected from R ¹³ , R ¹⁸ and R ¹⁹ is a methyl group. More preferably, R ¹³ , R ¹⁸ and R ¹⁹ are methyl groups, and R ¹ to R ¹² and R ¹⁴ to R ¹⁷ are hydrogen atoms.

Examples of the compound represented by the general formula (1a) include 1- [4- (1-hydroxy-1-methyl-ethyl) -phenyl] ethanone and phenols (unsubstituted or substituted alkyl, (At least one member selected from epichlorohydrin and epibromohydrin) obtained by the reaction of a phenol resin obtained by the reaction of an alkoxy group having 1 to 12 carbon atoms or a phenol having a halogen atom as a substituent) As a main component. Commercially available products include VG-3101L manufactured by Takeuchi Chemical Co., Ltd., NC-6000 and NC-6300 manufactured by Nippon Kayaku Co., Ltd., and the like.

As the compound having an epoxy group, for example, a compound represented by the following general formula (EP1) may be used in addition to the above-mentioned compounds.

[Chemical Formula 16]

In the formula (EP1), R ^EP1 to R ^EP3 each represent a hydrogen atom, a halogen atom or an alkyl group, and the alkyl group may have a cyclic structure or may have a substituent. R ^EP1 and R ^EP2 , R ^EP2 and R ^EP3 may be bonded to each other to form a ring structure. Examples of the substituent which the alkyl group may have include a hydroxyl group, a cyano group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, an alkylthio group, an alkylsulfonyl group, an alkylsulfonyl group, Alkylamido groups, and the like.

Q ^EP represents an organic group of single bond or n ^EP . R ^EP1 to R ^EP3 may also be bonded to Q ^EP to form a ring structure.

n ^EP represents an integer of 2 or more, preferably 2 to 10, more preferably 2 to 6. However, when Q ^EP is a single bond, n ^EP is 2.

When Q ^EP is n ^EP-valent organic group, a chain or a (also having 6 to 30 carbon atoms are preferable), cyclic n ^EP-valent saturated hydrocarbon group (having 2 to 20 carbon atoms is preferably also), n ^EP-valent direction group, or a chain or cyclic A divalent linking group such as an ether group, an amide group, a sulfonamide group, an alkylene group (preferably having 1 to 4 carbon atoms, and more preferably a methylene group) to saturated hydrocarbon or aromatic hydrocarbon, ) ₂ , or an organic group of n ^EP having a structure in which a combination of these is connected.

Specific examples are given below, but the present invention is not limited thereto.

[Chemical Formula 17]

As the compound having an epoxy group, an oligomer or polymer having an epoxy group in the side chain can also be preferably used. Examples of such a compound include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, and an aliphatic epoxy resin.

These compounds may be commercially available products or may be obtained by introducing an epoxy group into the side chain of the polymer.

As commercial products, for example, bisphenol A type epoxy resins include JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, (Manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 830, EPICLON 835 (above, DIC (registered trademark), and the like) as the bisphenol F type epoxy resin and EPICLON1055 (manufactured by DIC Corporation), and as the bisphenol F type epoxy resin, JER806, JER807, JER4004, JER4005, JER4007, JER152, JER154, JER157S70, JER157S65 (the above, Japan Epoxy Resin Co., Ltd.), and the like are available as the phenol novolak type epoxy resin, and LCE-21, RE-602S (manufactured by Nippon Kayaku Co., EPICLON N-670, EPICLON N-670, EPICLON N-670, EPICLON N-770 (manufactured by DIC Corporation) (Manufactured by Nippon Kayaku Co., Ltd.), EPICLON N-680, EPICLON N-690, EPICLON N-690 and EPICLON N-695 in (Manufactured by ADEKA Corporation), Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE 3150, EPOLEAD PB 3600, and EPOLEAD PB 3600, which are manufactured by ADEKA RESIN EP-4080S, EP- PB 4700 (manufactured by Daicel Chemical Industries Ltd.), Denacol EX-212L, EX-214L, EX-216L, EX-321L and EX-850L (manufactured by Nagase ChemteX Corporation) . In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S and EP-4011S (manufactured by ADEKA), NC-2000, NC-3000, NC-7300, XD- -501, EPPN-502 (manufactured by ADEKA Corporation) and JER1031S (manufactured by Japan Epoxy Resin Co., Ltd.).

EPICLON HP-4700 (manufactured by DIC Corporation), EPICLON N-695 (manufactured by Mitsubishi Kagaku K.K.), DIC (manufactured by Mitsubishi Kagaku K.K.), and the like are commercially available as commercial products of epoxy group- Ltd.) can be preferably used.

In the case of synthesizing by introduction into the side chain of the polymer, the introduction reaction is carried out, for example, by using a tertiary amine such as triethylamine or benzylmethylamine, a quaternary ammonium salt such as dodecyltrimethylammonium chloride, tetramethylammonium chloride or tetraethylammonium chloride , Pyridine, triphenylphosphine or the like as a catalyst in an organic solvent at a reaction temperature of 50 to 150 ° C for several to several hours. The introduction amount of the alicyclic epoxy unsaturated compound is preferably controlled so that the acid value of the obtained polymer is in a range satisfying 5 to 200 KOH mg / g.

As the epoxy unsaturated compound, a compound having a glycidyl group as an epoxy group such as glycidyl (meth) acrylate or allyl glycidyl ether may be used, and it is preferably an unsaturated compound having an alicyclic epoxy group. As such, for example, the following compounds can be exemplified.

[Chemical Formula 18]

In the present invention, the compound having an epoxy group may be used alone or in combination of two or more. The compound having an epoxy group is preferably composed substantially only of the compound represented by the general formula (1). The phrase "substantially composed of the compound represented by the general formula (1)" means that the content of the compound having an epoxy group other than the compound represented by the general formula (1) in the total amount of the epoxy group-containing compound is 3 mass% By mass, more preferably 1% by mass or less, further preferably 0.01% by mass or less, and most preferably, no content.

The total content of the compound having an epoxy group in the coloring composition of the present invention varies depending on whether a low-molecular compound is blended or a high-molecular compound is blended, but it is preferably 5 to 40% by mass relative to the total solid content (mass) , More preferably from 5 to 35 mass%, and particularly preferably from 5 to 30 mass%. By controlling the mixing amount, the color mixing can be suppressed more effectively.

<<< Other Polymerizable Compounds >>>

Examples of other polymerizable compounds include compounds having an ethylenically unsaturated group having at least one addition-polymerizable ethylene group and a boiling point of at least 100 캜 under atmospheric pressure. Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; (Meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylol ethane tri (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylol propol paint (acryloyloxypropyl) ether (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as tri (acryloyloxyethyl) isocyanurate, glycerin or trimethylol ethane, and (meth) acrylate, Japanese Examined Patent Publication 48 (Meth) acrylates described in JP-A-41708, JP-A-50-6034, JP-A-51-37193, Polyester acrylates described in JP-B-48-64183, JP-A-49-43191, JP-A-52-30490, epoxies which are reaction products of epoxy resins and (meth) acrylic acid And polyfunctional acrylates and methacrylates such as acrylates, and mixtures thereof.

(Meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether such as glycidyl (meth) acrylate and a compound having an ethylenic unsaturated group.

As other preferable polymerizable compounds, those having a fluorene ring and having an ethylenic unsaturated group as a bifunctional group, such as those described in JP-A-2010-160418, JP-A-2010-129825 and JP-B-4364216, Or more, and a carboxy resin can also be used.

As the compound having at least one addition-polymerizable ethylenic unsaturated group having a boiling point of 100 占 폚 or higher at normal pressure, the compounds described in paragraphs [0254] to [0257] of Japanese Laid-Open Patent Publication No. 2008-292970 are also suitable.

In addition to the above, radically polymerizable monomers represented by the following general formulas (MO-1) to (MO-5) 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.

[Chemical Formula 19]

[Chemical Formula 20]

In the general formula, n is 0 to 14, and m is 1 to 8. R and T present in plural in one molecule may be the same or different.

At least one of the plurality of Rs present in each of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5) is -OC (═O) CH═CH ₂ or -OC (═O) represents a group represented by _{C (CH 3) = CH 2} .

As specific examples of the polymerizable compounds represented by formulas (MO-1) to (MO-5), compounds described in paragraphs 0248 to 0251 of Japanese Laid-Open Patent Publication No. 2007-269779 are suitably used in the present invention .

Further, in JP-A No. 10-62986, a compound obtained by adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in the specific examples of the general formulas (1) and (2) and then adding (meth) Can also be used as a polymerizable compound.

(KAYARAD D-330 manufactured by Nippon Kayaku Kabushiki Kaisha) and dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol triacrylate (Trade name: KAYARAD D-310, manufactured by Nippon Kayaku K.K.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) And structures in which these (meth) acryloyl groups are interposed between ethylene glycol and propylene glycol residues. These oligomer types can also be used.

The other polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group and a phosphoric acid group as a polyfunctional monomer. 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 nonylromatic carboxylic acid anhydride is reacted with the hydroxyl group of the above- . 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.

