JP2016147977A - Coloring composition, colored cured film, and solid state image sensor and display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition suitable for forming a colored cured film having high brightness.SOLUTION: A coloring composition comprises (A) colorant, (B) binder resin and (C) polymerizable compound, (A) colorant comprises C.I.Pigment Violet 19 and red colorant, and a content of the C.I.Pigment Violet 19 is more than 0 mass% and less than 30 mass% of the total colorant content.SELECTED DRAWING: None

Description

  The present invention relates to a colored composition, a colored cured film, and a solid-state imaging device and a display device. More specifically, the present invention relates to a transmissive or reflective color liquid crystal display device, solid-state imaging device, organic EL display device, electronic paper, and the like. The present invention relates to a colored composition used for forming a colored cured film used, a colored cured film formed using the colored composition, and a solid-state imaging device and a display element including the colored cured film.

  In producing a color filter using a colored radiation-sensitive composition, a pigment-dispersed colored radiation-sensitive composition is applied on a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape. There is known a method (for example, see Patent Documents 1 and 2) in which pixels of three primary colors of red, green, and blue are arranged on a substrate by irradiation (hereinafter referred to as “exposure”) and development. In addition, a method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (see, for example, Patent Document 3) is also known. Furthermore, a method for obtaining pixels of each color by an ink jet method using a pigment-dispersed colored resin composition is also known (for example, see Patent Document 4).

  Examples of the colorant used for forming the red pixel of the color filter include C.I. I. Pigment red 254 and C.I. I. Pigment Red 177 is widely used. It is known that a red pixel excellent in luminance can be formed by using these pigments (see, for example, Patent Documents 5 to 9).

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A Japanese Patent No. 3911875 Japanese Patent No. 4218999 JP 2007-124202 A JP 2007-133131 A JP 2010-048927 A

  However, in response to the recent demand for a colored cured film with higher brightness, C.I. I. Pigment red 254 and C.I. I. At present, it is not possible to sufficiently meet such a demand only by using Pigment Red 177. Therefore, at present, development of a coloring composition suitable for forming a colored cured film having high luminance is strongly demanded.

  Accordingly, an object of the present invention is to provide a coloring composition suitable for forming a colored cured film having high luminance. Furthermore, the subject of this invention is providing the solid-state image sensor and display element which comprise the colored cured film formed using the said coloring composition, and this colored cured film.

As a result of intensive studies, the present inventors have determined that C.I. I. It discovered that the said subject could be solved by using together the pigment violet 19 and a red coloring agent.
That is, the present invention is a colored composition containing (A) a colorant, (B) a binder resin and (C) a polymerizable compound, wherein (A) the colorant is C.I. I. Pigment violet 19 and a red colorant; I. The present invention provides a colored composition in which the content ratio of Pigment Violet 19 is more than 0% by mass and less than 30% by mass with respect to all the colorants.

  The present invention also provides C.I. I. Pigment violet 19 and a red colorant; I. The present invention provides a colored cured film in which the content ratio of Pigment Violet 19 exceeds 0% by mass and less than 30% by mass with respect to all colorants, and a solid-state imaging device and a display element including the colored cured film. The “colored cured film” as used herein means each color pixel used in a solid-state image sensor or a display element.

  By using the colored composition of the present invention, it is possible not only to form a colored cured film with high brightness, but also to form a colored cured film having excellent color separation properties.

  Therefore, the colored composition of the present invention can be used very suitably for production of solid-state imaging devices such as CMOS image sensors, and display devices such as color liquid crystal display devices, organic EL display devices, and electronic paper.

Hereinafter, the present invention will be described in detail.
Coloring composition will be described in detail components of the colored composition of the present invention.

-(A) Colorant-
The coloring composition of the present invention includes C.I. I. It is essential to contain Pigment Violet 19 and a red colorant. The colored cured film formed using the colored composition of the present invention is suitable for a color filter of a display element or a solid-state image sensor, and particularly for forming a red cured film of a color filter used for a display element or a solid-state image sensor. Is preferred.

  The coloring composition of the present invention includes C.I. I. Although it is essential that the content ratio of Pigment Violet 19 is more than 0% by mass and less than 30% by mass with respect to all the colorants, C.I. I. It is preferable that the content ratio of the pigment red 170 is as follows.

  For example, when the colored composition of the present invention is used for forming a red cured film of a color filter used in a solid-state imaging device, C.I. I. The content ratio of Pigment Violet 19 is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 7% by mass or more, and preferably 27% by mass or less, and 25% by mass or less with respect to the total colorant. Is more preferable, and 22 mass% or less is still more preferable.

  In addition, when the colored composition of the present invention is used for forming a red cured film of a color filter used for a display element, C.I. I. The content ratio of Pigment Violet 19 is preferably 3% by mass or more, more preferably 5% by mass or more, more preferably 25% by mass or less, and more preferably 23% by mass or less with respect to the total colorant.