The multifunctional monomer having an acid group is preferably a multifunctional monomer having an aliphatic polyhydroxy compound and an ester of an unsaturated carboxylic acid and having an acid group by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a nonaromatic carboxylic acid anhydride , And particularly preferably, in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers made by Toagosei Co., Ltd.

These monomers may be used singly or in combination of two or more in view of difficulty in using a single compound in the production process. If necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as a monomer.

The preferable acid value of the polyfunctional monomer having an acid group is 0.1 mg KOH / g to 40 mg KOH / g, particularly preferably 5 mg KOH / g to 30 mg KOH / g. If the acid value of the polyfunctional monomer is too low, the development and dissolution characteristics are deteriorated. If the acid value is too high, the production and handling become difficult, and the photopolymerization performance deteriorates and the curability such as surface smoothness of the pixel becomes poor. Therefore, when two or more kinds of polyfunctional monomers having different acid groups are used in combination or when polyfunctional monomers having no acid group are used in combination, it is preferable to adjust the acid groups as the entire polyfunctional monomer to fall within the above range.

Also, as another polymerizable compound, it is also a preferred embodiment to contain a polyfunctional monomer having a caprolactone structure.

The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in its molecule, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, (Meth) acrylic acid and? -Caprolactone obtained by esterifying polyhydric alcohols such as glycerin, diglycerol, trimethylolmelamine and the like with (meth) acrylic acid and? -Caprolactone, Modified polyfunctional (meth) acrylate. Among them, a polyfunctional monomer having a caprolactone structure represented by the following general formula (Z-1) is preferable.

[Chemical Formula 21]

In the general formula (Z-1), all six R's are groups represented by the following general formula (Z-2), or one to five of the six R's are groups represented by the general formula (Z-2) And the remainder is a group represented by the following general formula (Z-3).

[Chemical Formula 22]

In the general formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bonding bond.

(23)

In the general formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and "*" represents a bonding bond.

Such a polyfunctional monomer having a caprolactone structure is commercially available, for example, as KAYARAD DPCA series from Nippon Kayaku Co., and DPCA-20 (m = 1 in the above formulas (1) to (3) (2) = 2, R ¹ are both a hydrogen atom), the group represented by, DPCA-30 (the same formula, m = 1, equation (2) of the group represented by = 3, R ¹ is hydrogen atom DPCA-120 (the same formula, m = 1, the number of groups represented by formula (2) = 6 and R ¹ are all hydrogen atoms), DPCA-120 The number of groups represented by formula (2) = 6, and R ¹ are all hydrogen atoms).

The polyfunctional monomers having a caprolactone structure may be used alone or in combination of two or more.

The other polymerizable compound is preferably at least one selected from the group of compounds represented by the following general formula (Z-4) or (Z-5).

&Lt; EMI ID =

E in the formulas (Z-4) and (Z-5) each independently represents - ((CH ₂ ) y CH ₂ O) - or - ((CH ₂ ) yCH (CH ₃ ) , Y represents each independently an integer of 0 to 10, and X represents, independently of each other, an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.

In the general formula (Z-4), the sum of the acryloyl group and the methacryloyl group is 3 or 4, m is independently an integer of 0 to 10, and the sum of m is an integer of 0 to 40 to be. Provided that when the sum of each m is 0, any one of X is a carboxyl group.

In the general formula (ii), the sum of the acryloyl group and the methacryloyl group is 5 or 6, and each n independently represents an integer of 0 to 10, and the sum of n is an integer of 0 to 60. Provided that when the sum of each n is 0, any one of X is a carboxyl group.

In the general formula (Z-4), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. The sum of m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and an integer of 4 to 8 is particularly preferable.

In the general formula (Z-5), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.

The sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.

The - ((CH ₂ ) yCH ₂ O) - or - ((CH ₂ ) yCH (CH ₃ ) O) - in the general formula (Z-4) or the general formula A form in which the terminal is bonded to X is preferable.

The compounds represented by the general formula (Z-4) or (Z-5) may be used singly or in combination of two or more. Particularly, in the general formula (ii), all of the six X's are preferably acryloyl groups.

The total content of the compound represented by the formula (Z-4) or (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.

The compound represented by the general formula (Z-4) or the general formula (Z-5) can be produced by subjecting pentaerythritol or dipentaerythritol, which is a conventionally known process, to a ring opening skeleton And a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride on the terminal hydroxyl group of the ring-opening skeleton. Each process is a well-known process, and a person skilled in the art can easily synthesize a compound represented by the formula (Z-4) or the formula (Z-5).

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

(A), (b), (f), (f), (f) and (f) , (e) and (f) are preferable.

(25)

(26)

Examples of commercially available products of the polymerizable compounds represented by the general formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains of Satomar Co., DPCA-60, which is a hexafunctional acrylate having six pentylene oxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

As another polymerizable compound, a compound having an alkoxymethyl group may also be used. As the compound having an alkoxymethyl group, for example, the following compounds may be mentioned as an example.

(27)

Other polymerizable compounds are described in JP-A-48-41708, JP-A-51-37193, JP-A-2-32293, and JP-A-2-16765 Butene-containing acrylate, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, Yutein compounds having an oxide-based skeleton are also suitable. Examples of the polymerizable compound include compounds having an amino or sulfide structure in the molecule, such as those described in JP-A-63-277653, JP-A-63-260909 and JP-A-1-105238 By using the polymerizable compounds, a curable composition having an extremely high photosensitive speed can be obtained.

UA-7200 (manufactured by Shin Nakamura Kagaku), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H (manufactured by Sanyo Chemical Industries, Ltd.) , UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyowa Chemical Industry Co., Ltd.).

The details of the structure of the polymerizable compound, whether or not the polymerizable compound is used alone, whether or not the polymerizable compound is used alone, and the amount thereof to be added can be arbitrarily set in accordance with the final performance design of the coloring composition. For example, from the viewpoint of sensitivity, a structure having a large number of unsaturated groups per molecule is preferable, and in most cases, a bifunctionality or more is preferable. Further, from the viewpoint of enhancing the strength of the cured film formed by the coloring composition, it is preferable to use trifunctional or more functional groups and the number of functional groups different from each other (e.g., acrylic acid ester, methacrylic acid ester, styrene series compound, vinyl ether group compound) A method of controlling both sensitivity and strength is also effective. It is also preferable to use a polymerizable compound having three or more functional groups and having different ethylene oxide chain lengths from the viewpoint that the developability of the colored composition can be controlled and an excellent pattern forming ability can be obtained.

The compatibility and dispersibility with other components (for example, a photopolymerization initiator, a dispersant, an alkali-soluble resin, etc.) contained in the coloring composition is also an important factor in selecting and using a polymerizable compound. For example, The compatibility may be improved by the use of the purity compound or by the combined use of two or more species. It is also possible to select a specific structure from the viewpoint of improving adhesion with a hard surface such as a support.

When other polymerizable compounds are compounded in the coloring composition of the present invention, the content of the other polymerizable compound is preferably 1 to 40 mass%, more preferably 1 to 30 mass%, based on the total solid content in the coloring composition. The other polymerizable compounds may be used singly or in combination of two or more kinds. When two or more kinds are included, the total amount is preferably in the above range.

<< Organic solvents >>

The coloring composition of the present invention preferably contains an organic solvent.

The organic solvent is not particularly limited so long as it satisfies the solubility of each component and the coating property of the coloring composition, but is preferably selected in consideration of solubility, coating ability and safety of an ultraviolet absorber, a polymerizable compound, a resin (dispersant) .

Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl 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 Ethyl propionate, ethyl 2-ethoxypropionate), propyl 2-hydroxypropionate (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, , Methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy- Examples of the ethers include diethyleneglycol dimethylether, tetraethyleneglycol dimethylether, tetraethyleneglycol dimethylether, tetraethyleneglycol dimethylether, and tetraethyleneglycol dimethacrylate, as methyl, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Ether, diethylene glycol Propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc., and ketones such as ethylene glycol monomethyl ether acetate, Methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and the like, and examples of the aromatic hydrocarbon include toluene, xylene, and the like.

It is also preferable that these organic solvents are mixed with two or more kinds from the viewpoint of improving the shape of the coated surface. 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, propylene glycol methyl ether, and propylene glycol methyl ether acetate, Particularly, a mixed solution composed of cyclohexanone, ethyl 3-ethoxypropionate and propylene glycol methyl ether acetate is preferable.

The content of the organic solvent in the coloring composition of the present invention is preferably such that the total solid content of the coloring composition is 5 to 80 mass%, more preferably 5 to 60 mass% , More preferably from 10 to 50 mass%, and particularly preferably from 10 to 40 mass%.

<< Other Ingredients >>

The composition of the present invention may further contain a surfactant, an acid anhydride, a curing agent, a curing catalyst, a photopolymerization initiator, a Group 2 element ion, an alkali-soluble resin, etc., in addition to the above- Can be blended.

<<< Surfactant >>>

The coloring composition of the present invention is preferably added with various surfactants 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 coloring composition of the present invention contains the fluorine-containing surfactant, the uniformity of the coating thickness and the liquid-repellency (liquid-repellency) can be improved in that the liquid property (particularly, fluidity) Can be further improved.

That is, in the case of forming a film using a coating liquid to which a coloring composition containing a fluorine-containing surfactant is applied, the wettability of the surface to be coated is improved by lowering the interfacial tension between the surface to be coated and the coating liquid, Thereby improving the stability. Thus, 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 appropriately form a film having a uniform thickness with a small thickness deviation.

The fluorine content in the fluorine surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. The fluorine-containing surfactant having a fluorine content within this range is effective from the viewpoints of the uniformity of the thickness of the coating film and the liquid-repellency, and the solubility in the coloring 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, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S393 and KH-40 (manufactured by Asahi Glass Co., Ltd.) have.

Specific examples of the nonionic surfactants include glycerol, trimethylol propane, trimethylol ethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerin ethoxylate and the like), polyoxyethylene Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol diallylate, polyethylene glycol Diisostearate and consumptive fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904 and 150R1 from BASF) Ltd.) and the like.

Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) Acrylic acid-based (co) polymer Polflor No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusoh 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.

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

The coloring composition of the present invention may or may not contain a surfactant. When contained, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 0.5% by mass, based on the total solid content of the coloring composition. To 1.0% by mass.

<<< Acid anhydride >>>

When the coloring composition of the present invention contains a compound having an epoxy group, it may contain an acid anhydride. By containing an acid anhydride, the crosslinking property by thermal curing of a compound having an epoxy group can be improved.

Examples of the acid anhydride include phthalic anhydride, nadic anhydride, maleic anhydride, and succinic anhydride. Among them, phthalic anhydride is preferable because the acid anhydride has little effect on pigment dispersion.

The content of the acid anhydride in the coloring composition is preferably in the range of 10 to 40 mass%, more preferably in the range of 15 to 30 mass%, with respect to the mass of the compound having an epoxy group. When the content of the acid anhydride is 10 mass% or more, the crosslinking density of the compound having an epoxy group is improved and the mechanical strength can be increased. When it is 30 mass% or less, it is advantageous to increase the concentration of the colorant.

<<< Hardener >>>

When the coloring composition of the present invention contains a compound having an epoxy group, it may contain a curing agent. Since the curing agent has a great variety of types and properties, availability time, viscosity, curing temperature, curing time, and heat generation are very different depending on the kind, it is preferable to select a suitable curing agent depending on the purpose of use, use conditions, working conditions and the like . As for the hardener, it is explained in detail in Chapter 5 of "Epoxy resin (Shokodo)" Hiroshi Kakihi. Examples of the curing agent are shown below.

Examples of catalytically acting compounds that react stoichiometrically with tertiary amines, boron trifluoride-amine complexes and epoxy groups include polyamines, acid anhydrides and the like; Examples of the room temperature curing include diethylenetriamine, polyamide resin, middle temperature curing, diethylaminopropylamine, tris (dimethylaminomethyl) phenol; Examples of high temperature curing include phthalic anhydride, metaphenylene diamine, and the like. As for the amines, the aliphatic polyamines include diethylene triamine; As aromatic polyamines, there may be mentioned metaphenylene diamine; Examples of tertiary amines include tris (dimethylaminomethyl) phenol; Examples of the acid anhydride include phthalic anhydride, polyamide resin, polysulfide resin, boron trifluoride-monoethylamine complex; Examples of the initial condensate of synthetic resin include phenol resin, and dicyandiamide. Phthalimide may also be used. Phthalimide is particularly preferred. Since phthalimide has a structure similar to that of the zinc phthalocyanine pigment, it is liable to exist in the vicinity of the zinc phthalocyanine pigment. As a result, the reaction of the compound having an epoxy group occurs in the vicinity of the halogenated zinc phthalocyanine pigment, thereby effectively suppressing sublimation and heat transfer of the zinc phthalocyanine pigment.

Phthalimide is preferably a compound represented by the following general formula (1).

(28)

In the general formula (1), A ¹ to A ⁴ each independently represent a hydrogen atom, a halogen atom, or a methyl group.

At least one of A ¹ to A ⁴ is preferably selected from a chlorine atom and a bromine atom, and it is more preferable that all of A ¹ to A ⁴ are selected from a chlorine atom and a bromine atom. Phthalimides having a structure in which at least one of A ¹ to A ⁴ is selected from a chlorine atom and a bromine atom are more similar to the structure of a zinc phthalocyanine pigment, The non-pigment can come close to the phthalimide at a suitable distance, and the effect is more easily obtained.

In addition, A ¹ ~ A ^4, the general formula (A1) halogenated zinc and not between the phthalocyanine pigment to be represented by X ¹ ~ the same as X ^4, or the same as X ⁵ ~ X ^8, or X ⁹ ~ It is preferably the same as X ¹² , or the same as X ¹³ to X ¹⁶ . According to this embodiment, since the structure of the phthalimide is similar to the structure of the zinc phthalocyanine pigment, the zinc phthalocyanine pigment can come close to the phthalimide at a suitable distance, The above effect is more easily obtained.

These curing agents react with the epoxy groups by heating and polymerize to increase the crosslinking density and cure. In order to make the film thinner, it is preferable that the binder and the curing agent both have a smallest amount, and in particular, the curing agent is preferably 35 mass% or less, preferably 30 mass% or less, more preferably 25 mass% or less with respect to the compound having an epoxy group desirable.

When phthalimide is contained, the content of phthalimide in the total solid content in the coloring composition is preferably 0.01 to 5% by mass.

<<< Curing Catalyst >>>

When the coloring composition of the present invention contains a compound having an epoxy group, it may contain a curing catalyst. In order to realize a composition having a high colorant concentration, in addition to curing by reaction with a curing agent, curing by reaction between epoxy groups is effective. For this reason, a curing catalyst may be used without using a curing agent. The amount of the curing catalyst to be added is preferably about 1/10 to 1/1000, preferably about 1/20 to 1/500, more preferably about 1/30 to 1/100, It is possible to cure in a slight amount of about 1/250.

<<< photopolymerization initiator >>>

The coloring composition of the present invention may contain a photopolymerization initiator from the viewpoint of further improving the sensitivity.

The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is preferable to have photosensitivity to a visible ray from an ultraviolet ray region. In addition, it may be an activator that generates an active radical by generating some action with a photoexcited sensitizer, or may be an initiator that initiates cationic polymerization depending on the type of the monomer.

As the photopolymerization initiator, for example, reference can be made to the disclosure of Japanese Patent Application Laid-Open No. 2013-54080, paragraphs 0178 to 0226, the contents of which are incorporated herein by reference.

The coloring composition of the present invention does not need to contain a photopolymerization initiator. The content of the photopolymerization initiator is preferably from 0 to 50 mass%, more preferably from 0.5 to 30 mass%, more preferably from 0.5 to 30 mass%, based on the total solid content of the coloring composition of the present invention. More preferably 1 to 20% by mass.

When the coloring composition of the present invention is used for a trietching process, it is preferable that the coloring composition of the present invention contains substantially no photopolymerization initiator. When the photopolymerization initiator is not substantially contained, the content of the photopolymerization initiator is preferably 1% by mass or less, more preferably 0.1% by mass or less, and particularly preferably 0% by mass, based on the total solid content of the coloring composition of the present invention Do.

<< Group 2 Element Ion >>

The coloring composition of the present invention preferably contains a second group element ion. By containing the Group 2 element ions in the coloring composition of the present invention, the viscosity stability of the coloring composition can be improved. Further, precipitation of needle-like crystals at high temperature heating can be suppressed.

Examples of the Group 2 element ion include beryllium ion, magnesium ion, calcium ion, strontium ion, barium ion and the like. A magnesium ion, or a calcium ion is preferable, and a calcium ion is particularly preferable. Calcium ions are particularly excellent in improvement of viscosity stability.

When the coloring composition of the present invention contains a Group 2 element ion, the content of the Group 2 element ion relative to the mass of the zinc phthalocyanine pigment is preferably 30 to 300 mass ppm. When the content of the Group 2 element ion is within the above range, the viscosity stability is good. Further, it is possible to obtain a coloring composition in which needle-shaped crystals are hardly precipitated.

<<< Alkali-soluble resin >>>

The coloring composition of the present invention may contain an alkali-soluble resin.

The molecular weight of the alkali-soluble resin is not particularly limited, but Mw is preferably 5000 to 100,000. Mn is preferably 1,000 to 20,000.

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.

The alkali-soluble resin can be referred to the description of Japanese Patent Laid-Open Publication No. 2012-208494, paragraphs 0558 to 0571 (corresponding to United States Patent Application Publication No. 2012/0235099 [0685] to [0700]), Quot;

The coloring composition of the present invention may contain no alkali-soluble resin, but when contained, the content of the alkali-soluble resin is preferably from 1 to 15% by mass, more preferably from 2 to 5% by mass based on the total solid content of the coloring composition. To 12% by mass, and particularly preferably 3% to 10% by mass.

The coloring composition of the present invention may contain only one alkali-soluble resin, or may contain two or more kinds of alkali-soluble resins. When two or more kinds are included, the total amount is preferably in the above range.

In addition, various additives such as fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents and the like can be added to the coloring composition of the present invention, if necessary. Examples of these additives include those described in paragraphs 0155 to 0156 of Japanese Patent Application Laid-Open No. 2004-295116.