Examples of the red colorant contained in the coloring composition of the present invention include a red pigment and a red dye. As the red pigment, for example, a compound classified as a pigment in a color index (CI; issued by The Society of Dyers and Colorists), that is, a color index (CI) number as shown below is given. Can be mentioned.
C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 5, C.I. I. Pigment red 17, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 41, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 48: 5, C.I. I. Pigment red 49, C.I. I. Pigment red 49: 1, C.I. I. Pigment red 49: 2, C.I. I. Pigment red 49: 3, C.I. I. Pigment red 52: 1, C.I. I. Pigment red 52: 2, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 54, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 58, C.I. I. Pigment red 58: 1, C.I. I. Pigment red 58: 2, C.I. I. Pigment red 58: 3, C.I. I. Pigment red 58: 4, C.I. I. Pigment red 60: 1, C.I. I. Pigment red 63, C.I. I. Pigment red 63: 1, C.I. I. Pigment red 63: 2, C.I. I. Pigment red 63: 3, C.I. I. Pigment red 64: 1, C.I. I. Pigment red 68, C.I. I. Pigment red 81, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 200, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 209, C.I. I. Pigment red 214, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 224, C.I. I. Pigment red 237, C.I. I. Pigment red 239, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 247, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 262, C.I. I. Red pigments such as CI Pigment Red 272;

  Examples of red dyes include xanthene compounds, triarylmethane compounds, cyanine compounds, anthraquinone compounds, and dipyrromethene compounds. Specific examples include compounds classified as red dyes among the compounds classified as dyes in the color index (CI; issued by The Society of Dyers and Colorists).

  Among such red colorants, when the colored composition of the present invention is used for forming a red cured film of a color filter used in a solid-state imaging device, the pigment and diketo represented by the following formula (1) as a red colorant It is preferable to include at least one selected from pyrrolopyrrole pigments.

[In Formula (1),
R represents a hydrogen atom or a monovalent organic group,
X ¹ and X ² each independently represent a hydrogen atom or a metal atom. ]
The monovalent organic group in formula (1) is preferably a monovalent hydrocarbon group, and specific examples include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. .
The aliphatic hydrocarbon group may be in the form of either a straight chain or a branched chain, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. 1-30 are preferable, as for carbon number of an aliphatic hydrocarbon group, 1-15 are more preferable, 1-8 are still more preferable, and 1-4 are especially preferable. Most preferred are a methyl group and an ethyl group. Examples of the alkenyl group include ethenyl group and 1-propenyl group. Examples of the alkynyl group include ethynyl group and 1-propynyl group.

The alicyclic hydrocarbon group may be saturated or unsaturated, and the alicyclic hydrocarbon group preferably has 3 to 30 carbon atoms, and more preferably 3 to 12 carbon atoms. Examples of such an alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a 1-cyclohexenyl group, a tricyclodecanyl group, a decahydro-2-naphthyl group, an adamantyl group, and tricyclo [5.2.1. 0 ^2,6 ] decan-8-yl group, pentacyclopentadecanyl group, isobornyl group, dicyclopentenyl group, tricyclopentenyl group and the like.

  Specific examples of the aromatic hydrocarbon group include a phenylene group, a naphthylene group, a biphenylene group, and an anthrylene group.

The hydrocarbon group may further have a substituent, and examples of such a substituent include a halo group, a hydroxyl group, and an alkoxy group having 1 to 6 carbon atoms.
Examples of the metal atom in X ¹ and X ² include alkali metals such as lithium, sodium, potassium, rubidium and cesium, and alkaline earth metals such as magnesium, calcium and barium. Of these, sodium, calcium, and barium are preferable.
Examples of the pigment represented by the formula (1) include C.I. I. Pigment red 57, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 57: 2, C.I. I. Pigment red 57: 3, and C.I. I. Pigment Red 57: 1 is preferable.

  As the diketopyrrolopyrrole pigment, a compound represented by the following formula (2) is preferable.

[In Formula (2),
Y ¹ and Y ² each independently represent a hydrogen atom, a halogen atom or an aryl group. ]
In the formula (2), examples of the halogen atom in Y ¹ and Y ² include a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom and a bromine atom are preferable.
Examples of the aryl group in Y ¹ and Y ² include a phenyl group and a naphthyl group, and a phenyl group is preferable.
Examples of such diketopyrrolopyrrole pigments include C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment Red 264, pigments represented by formula (2) where Y ¹ = Y ² = bromine atom are mentioned. I. Pigment red 254, C.I. I. Pigment Red 264, a pigment in which Y ¹ = Y ² = bromine atom in Formula (2) is preferred, C.I. I. Pigment Red 254 is more preferable.
On the other hand, when the colored composition of the present invention is used for forming a red cured film of a color filter used for a display element, it contains at least one selected from a red pigment having an azo bond and a diketopyrrolopyrrole pigment as a red colorant. Is preferred.
Examples of red pigments having an azo bond include C.I. I. Pigment red 166, C.I. I. Pigment red 208, C.I. I. Pigment red 214 and C.I. I. Preferably at least one selected from the group consisting of CI Pigment Red 242, I. Pigment red 208, C.I. I. Pigment red 214, C.I. I. Pigment Red 242 is more preferable, and C.I. I. Pigment red 208, C.I. I. Pigment Red 242 is more preferable.
Examples of the diketopyrrolopyrrole pigment include the same as those described above. I. Pigment red 254, C.I. I. Pigment Red 264, a pigment in which Y ¹ = Y ² = bromine atom in Formula (2) is preferred, C.I. I. Pigment Red 254 is more preferable.

In the coloring composition of the present invention, the red colorant can be used alone or in admixture of two or more.
When the colored composition of the present invention is used for forming a red cured film of a color filter used in a solid-state imaging device, C.I. I. The content ratio of Pigment Violet 19 and the red colorant is C.I. I. Pigment Violet 19: Red colorant = 1: 99 to 50:50 is preferable, 3:97 to 40:60 is more preferable, 5:95 to 30:70 is still more preferable, and 10:90 to 25:75 is particularly preferable. .

  The colored composition of the present invention preferably further contains a yellow colorant.