The coloring composition of the present invention may contain a sensitizer or light stabilizer described in paragraph 0078 of Japanese Patent Application Laid-Open No. 2004-295116 or a thermal polymerization inhibitor described in paragraph 0081 of the same.

&Lt; Production method of colored composition >

The coloring composition of the present invention can be prepared by mixing the respective components described above.

In preparing the coloring composition of the present invention, each component constituting the coloring composition may be blended at one time, or each component may be dissolved and dispersed in a solvent and then blended continuously. In addition, the order of application and the working conditions at the time of compounding are not particularly limited. For example, the coloring composition may be prepared by dissolving and dispersing the entire components in a solvent at the same time. If necessary, each component may be appropriately prepared as two or more solutions and dispersions, and they are mixed It may be prepared as a composition.

The coloring composition of the present invention is preferably blended with other components in which the pigment is dispersed by a resin (dispersant).

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

The filter used for the filter filtration can be used without particular limitation as long as it is a filter conventionally used for filtration.

Examples of the material of the filter include fluororesins such as PTFE (polytetrafluoroethylene); Polyamide based resins such as nylon-6, nylon-6,6 and the like; And polyolefin resins (including high density and ultrahigh molecular weight) such as polyethylene and polypropylene (PP). 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, it is possible to more effectively remove fine particles and further reduce the turbidity.

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, filtration may first be performed using a first filter, and then filtration may be performed using a second filter having a different pore diameter from the first filter.

At that 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 cured film obtained by curing the coloring composition of the present invention is suitably used for forming a coloring pattern of a color filter because different colors do not mix with each other on the surface. The coloring composition of the present invention is suitably used for forming a coloring pattern of a solid-state imaging element (for example, a CCD, a CMOS or the like) or a color filter used for an image display apparatus such as a liquid crystal display . Among them, a color filter for a solid-state image pickup device such as CCD and CMOS can be suitably used for production. In addition, the coloring composition of the present invention can be preferably used as a coloring composition for dry etching.

&Lt; Cured Film, Pattern Forming Method, Color Filter, and Manufacturing Method of Color Filter >

Next, the cured film, the pattern forming method and the color filter according to the present invention will be described in detail with reference to its manufacturing method. A method of manufacturing a color filter using the pattern forming method of the present invention will also be described.

The cured film of the present invention is obtained by curing the coloring composition of the present invention. Such a cured film is preferably used for a color filter.

In the pattern forming method of the present invention, the coloring composition of the present invention is applied on a support to form a coloring composition layer, and unnecessary portions are removed to form a coloring pattern.

The pattern forming method of the present invention can be suitably applied to the formation of a colored pattern (pixel) of a color filter.

The coloring composition of the present invention may be patterned by a dry etching method, or a pattern may be formed by a so-called photolithography method to produce a color filter.

That is, as a first embodiment of the pattern forming method of the present invention, a step of applying a coloring composition onto a support to form a coloring composition layer, curing to form a coloring layer, a step of forming a photoresist layer on the coloring layer , A step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and a step of dry-etching the colored layer using the resist pattern as an etching mask. When the coloring composition of the present invention is used in a pattern forming method including a step of dry etching, it may be a photocurable composition or a thermosetting composition. In the case of a thermosetting composition, it is preferable to use a compound having an epoxy group as the curing compound.

As a second embodiment of the pattern forming method of the present invention, there is provided a method of forming a pattern, comprising the steps of forming a colored composition layer by applying a colored composition on a support, exposing the colored composition layer in a pattern shape, A pattern forming method including a step of forming a colored pattern is exemplified.

Such a pattern formation method is used in the production of a colored layer of a color filter. That is, the present invention also discloses a method of manufacturing a color filter including the pattern forming method of the present invention.

The details of these will be described below.

Hereinafter, each step in the pattern forming method of the present invention will be described in detail with reference to a method of manufacturing a color filter for a solid-state imaging device, but the present invention is not limited to this method. Hereinafter, a color filter for a solid-state imaging device may be simply referred to as a "color filter ".

A method of manufacturing a color filter of the present invention will be described with reference to specific examples with reference to Figs. 1 to 9. Fig.

First, as shown in the schematic sectional view of FIG. 1, a first colored layer 11 is formed on a support (not shown) by using the coloring composition of the present invention (also referred to as a first coloring composition) ).

The formation of the first colored layer 11 can be carried out by coating the colored composition on a support by a coating method such as spin coating, slit coating or spray coating and drying to form a colored layer.

The thickness of the first colored layer 11 is preferably in the range of 0.3 to 1.0 mu m, more preferably in the range of 0.35 to 0.8 mu m, and still more preferably in the range of 0.35 to 0.7 mu m.

As the curing method, it is preferable that the first colored layer 11 is heated and cured by a heating device such as a hot plate or an oven. The heating temperature is preferably 120 ° C to 250 ° C, more preferably 160 ° C to 230 ° C. The heating time varies depending on the heating means, but usually about 3 to 30 minutes when heating on a hot plate, and usually about 30 to 90 minutes when heating in an oven.

Subsequently, the first colored layer 11 is patterned by dry etching so as to form a through-air group (step (B)).

The first coloring pattern may be a coloring pattern provided as a first coloring tone on the support. In some cases, the first coloring pattern may be formed on a support having an already prepared pattern, for example, a coloring provided as a pattern after the second coloring tone or the third coloring tone Pattern.

In the dry etching, the first colored layer 11 can be etched using an etching gas using the patterned photoresist layer as a mask. For example, as shown in the schematic sectional view of FIG. 2, first, a photoresist layer 51 is formed on the first colored layer 11.

Specifically, a positive or negative radiation-sensitive composition is applied (preferably applied) on the colored layer and dried to form a photoresist layer. In forming the photoresist layer 51, it is preferable to further perform the pre-baking treatment. Particularly, as the photoresist forming process, it is preferable that the post-exposure baking (PEB) and post-baking baking (post baking) are performed.

As the photoresist, for example, a positive radiation-sensitive composition is used. Examples of the positive radiation-sensitive composition include positive photoresists suitable for positive photoresists sensitive to radiation such as deep ultraviolet rays, electron rays, ion beams and X-rays, including ultraviolet rays (g line, h line and i line) Type resist composition may be used. Among the radiation, g line, h line and i line are preferable, and among them, i line is preferable.

Specifically, as the positive radiation-sensitive composition, a composition containing a quinone diazide compound and an alkali-soluble resin is preferable. A positive radiation-sensitive composition containing a quinone diazide compound and an alkali-soluble resin is a composition wherein a quinone diazide group is decomposed by irradiation with light having a wavelength of 500 nm or less to generate a carboxyl group and consequently alkali-soluble from an alkali insoluble state . This positive type photoresist has remarkably excellent resolving power and is used in the production of integrated circuits such as IC and LSI. As the quinone diazide compound, a naphthoquinone diazide compound can be mentioned.

The thickness of the photoresist layer 51 is preferably 0.1 to 3 占 퐉, more preferably 0.2 to 2.5 占 퐉, and still more preferably 0.3 to 2 占 퐉. The application of the photoresist layer 51 can be suitably performed using the coating method of the first colored layer 11 described above.

Next, as shown in the schematic sectional view of FIG. 3, the photoresist layer 51 is exposed and developed to form a resist pattern (patterned photoresist layer) 52 provided with a resist through-air group 51A.

The formation of the resist pattern 52 can be performed by suitably optimizing the conventionally known photolithography technique without any particular limitation. The resist through-air group 51A is provided in the photoresist layer 51 by exposure and development so that a resist pattern 52 as an etching mask used in the next etching is provided on the first coloring layer 11 .

The exposure of the photoresist layer 51 can be performed by exposing the positive or negative radiation-sensitive composition to g-line, h-line or i-line, preferably i-line, through a predetermined mask pattern have. After the exposure, the photoresist is removed in accordance with the region where the coloring pattern is to be formed by developing with a developer.

Any developer which can dissolve the exposed portions of the positive resist and the uncured portions of the negative resist without affecting the first colored layer containing the colorant can be used. For example, a combination of various organic solvents or an alkaline aqueous solution Can be used. As the alkaline aqueous solution, an alkaline aqueous solution prepared by dissolving the alkaline compound in an amount of 0.001 to 10 mass%, preferably 0.01 to 5 mass%, is suitable. The alkaline compound may be, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide , Choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, and the like. When an alkaline aqueous solution is used as a developing solution, cleaning treatment is generally performed with water after development.

Next, as shown in the schematic sectional view of FIG. 4, the resist pattern 52 is used as an etching mask to pattern the first colored layer 11 by dry etching so that the penetrating air group 120 is formed. Thereby, the first colored pattern 12 is formed. Here, the penetrating air group 120 has a first through hole group group 121 and a second through hole group group 122.

The penetrating air group 120 is provided on the first colored layer 11 in the form of a checkerboard. Therefore, the first coloring pattern 12 in which the through-air group 120 is provided in the first coloring layer 11 has a plurality of rectangular first coloring pixels in the form of a checkerboard.

More specifically, the first colored layer 11 is dry-etched using the resist pattern 52 as an etching mask. Representative examples of the dry etching are disclosed in Japanese Laid-Open Patent Application No. 59-126506, Japanese Laid-Open Patent Publication Nos. 59-46628, 58-9108, 58-2809, 57-148706, 61-41102 Quot;

The dry etching is preferably carried out in the following manner, from the viewpoint of forming the cross section of the pattern closer to a rectangle or further reducing the damage to the support.

A first step of etching using a mixed gas of a fluorine-based gas and an oxygen gas (O ₂ ) to a region (depth) where the support is not exposed, and a second step of etching with nitrogen gas (N ₂ ) and using a mixed gas of oxygen gas (O _2), preferably in the form including the over-etching is performed after the substrate is etched in the second step for performing etching up to the vicinity of areas (D) are exposed and the support is exposed desirable. Hereinafter, a specific method of dry etching, etching in the first step, etching in the second step, and overetching will be described.

Dry etching is performed by obtaining etching conditions in advance by the following method.

(1) The etching rate (nm / min) in the first etching step and the etching rate (nm / min) in the second etching step are respectively calculated.

(2) The time for etching the desired thickness by the etching of the first step and the time for etching the desired thickness by the etching of the second step are respectively calculated.

(3) The etching of the first step is performed according to the etching time calculated in (2) above.

(4) The second-stage etching is performed according to the etching time calculated in (2) above. Alternatively, the etching time may be determined by end point detection, and the etching of the second step may be performed according to the determined etching time.

(5) Overetching time is calculated for the total time of (3) and (4), and overetching is performed.

As the mixed gas used in the etching process in the first step, fluorine-based gas and oxygen gas (O ₂ ) are preferably included from the viewpoint of processing the organic material as the etching film into a rectangular shape. The etching process in the first step is performed by etching to a region where the support is not exposed, so that damage to the support can be avoided.

The etching step and the overetching step in the second step are carried out in such a manner that after the etching is carried out up to the region where the support is not exposed by the mixed gas of the fluorine gas and the oxygen gas in the etching step of the first step, , A mixed gas of nitrogen gas and oxygen gas is preferably used for the etching treatment.

It is important that the ratio of the etching amount in the first etching step to the etching amount in the second etching step is determined so as not to hinder the rectangularity due to the etching treatment in the first etching step. The latter ratio in the total etching amount (the sum of the etching amount in the first etching step and the etching amount in the second etching step) is preferably in a range of more than 0% and not more than 50% And more preferably 10 to 20%. The etching amount refers to the remaining film thickness of the etched film.

It is preferable that the etching includes an overetching treatment. The overetching treatment is preferably performed by setting an overetching ratio. It is preferable that the overetching ratio is calculated from the first etching treatment time. The overetching ratio can be arbitrarily set. It is preferably 30% or less of the etching treatment time in the etching step, more preferably 5 to 25% in terms of etching resistance of the photoresist and maintaining the rectangularity of the etched pattern , And particularly preferably 10 to 15%.

Subsequently, as shown in the schematic sectional view of FIG. 5, the resist pattern (i.e., etching mask) 52 remaining after etching is removed. The removal of the resist pattern 52 is performed by applying a removing liquid or a solvent onto the resist pattern 52 to make the resist pattern 52 removable and removing the resist pattern 52 by using cleaning water And the like.

As a step of applying a removing liquid or a solvent to the resist pattern 52 to make the resist pattern 52 removable, for example, a removing liquid or a solvent is provided on at least the resist pattern 52, And stagnating to form a puddle. The time for stucking the peeling liquid or the solvent is not particularly limited, but is preferably several tens of seconds to several minutes.

As the step of removing the resist pattern 52 by using the washing water, washing water is sprayed onto the resist pattern 52 from, for example, a spraying or shower spraying nozzle to remove the resist pattern 52 Process. As the washing water, pure water can be preferably used. As the injection nozzle, there can be mentioned a spray nozzle including the entire support within its spray range, and a spray nozzle having a movable range of its movable range including the entire support. When the spray nozzle is movable, the resist pattern 52 can be more effectively removed by moving the support body from the center of the support to the end of the support two or more times and spraying the cleaning water during the process of removing the resist pattern 52.

The release liquid generally contains an organic solvent, but may further contain an inorganic solvent. Examples of the organic solvent include organic solvents such as 1) hydrocarbon-based compounds, 2) halogenated hydrocarbon-based compounds, 3) alcohol compounds, 4) ether or acetal compounds, 5) ketones or aldehyde compounds, A polyol compound, 7) a polyhydric alcohol compound, 8) a carboxylic acid or an acid anhydride compound, 9) a phenol compound, 10) a nitrogen compound, 11) a sulfur compound, 12) a fluorine compound. The release liquid preferably contains a nitrogen-containing compound, and more preferably includes an uncyclosed nitrogen compound and a cyclic nitrogen compound.

The non-cyclic nitrogen compound is preferably a non-cyclic nitrogen compound having a hydroxyl group. Specific examples thereof include mono isopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N, N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, diethanolamine, Triethanolamine and the like. Of these, monoethanolamine, diethanolamine and triethanolamine are preferable, and monoethanolamine (H ₂ NCH ₂ CH ₂ OH) is more preferable. Examples of cyclic nitrogen compounds include isoquinoline, imidazole, N-ethylmorpholine, epsilon -caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, , pyrrolidine, N-methyl-2-pyrrolidone, N-phenylmorpholine, pyrrolidine, Pyridine, 2,4-lutidine, 2,6-lutidine and the like, preferably N-methyl-2-pyrrolidone and N-ethylmorpholine, 2-pyrrolidone (NMP).

It is preferable that the exfoliating liquid contains a non-cyclic nitrogen compound and a cyclic nitrogen compound. Among them, as the non-cyclic nitrogen compound, at least one selected from monoethanolamine, diethanolamine, and triethanolamine, , And as the cyclic nitrogen compound, at least one selected from N-methyl-2-pyrrolidone and N-ethylmorpholine is more preferable, and monoethanolamine and N-methyl- It is more preferable to include them.

The removal of the resist pattern 52 on the first colored pattern 12 may be performed only when the removal of the resist pattern 52 by the stripping liquid is carried out and even if the deposit as an etching product adheres to the side wall of the first colored pattern 12, It may not be completely removed. The sediment means that the etching product adheres to the side wall of the colored layer and is deposited.

As the peeling liquid, it is preferable that the content of the non-cyclic nitrogen compound is 9 parts by mass or more and 11 parts by mass or less based on 100 parts by mass of the peeling liquid, and the content of the cyclic nitrogen compound is 65 parts by mass or more to 70 parts by mass By mass or less. It is preferable that the exfoliating liquid is a mixture of the non-cyclic nitrogen compound and the cyclic nitrogen compound diluted with pure water.

Subsequently, as shown in the schematic cross-sectional view of FIG. 6, the second coloring and radiation-sensitive compositions are embedded in the through-holes in the first through-hole section group 121 and the second through-hole section group 122 On the first coloring layer (that is, the first coloring pattern 12 in which the penetrating air group 120 is formed in the first coloring layer 11) so as to form a plurality of second coloring pixels, The second coloring and radiation-sensitive layer 21 is laminated by the composition (step (c)). Thereby, in the through-air group 120 of the first colored layer 11, the second colored pattern 22 having a plurality of second colored pixels is formed. Here, the second colored pixel is a square pixel. The formation of the second coloring and radiation-sensitive layer 21 can be carried out in the same manner as the method of forming the first coloring layer 11 described above.

The thickness of the second coloring and radiation-sensitive layer 21 is preferably in the range of 0.3 to 1 mu m, more preferably in the range of 0.35 to 0.8 mu m, and still more preferably in the range of 0.35 to 0.7 mu m.

The second coloring radiation-sensitive layer 21 is exposed and developed at a position 21A corresponding to the first through hole group group 121 provided in the first coloring layer 11, A plurality of second colored pixels 22R provided in the through holes of the stratum corneum 21 and the second through hole group 122 are removed (step (d)) (see the schematic sectional view of Fig. 7) .

Next, as shown in the schematic cross-sectional view of FIG. 8, the third coloring and radiation-sensitive composition is buried in the respective through-holes in the second through-hole section group 122 so that a plurality of third colored pixels are formed And the third coloring and radiation-sensitive composition on the first coloring layer (that is, the first coloring pattern 12 formed by forming the second coloring pattern 22 in the first through-hole section group 121) Thereby forming a coloring and radiation-sensitive layer 31 (step (e)). Thus, in the second through hole group group 122 of the first colored layer 11, a third colored pattern 32 having a plurality of third colored pixels is formed. Here, the third colored pixel is a square-shaped pixel. The formation of the third coloring radiation-sensitive layer 31 can be performed in the same manner as the method of forming the first coloring layer 11 described above.

The thickness of the third coloring radiation-sensitive layer 31 is preferably in the range of 0.3 to 1 mu m, more preferably in the range of 0.35 to 0.8 mu m, and still more preferably in the range of 0.35 to 0.7 mu m.

By exposing and developing the third coloring and radiation-sensitive layer 31 to a position 31A corresponding to the second through hole group group 122 provided in the first coloring layer 11, 9 by removing the radiation-sensitive layer 31. The color filter 12 having the first coloring pattern 12, the second coloring pattern 22, and the third coloring pattern 32 100) is prepared (step (f)).