  Examples of such yellow colorants include yellow pigments and yellow dyes. Examples of yellow pigments include C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 61, C.I. I. Pigment yellow 61: 1, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 100, C.I. I. Pigment yellow 104, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 133, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 169, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 183, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 191, C.I. I. Pigment yellow 191: 1, C.I. I. Pigment yellow 206, C.I. I. Pigment yellow 209, C.I. I. Pigment yellow 209: 1, C.I. I. Pigment yellow 211, C.I. I. Pigment yellow 212, C.I. I. And CI Pigment Yellow 215.

  As the yellow dye, a known dye exhibiting a yellow color, such as an anthraquinone dye, an azo dye, or a pyridone azo dye, can be used. Specific examples include compounds classified as yellow dyes among the compounds classified as dyes in the color index (CI; issued by The Society of Dyers and Colorists).

  Among these, the following colorants are preferable as the yellow colorant.

  When the colored composition of the present invention is used for forming a red cured film of a color filter used in a solid-state image sensor, examples of the yellow colorant include C.I. I. Pigment yellow 139, C.I. I. An isoindoline pigment such as CI Pigment Yellow 185 is preferable. I. Pigment Yellow 185 is more preferable.

  When the colored composition of the present invention is used for forming a red cured film of a color filter used for a display element, examples of the yellow colorant include C.I. I. Pigment yellow 139, C.I. I. An isoindoline pigment such as CI Pigment Yellow 185 is preferable. I. Pigment Yellow 139 is more preferable.

  When the coloring composition of this invention contains a yellow coloring agent, it is preferable to make the content rate of a yellow coloring agent into the following aspect.

  For example, when the colored composition of the present invention is used for forming a red cured film of a color filter used for a solid-state imaging device, the content of the yellow colorant is preferably more than 0% by mass with respect to the total colorant, and 5% by mass. % Or more is more preferable, 10% by mass or more is more preferable, 40% by mass or less is preferable, and 25% by mass or less is more preferable.

  Moreover, when using the coloring composition of this invention for red cured film formation of the color filter used for a display element, 3-40 mass% is preferable with respect to all the coloring agents, and 5-30 mass%. The mass% is more preferable, and 10 to 25 mass% is still more preferable. By such an aspect, a colored cured film with high luminance can be formed.

  The coloring composition of the present invention may contain other colorants other than those described above to the extent that the effects of the present invention are not affected. Specific examples include organic pigments, lake pigments, and dyes classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists).

  The coloring composition of this invention is used suitably for formation of a red cured film.

  Especially, the solid-state image sensor which has a red pixel with favorable color separation property can be produced with a thin film by using for formation of the red cured film of the color filter used for a solid-state image sensor. Moreover, the organic EL display element which has a high-intensity red pixel can be produced with a thin film by using it for formation of the red cured film of the color filter used for an organic EL display element.

  When the colored composition of the present invention is used for forming a red cured film of a color filter used in a solid-state image sensor, (A) as a colorant, C.I. I. It is preferable that the content rate of the pigment violet 19 is 5-27 mass% with respect to all the coloring agents, and it contains a red coloring agent and a yellow coloring agent, More preferably, C.I. I. The content ratio of Pigment Violet 19 is 7 to 25% by mass with respect to the total colorant, and includes a diketopyrrolopyrrole pigment and an isoindoline pigment.

  Moreover, when using the coloring composition of this invention for formation of the red cured film of the color filter used for a display element, as (A) a coloring agent, C.I. I. Pigment violet 19, red colorant and isoindoline pigment, or C.I. I. It is preferable that it contains at least one selected from Pigment Violet 19 and a red pigment having an azo bond and a diketopyrrolopyrrole pigment.

  In the present invention, C.I. I. Pigment Violet 19, a red pigment used as a red colorant, and other pigments that are optionally mixed are used after being purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. You can also. Further, these pigments may be used by modifying the particle surface with a resin, if desired. Examples of the resin that modifies the particle surface of the pigment include vehicle resins described in JP-A No. 2001-108817, and various commercially available resins for dispersing pigments. The organic pigment may be used after the primary particles are refined by so-called salt milling. As a salt milling method, for example, a method disclosed in Japanese Patent Laid-Open No. 8-179111 can be employed.

  In the present invention, C.I. I. In addition to Pigment Violet 19, the red colorant, and other colorants that are optionally mixed, at least one selected from known dispersants and dispersion aids may also be included.

  Known dispersants include, for example, urethane dispersants, polyethylene imine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants. Dispersants, polyester-based dispersants, (meth) acrylic-based dispersants and the like can be mentioned. Examples of commercially available products include Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN22102 (above, Big Chemie ( BYK))) and other (meth) acrylic dispersants, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-17 , Dispersbyk-182 (above, manufactured by BYK Corporation), urethane dispersants such as Solsperse 76500 (manufactured by Lubrizol Corporation), and polyethyleneimine dispersions such as Solsperse 24000 (manufactured by Lubrizol Corporation) Other than polyester dispersants such as the additives, Azisper PB821, Azisper PB822, Azisper PB880, Azisper PB881 (Ajinomoto Fine Techno Co., Ltd.), BYK-LPN21324 (Bikchemy (BYK) Co.) it can.

  In this invention, a dispersing agent can be used individually or in mixture of 2 or more types.

  In the present invention, the content of the dispersant is preferably 5 to 300 parts by mass, more preferably 10 to 200 parts by mass, and still more preferably 15 to 100 parts by mass with respect to 100 parts by mass of the (A) colorant. -50 mass parts is still more preferable.

  Examples of the dispersion aid include pigment derivatives. Specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivative of quinophthalone.

  (A) The content of the colorant is usually 5 to 70% by mass, preferably 10 to 60% by mass, more preferably in the solid content of the colored composition, from the viewpoint of forming a pixel having high luminance and excellent coloring power. Is 15 to 55% by mass, and 20 to 50% by mass is particularly preferable. Here, solid content is components other than the solvent mentioned later.

-(B) Binder resin-
Although it does not specifically limit as (B) binder resin in this invention, It is preferable that it is resin which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter also referred to as “carboxyl group-containing polymer”) is preferable. For example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). And a copolymer of another copolymerizable ethylenically unsaturated monomer (hereinafter also referred to as “unsaturated monomer (b2)”). .

  Examples of the unsaturated monomer (b1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meta ) Acrylate, p-vinylbenzoic acid and the like.

  These unsaturated monomers (b1) can be used alone or in admixture of two or more.

Moreover, as said unsaturated monomer (b2), for example,
N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;
Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (polymerization degree 2 10) methyl ether (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate Glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[( (Meth) acrylic acid esters such as (meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane;
Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane ;
Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.

  These unsaturated monomers (b2) can be used alone or in admixture of two or more.

  In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 to 50% by mass. More preferably, it is 10 to 40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, a colored composition excellent in alkali developability and storage stability can be obtained.

  Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. No. 10, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, etc. Coalescence can be mentioned.

  In the present invention, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, JP-A-11-140144, As disclosed in Kaikai 2008-181095 and the like, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used as a binder resin.

  The binder resin in the present invention has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran), usually 1,000 to 100,000, preferably Is 3,000 to 50,000. By setting it as such an aspect, the remaining-film rate of a film, a pattern shape, heat resistance, an electrical property, and the resolution can be improved further, and generation | occurrence | production of the dry foreign material at the time of application | coating can be suppressed at a high level.

  Further, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin in the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 3. .0. In addition, Mn here says the number average molecular weight of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran).

  The binder resin in the present invention can be produced by a known method. For example, it is disclosed in JP2003-222717A, JP2006-259680A, International Publication No. 2007/029871, etc. The structure, Mw, and Mw / Mn can be controlled by the method.

  In this invention, binder resin can be used individually or in mixture of 2 or more types.

  In the present invention, the content of the binder resin is usually 5 to 1,000 parts by mass, preferably 10 to 500 parts by mass, and more preferably 20 to 150 parts by mass with respect to 100 parts by mass of the colorant (A). . By setting it as such an aspect, in addition to the further improvement of coloring power and a brightness | luminance, alkali developability, the storage stability of a coloring composition, pattern shape, and chromaticity characteristic can be improved.

-(C) Polymerizable compound-
In the present invention, the polymerizable compound refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, the polymerizable compound is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups.

  Specific examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound and (meth) acrylic acid, a polyfunctional (meta) modified with caprolactone. ) Acrylate, alkylene oxide modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate obtained by reacting hydroxyl-functional (meth) acrylate and polyfunctional isocyanate, hydroxyl-functional (meth) acrylate and acid anhydride The polyfunctional (meth) acrylate which has a carboxyl group obtained by making a product react can be mentioned.

  Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; and 3 such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of aliphatic polyhydroxy compounds having a valence higher than that. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol diester. A methacrylate etc. can be mentioned. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid. Examples thereof include dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

  Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. The alkylene oxide-modified polyfunctional (meth) acrylate is at least one selected from bisphenol A di (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide, ethylene oxide and propylene oxide. Modified with at least one selected from trimethylolpropane tri (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from modified isocyanuric acid tri (meth) acrylate, ethylene oxide and propylene oxide Pen modified with at least one selected from pentaerythritol tri (meth) acrylate, ethylene oxide and propylene oxide. Dipentaerythritol modified with at least one selected from dipentaerythritol penta (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from taerythritol tetra (meth) acrylate, ethylene oxide and propylene oxide Examples include hexa (meth) acrylate.

  Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. The melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and is a concept including melamine, benzoguanamine or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′. , N′-tetra (alkoxymethyl) benzoguanamine, N, N, N ′, N′-tetra (alkoxymethyl) glycoluril and the like.

  Among these polymerizable compounds, polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylates, polyfunctional urethanes (Meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group, N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′, N ′ -Tetra (alkoxymethyl) benzoguanamine is preferred. Among the polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Among polyfunctional (meth) acrylates having a carboxyl group, erythritol hexaacrylate is obtained by reacting pentaerythritol triacrylate and succinic anhydride, and reacting dipentaerythritol pentaacrylate and succinic anhydride. The compound is particularly preferable in that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and background stains and film residues are hardly generated on the unexposed substrate and the light shielding layer.

  In this invention, (C) polymeric compound can be used individually or in mixture of 2 or more types.

  The content of the polymerizable compound (C) in the present invention is preferably 10 to 1,000 parts by weight, more preferably 15 to 500 parts by weight, with respect to 100 parts by weight of the (A) colorant. Is preferred. By adopting such an embodiment, curability and alkali developability are further improved, and in addition to further improvement in coloring power and brightness, background stains, film residue, etc. on the unexposed substrate or on the light shielding layer Occurrence can be suppressed at a high level.

-(D) Photopolymerization initiator-
The coloring composition of the present invention can contain a photopolymerization initiator. Thereby, radiation sensitivity can be provided to a coloring composition. The photopolymerization initiator used in the present invention is a compound that generates an active species capable of initiating polymerization of the polymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray.

  Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, A diazo compound, an imide sulfonate compound, etc. can be mentioned.

  In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. The photopolymerization initiator is preferably at least one selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, a triazine compound, and an O-acyloxime compound.

  Among the preferred photopolymerization initiators in the present invention, specific examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2, 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like can be mentioned.