The second coloring and radiation-sensitive composition and the third coloring and radiation-sensitive composition described above each contain a coloring agent. The coloring agent may be the same as that described above in the coloring composition of the present invention because one of the second colored pixel and the third colored pixel is a red transmissive portion and the other is a blue transmissive portion, Or a blue transmissive portion. The colorant contained in the coloring composition for forming the red transmission portion is preferably at least one selected from the points described in paragraphs [0037] and [0039] of Japanese Laid-Open Patent Publication No. 2012-172003, the content of which is incorporated herein by reference. The colorant contained in the coloring composition for forming the blue transmissive portion was CI Pigment Violet 1, 19, 23, 27, 32, 37, 42 and CI Pigment Blue 1, 2, 15, 15: 1, 15: : 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79,

The content of the colorant composition in the total solid content is preferably 30 mass% or more, more preferably 35 mass% or more, and most preferably 40 More preferably, it is at least% by mass. The content of the colorant composition relative to the total solid content is usually 90% by mass or less, preferably 80% by mass or less.

It is preferable that each of the second coloring and radiation-sensitive composition and the third coloring and radiation-sensitive composition is a negative-type radiation-sensitive composition. As the negative radiation sensitive composition, a negative radiation sensitive composition which is sensitive to radiation such as deep ultraviolet rays, electron rays, ion beams and X rays including ultraviolet rays (g line, h line, i line) . Among the radiation, g line, h line and i line are preferable, and among them, i line is preferable.

Specifically, as the negative radiation sensitive composition, a composition containing a photopolymerization initiator, a polymerization component (polymerizable compound), and a binder resin (alkali-soluble resin or the like) and the like is preferable. For example, JP- [0016] to [0064] of Japanese Patent No. 326453. In such a negative-tone radiation-sensitive composition, the photopolymerization initiator initiates the polymerization reaction of the polymerizable compound by irradiation with radiation, and as a result, the alkali-soluble state becomes alkali-insoluble.

Exposure to the second coloring and radiation-sensitive layer 21 and the third coloring and radiation-sensitive layer 31 can be performed by exposure to g-line, h-line, i-line, or the like, preferably i-line.

The development to be performed after exposure is usually carried out by developing with a developing solution.

The developing solution may be the same as the developing solution described above in the exposure and development of the photoresist layer 51.

When an alkaline aqueous solution is used as a developing solution, cleaning treatment is generally performed with water after development.

The length of one side of the first colored pixel, the second colored pixel, and the third colored pixel (when the pixel is a rectangle, the length of the short side, and when the pixel is a square, the length of one side) Is preferably 0.5 to 1.7 탆, more preferably 0.6 to 1.5 탆.

&Lt; Method of pattern-forming the colored composition layer by photolithography method >

In the method of manufacturing a color filter of the present invention, the colored composition layer may be pattern-formed by photolithography. For details of the photolithography method, refer to Japanese Patent Laid-Open Publication No. 2013-227497, paragraphs 0173 to 0185, the contents of which are incorporated herein by reference.

Since the color filter of the present invention is formed by the coloring composition having a high coloring agent concentration, the thickness of the coloring pattern can be made very thin (for example, 0.7 μm or less). In addition, since different colors do not remain on the surface and color mixing is unlikely to occur, a color filter in which crosstalk (mixed color of light) is suppressed can be obtained.

The color filter of the present invention can be suitably used for a solid-state image pickup device such as a CCD and a CMOS, and is particularly suitable for a high-resolution CCD or CMOS exceeding one million pixels. The color filter for a solid-state imaging device of the present invention can be used, for example, as a color filter disposed between a light-receiving portion of each pixel constituting a CCD or CMOS and a microlens for condensing.

The film thickness of the colored pattern (colored pixel) in the color filter of the present invention is preferably 0.1 to 1.0 μm, more preferably 0.1 to 0.8 μm. In the present invention, since the concentration of the coloring agent in the coloring pattern can be increased, such thinning becomes possible.

The size (pattern width) of the coloring pattern (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.

<Solid-state image sensor>

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

A plurality of photodiodes constituting a light receiving area of a solid-state image sensor (a CCD image sensor, a CMOS image sensor, or the like) and a transfer electrode made of polysilicon or the like are formed on a support, and only a photodiode light- A device shielding film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving portion, and having a color filter for a solid-state imaging device of the present invention .

It is also possible to use a configuration having a light-converging means (for example, a microlens or the like hereinafter) on the device protective layer and below the color filter (near the support), or a configuration having a condensing means on the color filter.

The color filter of the present invention can be used not only for a solid-state image pickup device but also for an image display device such as a liquid crystal display device and an organic EL display device, and is particularly suitable for use in a liquid crystal display device. The liquid crystal display device provided with the color filter of the present invention can display a high-quality image with a good color tone of the display image and excellent display characteristics.

For the definition of the display device and the details of each display device, refer to, for example, "Electronic display device (Sasaki Akio Kogyo Co., Ltd., Sakai, 1990 issued by Sakai Corporation)", "Display device (Ibukisumi Akira, ) Published in the first year of Heisei) ". The liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Uchida Tatsuo, published by Sakai High School Co., Ltd. in 1994) ". The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, the present invention can be applied to various types of liquid crystal display devices described in the "next generation liquid crystal display technology ".

The color filter of the present invention may be used in a color TFT type liquid crystal display device. The color TFT type liquid crystal display device is described in, for example, "Color TFT liquid crystal display (published by Kyoritsu Shootpan Co., Ltd., 1996) ". The present invention can also be applied to a liquid crystal display device such as a transverse electric field driving system such as an IPS or a pixel division system such as an MVA or an STN, TN, VA, OCS, FFS and R-OCB .

The color filter in the present invention can also be provided in a bright, high definition COA (Color-filter On Array) system. In the COA type liquid crystal display device, the required characteristics for the color filter layer may require the characteristics required for the interlayer insulating film, that is, the low dielectric constant and the peel liquid resistance, in addition to the above-mentioned usual required characteristics. The color filter of the present invention can provide a COA type liquid crystal display device having high resolution and long durability because of good color purity and light transmittance and excellent color tone of a colored pattern (pixel). Further, in order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.

These image display methods are described in, for example, page 43 of "EL, PDP, and LCD display technology and the latest trend in the market" (published by Toray Research Center Research Division, 2001).

The liquid crystal display device provided with the color filter in the present invention is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle compensation film in addition to the color filter in the present invention. The color filter of the present invention can be applied to a liquid crystal display device constituted by these known members. These members are described in, for example, "Market of Liquid Crystal Display Materials and Chemicals, 1994 (published by Shimaguchi Co., Ltd., CMC)", "2003 Current Status and Future Prospects of LCD Related Markets Published by Fuji Chimera Soken Co., Ltd., 2003).

Regarding the backlight, it is described in the SID meeting Digest 1380 (2005) (A. Konno et al.) And in the monthly display December 2005, pages 18-24 (Yamazaki Shimaya), 25-30 pages (Yagi Takaaki) .

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

Example

Hereinafter, the present invention will be described in more detail by way of examples. The materials, the amounts used, the ratios, the processing contents, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. Unless otherwise stated, "part" and "%" are based on mass.

PG 58 in Table 1 represents Pigment Green 58 (a zinc phthalocyanine pigment which is a halogenated phthalocyanine pigment). Further, P2-Fe represents a halogenated phthalocyanine pigment having Fe as a central metal. P2-Fr represents a halogenated phthalocyanine pigment having no center metal. In addition, P2-Al represents a halogenated phthalocyanine pigment having Al as a central metal. Further, P2-Ti represents a halogenated phthalocyanine pigment having Ti as a central metal. Further, P2-Sn represents a halogenated phthalocyanine pigment having Sn as a center metal. P2-Pb represents a halogenated phthalocyanine pigment having Pb as a center metal. P2-Ga represents a halogenated phthalocyanine pigment having Ga as a central metal. P2-V represents a halogenated phthalocyanine pigment having V as a central metal. Further, P2-Mo represents a halogenated phthalocyanine pigment having Mo as a central metal. Further, P2-Ta represents a halogenated phthalocyanine pigment having Ta as a central metal. P2-Nb represents a halogenated phthalocyanine pigment having Nb as a central metal. P2-Cu represents a halogenated phthalocyanine pigment having Cu as a central metal. PY 185 represents Pigment Yellow 185. PY 150 represents Pigment Yellow 150.

(Synthesis Example 1) Synthesis of zinc phthalocyanine pigment

Phthalonitrile, ammonia, and zinc chloride were used as raw materials to prepare zinc phthalocyanine. The 1-chloronaphthalene solution had absorption of light at 750 to 850 nm.