  Specific examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- And morpholinophenyl) butan-1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′- Bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 Examples include ', 5,5'-tetraphenyl-1,2'-biimidazole.

  In addition, when using a biimidazole compound as a photoinitiator, using a hydrogen donor together is preferable at the point which can improve a sensitivity. The term “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4′-bis (dimethylamino) benzophenone, and 4,4′-bis (diethylamino) benzophenone. Mention may be made of amine hydrogen donors. In the present invention, hydrogen donors can be used alone or in admixture of two or more, but one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. Is preferable in that the sensitivity can be further improved.

  Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) ) -S-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-eth Triazine compounds having a halomethyl group such as cistyryl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

  Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) ) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3- And dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime). As commercially available O-acyloxime compounds, NCI-831, NCI-930 (above, manufactured by ADEKA Corporation), DFI-020, DFI-091 (above, manufactured by Daito Chemix Corporation), and the like can also be used. .

  In this invention, when using photoinitiators other than biimidazole compounds, such as an acetophenone compound, a sensitizer can also be used together. Examples of such a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl. Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

  In the present invention, the content of the (D) photopolymerization initiator is preferably 0.01 to 120 parts by mass, more preferably 1 to 100 parts by mass, with respect to 100 parts by mass of the (C) polymerizable compound. 50 parts by mass is more preferable. By setting it as such an aspect, sclerosis | hardenability and a film characteristic can be improved more and coloring power and a brightness | luminance can be improved further.

-(E) Solvent-
The coloring composition of the present invention contains the above components (A) to (C) and other components optionally added, but is usually prepared as a liquid composition by blending an organic solvent. .

  (E) As a solvent, as long as (A)-(C) component and other components which comprise a coloring composition are disperse | distributed or melt | dissolved, and it does not react with these components, but has moderate volatility. Can be appropriately selected and used.

Among such organic solvents, for example,
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, (poly) alkylene glycol monoalkyl ethers such as tripropylene glycol monoethyl ether;
Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol;
Keto alcohols such as diacetone alcohol;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, (Poly) alkylene glycol monoalkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Glycol ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether;
Cyclic ethers such as tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Alkoxycarboxylates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-butyrate Fatty acid alkyl esters such as propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples thereof include amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone, and lactams.

  Among these organic solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate from the viewpoints of solubility, pigment dispersibility, coatability, etc. , 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3-methoxypropion Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyrate Propionate, acetate n- butyl acetate i- butyl, formic acid n- amyl acetate, i- amyl, n- butyl propionate, ethyl butyrate, i- propyl butyrate n- butyl, ethyl pyruvate and the like are preferable.

  In this invention, a solvent can be used individually or in mixture of 2 or more types.

  (E) Although content of a solvent is not specifically limited, The quantity from which the total density | concentration of each component except the solvent of the coloring composition becomes 5-50 mass% is preferable, and it is 10-40 mass%. Is more preferred. By setting it as such an aspect, the coloring agent dispersion liquid with favorable dispersibility and stability and the coloring composition with favorable coating property and stability can be obtained.

-Additives-
The coloring composition of this invention can also contain a various additive as needed.

  Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorosurfactants and silicon surfactants; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropropi Adhesion promoters such as trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- t-butylphenol, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,9-bis [2- [3- (3-t-butyl-4-hydroxy) -5-methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxa-spiro [5 · 5] undecane, thiodiethylenebis [3- (3,5-di- antioxidants such as t-butyl-4-hydroxyphenyl) propionate]; 2- (3-t-butyl-5-methyl-2-hydroxy Nyl) -5-chlorobenzotriazole, alkoxybenzophenones, etc .; anti-aggregation agents such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol Residue improving agents such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. An improving agent etc. can be mentioned.

  The coloring composition of the present invention can be prepared by an appropriate method. Examples of the preparation method include (A) to (C) components together with (E) a solvent and other components optionally added. , Can be prepared by mixing. Among them, C.I. I. (A) a coloring agent containing Pigment Violet 19 (E) in the presence of a dispersing agent in a solvent, and optionally mixed with a part of (B) a binder resin while being pulverized using, for example, a bead mill or a roll mill. Disperse to give a colorant dispersion, and then add (C) a polymerizable compound, and (B) a binder resin, (D) a photopolymerization initiator, and an additional (E). A method of preparing by adding a solvent and other components and mixing them is preferred.

Colored cured film and method for forming the same The colored cured film of the present invention comprises C.I. I. Pigment violet 19 and a red colorant; I. The content ratio of Pigment Violet 19 is less than 30% by mass with respect to the total colorant, and can be formed using the colored composition of the present invention. As the colored cured film of the present invention, for example, there is a red cured film (red pixel) used for a color filter constituting a display element or a solid-state imaging element.

  Hereinafter, a colored cured film used for a color filter and a method for forming the same will be described.

  As a method for forming the colored cured film constituting the color filter, the following method is first exemplified. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide a portion where pixels are formed, if necessary. Next, for example, after applying a red liquid composition of the radiation-sensitive colored composition of the present invention on the substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Subsequently, after exposing this coating film through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is dissolved and removed. Thereafter, post-baking is performed to form a pixel array in which red pixel patterns (colored cured films) are arranged in a predetermined arrangement.

  Subsequently, using each radiation sensitive coloring composition of green or blue, application of each radiation sensitive coloring composition, pre-baking, exposure, development, and post-baking are performed in the same manner as described above to obtain a green pixel array and blue color. Are sequentially formed on the same substrate. Thereby, a color filter in which pixel arrays of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

  A black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithographic method. It can also be formed in the same manner as in the case of forming the above-mentioned pixel by using the coloring composition.

  Examples of the substrate used when forming the colored cured film include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.

  In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

  When applying the radiation-sensitive coloring composition to the substrate, an appropriate coating method such as spraying, roll coating, spin coating (spin coating), slit die coating (slit coating), bar coating, etc. In particular, it is preferable to employ a spin coating method or a slit die coating method.

  The conditions for heat drying in the pre-baking are usually about 70 to 110 ° C. and about 1 to 10 minutes.

  The coating thickness in the case of forming a cured film of the color filter used for the display element is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, as the film thickness after drying. Moreover, the coating thickness in the case of setting it as the cured film of the color filter used for a solid-state image sensor is 0.3-5 micrometers normally as a film thickness after drying, Preferably it is 0.5-2 micrometers.

  Examples of the radiation light source used when forming at least one selected from the pixel and the black matrix include, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, and a low pressure. Examples thereof include a lamp light source such as a mercury lamp, and a laser light source such as an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser. An ultraviolet LED can also be used as the exposure light source. The wavelength is preferably radiation in the range of 190 to 450 nm.

In general, the exposure dose of radiation is preferably 10 to 10,000 J / m ² .

  Examples of the alkali developer include sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-. An aqueous solution of undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene or the like is preferable.

  For example, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.

  As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.

  The post-baking conditions are usually 180 to 280 ° C. and about 10 to 60 minutes.

  The film thickness of the pixels formed in this manner is 0.5 to 8 μm, preferably 1 to 4 μm, when a colored cured film of a color filter used for a display element is used. Moreover, when setting it as the colored cured film of the color filter used for a solid-state image sensor, it is 0.3-4 micrometers normally, Preferably it is 0.5-2 micrometers.

  Further, as a second method for forming a colored cured film constituting a color filter, a method for obtaining pixels of each color by an ink jet method disclosed in JP-A-7-318723, JP-A-2000-310706, etc. Can be adopted. In this method, first, a partition having a light shielding function is formed on the surface of the substrate. Next, for example, a red liquid composition of the thermosetting coloring composition of the present invention is discharged into the formed partition wall by an inkjet apparatus, and then prebaked to evaporate the solvent. Next, this coating film is exposed as necessary and then cured by post-baking to form a red pixel pattern.

  Subsequently, using each thermosetting coloring composition of green or blue, a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate in the same manner as described above. Thereby, a color filter in which pixel patterns of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

  In addition, since the partition plays not only a light shielding function but also a function for preventing the color mixing of the thermosetting coloring compositions discharged in the respective sections, it is compared with the black matrix used in the first method described above. The film thickness is thick. Therefore, a partition is normally formed using a black radiation sensitive composition.

  The substrate used for forming the colored cured film, the light source of radiation, and the pre-baking and post-baking methods and conditions are the same as in the first method described above. In this way, the film thickness of the pixel formed by the ink jet method is approximately the same as the height of the partition wall.

  A protective film is formed on the pixel pattern thus obtained as necessary, and then a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer can be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, but may be a light-shielding spacer (black spacer). In this case, a colored radiation-sensitive composition in which a black colorant is dispersed is used.

  Since the color filter including the colored cured film of the present invention thus formed has extremely high luminance, a color liquid crystal display element, a color imaging tube element, a color sensor, an organic EL display element, electronic paper, a solid-state imaging element, etc. Very useful.

Display element The display element of the present invention comprises the colored cured film of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.

  The color liquid crystal display element provided with the colored cured film of the present invention may be a transmissive type or a reflective type, and can take an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween. Further, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (tin-doped indium oxide) electrode is formed are a liquid crystal layer. It is also possible to adopt a structure that is opposed to each other. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained. When the latter structure is adopted, the black matrix and the black spacer may be formed on either the substrate side on which the color filter is formed or the substrate side on which the ITO electrode is formed.

  The color liquid crystal display element including the colored cured film of the present invention can include a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). As the white LED, for example, a white LED that obtains white light by color mixing by combining a red LED, a green LED, and a blue LED, a white LED that obtains white light by color mixing by combining a blue LED, a red LED, and a green phosphor, and a blue LED White LED that obtains white light by mixing colors, red LED and green light emitting phosphor, white LED that obtains white light by mixing colors of blue LED and YAG phosphor, blue LED, orange light emitting phosphor and green light emitting fluorescence A white LED that obtains white light by color mixing by combining the body, a white LED that obtains white light by color mixing by combining an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor can be exemplified.

  The color liquid crystal display element having the colored cured film of the present invention includes TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, IPS (In-Plane Switching) type, VA (Vertical Alignment) type, OCB (Optical). An appropriate liquid crystal mode such as a Compensated Birefringence type is applicable.

  Moreover, the organic EL display element provided with the colored cured film of the present invention can take an appropriate structure, and examples thereof include a structure disclosed in JP-A-11-307242.

  Moreover, the electronic paper provided with the colored cured film of the present invention can take an appropriate structure, and examples thereof include a structure disclosed in Japanese Patent Application Laid-Open No. 2007-41169.