The halogenation of zinc phthalocyanine was carried out by mixing 45.5 parts of sulphuryl chloride, 54.5 parts of anhydrous aluminum chloride and 7 parts of sodium chloride at 40 ° C and adding 15 parts of zinc phthalocyanine pigment. 35 parts of bromine was added dropwise thereto, and the mixture was heated to 130 캜 for 19.5 hours and maintained for 1 hour. Thereafter, the reaction mixture was taken out in water to precipitate a crude zinc phthalocyanine crude pigment. This aqueous slurry was filtered, washed with hot water at 60 ° C, washed with 1% sodium hydrogen sulfate solution and hot water at 60 ° C and dried at 90 ° C to obtain 2.7 parts of purified zinc phthalocyanine pigments A .

1 part of refined halogenated phthalocyanine pigments A, 10 parts of crushed sodium chloride and 1 part of diethylene glycol were put into a double arm type kneader and kneaded at 100 ° C for 8 hours. After kneading, the mixture was taken out in 100 parts of water at 80 DEG C and stirred for 1 hour, followed by filtration, hot water washing, drying and pulverization to obtain a zinc phthalocyanine pigment.

The obtained halogenated phthalocyanine pigments were analyzed by mass spectrometry and halogen content analysis by flame combustion ion chromatography _{. The} average composition ZnPcBr ₉ _. ₈ Cl ₃ _. ₁ was H ₃ _.1. Pc is an abbreviation of phthalocyanine.

(Synthesis Example 2) Synthesis of halogenated phthalocyanine pigment having Fe as a central metal

A halogenated phthalocyanine pigment was synthesized in the same manner as in Synthesis Example 1, except that iron chloride was used instead of zinc chloride in Synthesis Example 1. The obtained halogenated phthalocyanine pigment was found to have an average composition of FePcBr _9.8 Cl _3.1 H _3.1 by mass analysis and analysis of the halogen content by flask combustion ion chromatography.

(Synthesis Example 3) Synthesis of halogenated phthalocyanine pigment without center metal

A halogenated phthalocyanine pigment was synthesized in the same manner as in Synthesis Example 1 except that diazabicyclo-undecene (DBU) was used instead of ammonia and zinc chloride in Synthesis Example 1. The obtained halogenated phthalocyanine pigment had an average composition of H ₂ PcBr _9.8 Cl _3.1 H _3.1 from mass analysis and analysis of the halogen content by flask combustion ion chromatography.

(Synthesis Example 4) Synthesis of halogenated phthalocyanine pigment having Al as a central metal

A halogenated phthalocyanine pigment was synthesized in the same manner as in Synthesis Example 1, except that aluminum chloride was used instead of zinc chloride in Synthesis Example 1. The obtained halogenated phthalocyanine pigment was found to have an average composition AlPcBr _9.8 Cl _3.1 H _3.1 by mass analysis and analysis of the halogen content by flask combustion ion chromatography.

(Synthesis Example 5) Synthesis of halogenated phthalocyanine pigment having Ti as a central metal

A halogenated phthalocyanine pigment was synthesized in the same manner as in Synthesis Example 1 except that titanium chloride was used instead of zinc chloride in Synthesis Example 1. The resulting halogenated phthalocyanine pigment was found to have an average composition of TiPcBr _9.8 Cl _3.1 H _3.1 from mass analysis and analysis of the halogen content by flask combustion ion chromatography.

(Synthesis Example 6) Synthesis of halogenated phthalocyanine pigment having Sn as a center metal

A halogenated phthalocyanine pigment was synthesized in the same manner as in Synthesis Example 1 except that tin chloride was used instead of zinc chloride in Synthesis Example 1. The obtained halogenated phthalocyanine pigment was found to have an average composition SnPcBr _9.8 Cl _3.1 H _3.1 by mass analysis and analysis of the halogen content by flask combustion ion chromatography.

(Synthesis Example 7) Synthesis of halogenated phthalocyanine pigment having Pb as a central metal

A halogenated phthalocyanine pigment was synthesized in the same manner as in Synthesis Example 1, except that lead chloride was used instead of zinc chloride in Synthesis Example 1. The obtained halogenated phthalocyanine pigment had an average composition PbPcBr of _9.8 Cl _3.1 H _3.1 from mass analysis and analysis of the halogen content by flask combustion ion chromatography.

(Synthesis Example 8) Synthesis of halogenated phthalocyanine pigment having Ga as a central metal

A halogenated phthalocyanine pigment was synthesized in the same manner as in Synthesis Example 1, except that gallium chloride was used instead of zinc chloride in Synthesis Example 1. The obtained halogenated phthalocyanine pigment was found to have an average composition of GaPcBr _9.8 Cl _3.1 H _3.1 by mass analysis and analysis of the halogen content by flask combustion ion chromatography.

(Synthesis Example 9) Synthesis of halogenated phthalocyanine pigment having V as a central metal

A halogenated phthalocyanine pigment was synthesized in the same manner as in Synthesis Example 1, except that vanadium chloride was used instead of zinc chloride in Synthesis Example 1. The obtained halogenated phthalocyanine pigment had an average composition of VPcBr _9.8 Cl _3.1 H _3.1 from mass analysis and analysis of the halogen content by flask combustion ion chromatography.

(Synthesis Example 11) Synthesis of halogenated phthalocyanine pigment having Mo as a central metal

A halogenated phthalocyanine pigment was synthesized in the same manner as in Synthesis Example 1 except that molybdenum chloride was used instead of zinc chloride in Synthesis Example 1. The obtained halogenated phthalocyanine pigment was found to have an average composition MoPcBr _9.8 Cl _3.1 H _3.1 by mass analysis and analysis of the halogen content by flask combustion ion chromatography.

(Synthesis Example 12) Synthesis of halogenated phthalocyanine pigment having Ta as a central metal

A halogenated phthalocyanine pigment was synthesized in the same manner as in Synthesis Example 1 except that tantalum chloride was used instead of zinc chloride in Synthesis Example 1. The obtained halogenated phthalocyanine pigment was found to have an average composition TaPcBr _9.8 Cl _3.1 H _3.1 by mass analysis and analysis of the halogen content by flask combustion ion chromatography.

(Synthesis Example 13) Synthesis of halogenated phthalocyanine pigment having Nb as a central metal

A halogenated phthalocyanine pigment was synthesized in the same manner as in Synthesis Example 1, except that niobium chloride was used instead of zinc chloride in Synthesis Example 1. The obtained halogenated phthalocyanine pigment had an average composition NbPcBr _9.8 Cl _3.1 H _3.1 from mass analysis and analysis of the halogen content by flask combustion ion chromatography.

(Synthesis Example 14) Synthesis of halogenated phthalocyanine pigment having Cu as a central metal

A halogenated phthalocyanine pigment was synthesized in the same manner as in Synthesis Example 1, except that copper chloride was used instead of zinc chloride in Synthesis Example 1. The obtained halogenated phthalocyanine pigment was found to have an average composition of CuPcBr _9.8 Cl _3.1 H _3.1 by mass analysis and analysis of the halogen content by flask combustion ion chromatography.

(Example 1)

11.4 parts of Pigment Green 58 as a zinc phthalocyanine pigment, 0.05 part of a halogenated phthalocyanine pigment having Fe as a central metal (halogenated iron phthalocyanine pigment), Pigment Yellow 185 2.9 parts, 1.4 parts of the pigment derivative A shown below, 15.6 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) solution containing 30 mass% of the following dispersant A and 68.7 parts of PGMEA as a solvent Were mixed and dispersed by a bead mill for 15 hours to prepare a green pigment dispersion.

&Lt; Preparation of a colored composition containing a green pigment &

76.4 parts of the Green pigment dispersion, 4.4 parts of the following curing compound A, 15.0 parts of PGMEA as a solvent and 4.2 parts of a 1% PGMEA solution of F-781 (manufactured by DIC Corporation) as a surfactant were uniformly added as a compound having an epoxy group And mixed to prepare a coloring composition containing a green pigment.

9.9 parts of Pigment Red 254, 4.4 parts of Pigment Yellow 139, 1.4 parts of pigment derivative A, 15.6 parts of PGMEA solution containing 30 mass% of dispersant A and 68.7 parts of PGMEA as a solvent were mixed and kneaded for 15 hours by a bead mill To prepare a red pigment dispersion.

The Red pigment-containing composition was prepared by uniformly mixing 76.4 parts of the Red pigment dispersion, 4.4 parts of the curable compound A, 15.0 parts of PGMEA as a solvent, and 4.2 parts of a 1% PGMEA solution of F-781 (manufactured by DIC) as a surfactant did.

&Lt; Preparation of glass wafer with undercoating layer >

A glass wafer with an undercoat layer used for evaluation was produced as follows.

(1) Preparation of composition for undercoat layer

19.2 parts of PGMEA, 36.7 parts of ethyl lactate (hereinafter EL), 41% of a binder (benzyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate) copolymer (molar ratio of 60:20:20) (P-methoxyphenol), 0.8 parts of F-781 (manufactured by DIC), and 30.5 parts of a photopolymerization initiator TAZ-107 (manufactured by DIC Corporation), 12.2 parts of dipentaerythritol hexaacrylate, Manufactured by Midori Kagaku Co., Ltd.) were uniformly mixed to prepare a composition for an undercoat layer.