Solid-state image sensor The solid-state image sensor of the present invention comprises the colored cured film of the present invention. In addition, the solid-state imaging device of the present invention can take an appropriate structure. For example, as one embodiment, by using the colored composition of the present invention to form a colored pixel (colored cured film) on a semiconductor substrate such as a CMOS substrate by the same operation as described above, particularly color separation is performed. It is possible to manufacture a solid-state imaging device having excellent properties.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

<Synthesis of binder resin>
Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 144 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 48 parts by mass of propylene glycol monomethyl ether acetate, 28.8 parts by mass of methacrylic acid, 18 parts by mass of butyl methacrylate, 18 parts by mass of methyl methacrylate, 2-ethylhexyl EO-modified acrylate (Toago A mixed solution of 18 parts by mass of M-120), 18 parts by mass of cyclohexyl methacrylate and 37.2 parts by mass of glycerol methacrylate, and 48 parts by mass of propylene glycol monomethyl ether acetate and 2,2′-azobis (2,4 -Dimethylvaleronitrile) 8.4 parts by mass of each mixed solution was added dropwise over 2 hours, and polymerization was carried out for 1 hour while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 90 ° C., and polymerization was further performed for 1 hour. Next, this solution was cooled to room temperature, and a resin (B-1 ′) solution was obtained by adding propylene glycol monomethyl ether acetate so that the nonvolatile content was 33% by mass. The obtained resin (B-1 ′) had Mw = 10,700, Mn = 5,600, and Mw / Mn = 1.91.

  Into a flask equipped with a condenser and a stirrer, the entire amount of the resin (B-1 ′) solution was added and the temperature of the solution was raised to 90 ° C., and then 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko KK). ) A mixed solution of 34.3 parts by mass (95 mol% with respect to the number of moles of glycerol methacrylate) and 0.36 parts by mass of 4-methoxyphenol was added dropwise over 15 minutes under air bubbling conditions, and this temperature was maintained. The addition reaction was carried out for 1.5 hours. Next, this solution was cooled to room temperature, and a binder resin solution was obtained by adding propylene glycol monomethyl ether acetate so that the nonvolatile content was 40% by mass. The obtained binder resin was Mw = 12,800, Mn = 6,000, and Mw / Mn = 2.13. Let the obtained solution be "binder resin solution (B-1)."

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 3 parts by mass of 2,2′-azobisisobutyronitrile and 100 parts by mass of propylene glycol monomethyl ether acetate, and subsequently 12 parts by mass of N-phenylmaleimide, 10 parts by mass of styrene, Methacrylic acid 20 parts by mass, 2-hydroxyethyl methacrylate 15 parts by mass, 2-ethylhexyl methacrylate 29 parts by mass, benzyl methacrylate 14 parts by mass and pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Sakai Chemical Industry Co., Ltd.) 5 A mass part was charged and the atmosphere was replaced with nitrogen. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 3 hours for polymerization. Thereafter, the temperature of the reaction solution was raised to 100 ° C., and further polymerized for 1 hour to obtain a solution containing 33.3% by mass of the binder resin (b-2). The obtained binder resin (b-2) had Mw of 9,700 and Mn of 5,700.
This solution containing 33.3% by mass of the binder resin (b-2) is referred to as a “binder resin solution (B-2)”.

<Synthesis of dispersant>
Synthesis example 3
A block having a repeating unit derived from dimethylaminoethyl methacrylate, butyl methacrylate, PME-200 (manufactured by NOF Corporation. Methoxypolyethylene glycol monomethacrylate) with reference to Example 1 of International Publication No. 2011/129078 Pamphlet And a block copolymer comprising a B block having repeating units derived from methacrylic acid (the copolymerization ratio of each repeating unit is dimethylaminoethyl methacrylate / butyl methacrylate / PME-200 / methacrylic acid = 22/47/26/5). And Mw is 10,000). This block copolymer is referred to as “dispersant (X-1)”.

<Preparation of colorant dispersion>
Preparation Example 1
As a coloring agent, C.I. I. 12.0 parts by mass of Pigment Violet 19, 13.0 parts by mass of BYK-LPN21116 (produced by BYK Co., Ltd., solid concentration = 40% by mass) as a dispersant, and a binder resin solution (B-1) as a binder resin ) Using 10.0 parts by mass (solid content concentration 40% by mass), 57.0 parts by mass of propylene glycol monomethyl ether acetate and 8.0 parts by mass of propylene glycol monoethyl ether as solvents, mixed and dispersed by a bead mill for 12 hours. Thus, a colorant dispersion (V-1) was prepared.

Preparation Examples 2 to 10
Colorant dispersions (R-1) to (R-8) and (Y-1) were prepared in the same manner as in Preparation Example 1 except that the type of colorant used in Preparation Example 1 was changed as shown in Table 1. Was prepared.

<Preparation and evaluation of coloring composition>
Example 1
Colorant dispersion (V-1) 79.0 parts by mass, Colorant dispersion (R-1) 421.0 parts by mass, Binder resin solution (B-1) 18.8 parts by mass (solid content concentration 40% by mass) ), 31.5 parts by weight of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (product name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) as a polymerizable compound, and 2-benzyl-2-dimethylamino as a photopolymerization initiator -1- (4-Morpholinophenyl) butan-1-one (Ciba Specialty Chemicals, trade name Irgacure 369) 3.9 parts by mass and NCI-831 (Adeka Co., Ltd.) 0.8 parts by mass , 0.3 part by mass of Megafac F-554 (manufactured by DIC Corporation) as a fluorosurfactant and propylene as a solvent 147.2 parts by weight of glycol monomethyl ether acetate, 255.0 parts by weight of 3-methoxybutyl acetate and 42.5 parts by weight of dipropylene glycol methyl ether acetate were mixed to give a colored composition (RS -1) was prepared. In addition, the coloring agent density | concentration in coloring composition (RS-1) is 40 mass%.

Evaluation of chromaticity characteristics The colored composition (RS-1) was applied on a glass substrate using a spin coater, and then pre-baked on a hot plate at 90 ° C. for 1 minute to form a coating film. The same operation was performed by changing the rotation speed of the spin coater to form three coating films having different film thicknesses.