(2) Fabrication of glass wafer with undercoat layer

On the 8-inch glass wafer, the composition for undercoat layer obtained above was uniformly coated with a spin coat to form a coating film, and the formed coating film was heat-treated on a hot plate at 120 캜 for 120 seconds. The spinning speed of the spin coat was adjusted so that the film thickness of the coated film after the heat treatment became 0.5 mu m. The coated film after the heat treatment was further treated in an oven at 220 캜 for one hour to cure the coated film to form an undercoat layer. In this manner, a glass wafer with an undercoat layer having an undercoat layer formed on an 8-inch glass wafer was obtained.

&Lt; Evaluation of residual color mixture &

The colored composition containing a green pigment was coated on a glass wafer with an undercoat layer so as to serve as a coating film having a thickness of 0.5 mu m by a spin coater and then heated at 200 DEG C for 5 minutes using a hot plate to cure the coating Thereby forming a colored film of Green. The film thickness of this colored film was 0.5 mu m.

Subsequently, a positive type photoresist "FHi622BC" (manufactured by Fuji Film Electronics Materials Co., Ltd.) was applied and prebaked to form a photoresist layer having a thickness of 0.8 mu m.

Subsequently, heat treatment was carried out for 1 minute at a temperature at which the photoresist layer or the atmosphere temperature reached 90 占 폚. Thereafter, development treatment was carried out for one minute with a developing solution "FHD-5" (manufactured by FUJIFILM ELECTRONIC MATERIALS CO., LTD.) And post baking treatment was further performed at 110 DEG C for one minute.

Next, dry etching of the colored film was performed in the following order.

The RF power: 800 W, the antenna bias: 400 W, the wafer bias: 200 W, the internal pressure of the chamber: 4.0 Pa, the substrate temperature: 50 캜, and the gas species of the mixed gas with a dry etching apparatus (U-621 manufactured by Hitachi High- And the flow rate of CF ₄ : 80 mL / min., O ₂ : 40 mL / min. And Ar: 800 mL / min.

Subsequently, in the same etching chamber, the gas species and the flow rate of the mixed gas were set to N ₂ : 500 mL / min, the RF power was 600 W, the antenna bias was 100 W, the wafer bias was 250 W, the chamber internal pressure was 2.0 Pa, (N ₂ / O ₂ / Ar = 10/1/10), O _{2 was} 50 mL / min, and Ar was 500 mL / min, and the second stage etching treatment and overetching treatment were performed for 28 seconds.

After the dry etching was performed under the above conditions, the resist was peeled off using a photoresist peeling solution "MS230C" (manufactured by FUJIFILM ELECTRONICS MATERIALS CO., LTD.) For 120 seconds to remove the resist, followed by washing with pure water and spin drying I did. Thereafter, dehydration baking treatment was performed at 100 캜 for 2 minutes. Thus, a colored film on which a colored pattern of Green was formed was obtained.

The maximum transmittance T0 was measured using spectroscopy of the resulting colored film (green coloring pattern) using MCPD-3000 (manufactured by Otsuka Denshi Co., Ltd.).

The red pigment-containing composition for color mixture evaluation was coated on the resulting colored film (green coloring pattern) using a spin coater so that the film thickness after drying became 0.5 탆, and heat treatment for 120 seconds using a hot plate at 100 캜 Baking) was performed. Subsequently, development, rinsing, and drying treatment were carried out without exposure by an i-line stepper exposure apparatus to develop and remove the red pigment-containing composition.

The maximum transmittance T1 was measured again using MCPD-3000 (manufactured by OTSUKA DENKI CO., LTD.) To measure the color of the colored film (green coloring pattern) after development and removal of the red pigment-containing composition. The spectral fluctuation (? T% = T0-T1) of the maximum transmittance was calculated and judged based on the following criteria. The smaller the? T%, the more preferable the less the color mixture of residues.

(Criteria)

A:? T% < 0.5%

B: 0.5%??? T% < 1.0%

C: 1.0%??? T <2.0%

D: 2.0%??? T <3.0%

E: 3.0%?? T%

In the above criterion, A to C are levels at which there is no practical problem, and A to B are particularly preferable.

(Examples 2 to 22)

A coloring composition was prepared in the same manner as in Example 1 except that the coloring agent, the dispersing agent, the kind of the curing compound, the amount of the coloring agent, and the content of the coloring agent relative to the total solid content in the coloring composition were changed to those shown in Table 1, 1, the color mixture evaluation was carried out.

(Comparative Examples 1 and 2)

A coloring composition was prepared in the same manner as in Example 1 except that the kind and amount of the coloring agent and the content of the coloring agent to the total solid content in the coloring composition were changed to the ratios shown in Table 1, .

Pigment Derivative A: The structure shown below

[Chemical Formula 29]

Pigment derivative B: Structure shown below

(30)

Dispersant A: The structure shown below

(31)

Dispersant B: Sorbus 24000 (a basic polymer dispersant manufactured by Nippon Rubrizon Co., Ltd.)

Curable compound A: A compound having the following structure, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) EHPE3150, Mw23000)

(32)

Curable compound B: The structure shown below (synthesized according to the method described in paragraph No. 0083 of JP-A No. 2013-11869)

(33)

Curable compound C: Dipentaerythritol hexaacrylate (structure shown below)

(34)

Curable compound D: Structure shown below

(35)

[Table 1]

As is apparent from the above results, it was confirmed that the first phthalocyanine pigment, which is a zinc phthalocyanine pigment, and the second phthalocyanine pigment, from the group consisting of Al, Ti, Fe, Sn, Pb, Ga, V, Mo, Ta, A second phthalocyanine pigment selected from halogenated phthalocyanine pigments having one kind selected as a central metal and halogenated phthalocyanine pigments having no center metal, In Examples 1 to 22, which used the coloring composition of the present invention, had little residual color mixture.

On the other hand, in Comparative Examples 1 and 2 which did not contain the second phthalocyanine pigment in the present invention, there was much residue color mixture.

Claims

A coloring composition comprising a colorant and a resin,
Wherein the colorant comprises a first phthalocyanine pigment which is a zinc phthalocyanine pigment, a halogenated phthalocyanine pigment having Fe as a central metal, and a halogenated phthalocyanine pigment not having a center metal, At least one second phthalocyanine pigment selected from non-pigments,
Wherein the content of the first phthalocyanine pigment in the total amount of the colorant is 50% by mass or more,
Wherein the content of the second phthalocyanine pigment in the total amount of the colorant is 0.01 to 1.00 mass%
Wherein the content of the coloring agent relative to the total solid content in the coloring composition is 50 mass% or more.

The method according to claim 1,
Wherein the content of the coloring agent relative to the total solid content in the coloring composition is 55 to 70 mass%.

The method according to claim 1 or 2,
Further comprising a compound having an epoxy group.

The method of claim 3,
Wherein the compound having an epoxy group has a structure in which at least two benzene rings are connected with a hydrocarbon group.

The method of claim 3,
A coloring composition wherein the compound having an epoxy group is represented by the following general formula (1);
(36)

The method according to claim 1 or 2,
A coloring composition used for forming a colored layer of a color filter.

A cured film obtained by curing the coloring composition according to claim 1 or 2.

A color filter having the cured film according to claim 7.

A step of applying a coloring composition according to claim 1 or 2 on a support to form a coloring composition layer and curing to form a coloring layer; a step of forming a photoresist layer on the coloring layer; A step of patterning the photoresist layer to obtain a resist pattern; and a step of dry-etching the colored layer using the resist pattern as an etching mask.

A method of manufacturing a color filter, comprising the pattern forming method according to claim 9.

A solid-state imaging device having the color filter according to claim 8.

An image display apparatus having the color filter according to claim 8.

The method according to claim 1,
The coloring composition further comprises a curable compound,
Wherein the curable compound is a polymerizable compound comprising any one of an ethylenic unsaturated bond, cyclic ether and methylol.

14. The method of claim 13,
Wherein the curable compound is a compound having two or more epoxy groups in one molecule.

14. The method of claim 13,
Wherein the curable compound is a compound having 2 to 5 epoxy groups in one molecule.

14. The method of claim 13,
Wherein the curable compound is a compound represented by any one of the following formulas (MO-1) to (MO-5), the following formulas (Z-1), (Z-4) and (Z-5).

[In the general formulas (MO-1) to (MO-5), n is independently 0 to 14, m is each independently 1 to 8, and * denotes bonded hands. R and T present in plural in one molecule may be the same or different.]

[In the general formula (Z-1), all six Rs are groups represented by the following general formula (Z-2), or one to five of the six R's are groups represented by the following general formula (Z-2) , And the remainder is a group represented by the following general formula (Z-3).]

[In the formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and * represents a bond.]

[In the formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and * represents a bond.]

E in the formulas (Z-4) and (Z-5) each independently represents - ((CH ₂ ) yCH ₂ O) - or - ((CH ₂ ) yCH (CH ₃ ) , Y represents independently an integer of 0 to 10, and X represents, independently of each other, an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group. m each independently represents an integer of 0 to 10, and each n independently represents an integer of 0 to 10.]

18. The method of claim 16,
The compound represented by the general formula (Z-4) or (Z-5) is a compound represented by the general formula (Z-4) or (Z- ). &Lt; / RTI >

[In the above formulas (a) to (f), the definitions of m and n are the same as those in the formulas (Z-4) and (Z-5)