Next, after cooling these substrates to room temperature, the coating film on the substrates was exposed to radiation containing each wavelength of 365 nm, 405 nm, and 436 nm at 600 J / m ² without using a high pressure mercury lamp. Exposed in quantity. After that, shower development was performed on these substrates by discharging a developer composed of 0.04% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter 1 mm). Thereafter, these substrates were washed with ultrapure water, air-dried, and then post-baked in a clean oven at 230 ° C. for 20 minutes to produce a red cured film.

Using the color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), the chromaticity coordinates (x, y) and the stimulus value in the CIE color system with a C light source and a 2-degree visual field for the obtained three red cured films (Y) was measured. From the measurement result, the stimulus value (Y) when the chromaticity coordinate value x = 0.85 was obtained. Moreover, the film thickness of the obtained cured film was measured using the alpha step IQ made from KLA-Tencor. The evaluation results are shown in Table 4.
In addition, it can be said that a brightness | luminance is so high that a stimulus value (Y) is large.

Examples 2-8 and Comparative Examples 1-10
In Example 1, colored compositions (RS-2) to (RS-18) were prepared in the same manner as in Example 1 except that the types and amounts of the components were changed as shown in Tables 2 to 3.

  Subsequently, the colored composition was evaluated in the same manner as in Example 1 except that the colored compositions (RS-2) to (RS-18) were used instead of the colored composition (RS-1). The evaluation results are shown in Table 4.

In Tables 2-3, each component is as follows.
C-1: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA)
D-1: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals)
D-2: NCI-831 (manufactured by ADEKA Corporation)
F-1: Megafuck F-554 (manufactured by DIC Corporation)
E-1: Propylene glycol monomethyl ether acetate E-2: 3-methoxybutyl acetate E-3: Dipropylene glycol methyl ether acetate

Table 4 shows the types of colorants contained in the colored composition and the content ratios together with the evaluation results. here,
V19: C.I. I. Pigment Violet 19
R149: C.I. I. Pigment Red 149
R166: C.I. I. Pigment Red 166
R177: C.I. I. Pigment Red 177
R208: C.I. I. Pigment Red 208
R214: C.I. I. Pigment Red 214
R242: C.I. I. Pigment Red 242
R254: C.I. I. Pigment Red 254
R264: C.I. I. Pigment Red 264
Y139: C.I. I. Pigment Yellow 139
It is.

<Preparation and evaluation of colored cured film for solid-state imaging device>
<Preparation of colorant dispersion>
Preparation Example 101
As a coloring agent, C.I. I. Pigment Violet 19 in 1.10 parts by mass, C.I. I. Pigment Red 264 is 8.36 parts by mass, C.I. I. 1.54 parts by weight of Pigment Yellow 185, 2.90 parts by weight of dispersant (X-1) as a dispersant, 2.90 parts by weight of binder resin (b-2) as a binder resin, and quinophthalone as a dispersion aid Using 0.80 parts by mass of the pigment derivative and 82.40 parts by mass of propylene glycol monomethyl ether acetate as a solvent, the mixture was dispersed and dispersed by a bead mill for 12 hours to prepare a colorant dispersion (A).

Preparation Examples 102-108
In Preparation Example 1, colorant dispersions (B) to (H) were prepared by changing the type and amount of each component as shown in Table 5.

In Table 5, each component is as follows.
Y185: C.I. I. Pigment Yellow 185
R179: C.I. I. Pigment Red 179
R57: 1: C.I. I. Pigment Red 57: 1
Y-1: Quinophthalone pigment derivative

Example 101
59.09 parts by mass of the colorant dispersion (A), 0.77 parts by mass of the binder resin solution (B-2) (solid content concentration of 33.3% by mass) as the binder resin, and Kayarad DPEA-12 as the polymerizable compound (Nippon Kayaku Co., Ltd., ethylene oxide modified dipentaerythritol hexaacrylate) 1.72 parts by mass, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- ( O-benzoyl oxime) (Ciba Specialty Chemicals Co., Ltd., Irgacure OXE01) 0.62 parts by mass, 1% by mass of propylene glycol monomethyl ether acetate of Megafac F-554 (manufactured by DIC Corporation) as a fluorosurfactant 0.25 parts by weight of the solution and propylene glycol monomethyl ether Acetate was mixed to obtain a colored composition (RS-101) having a solid concentration of 13% by mass. In addition, the coloring agent density | concentration in a coloring composition (RS-101) is 50 mass%.

Evaluation of Transmittance A colored composition (RS-101) was applied on a glass substrate by a spin coating method, and then heated at 100 ° C. for 180 seconds to form a coating film. Subsequently, the entire surface of the coating film on the substrate was exposed (exposure amount of 1,000 mJ / cm ² at a wavelength of 365 nm). Next, the coating film was brought into contact with an aqueous solution containing 0.05% by mass of tetramethylammonium hydroxide for 15 seconds, and then the coating film was washed with water. Then, the glass wafer which has a colored hardening film with a film thickness of 0.6 micrometer was obtained by heating for 300 second with a 200 degreeC hotplate.

  Using a spectrophotometer (manufactured by JASCO Corporation, V-7300), the transmittance (% T) of the glass wafer having the colored cured film was measured, and the transmittance at the following measurement points was determined. The results are shown in Table 7. However, the transmittance | permeability of Table 7 is a value compared with a glass substrate.

Evaluation method Measurement point 1: Transmittance at 415 nm. If it is 15% or less, purple to blue light can be efficiently shielded. It is more preferable if it is 13% or less.
Measurement point 2: transmittance at 500 nm. If it is 10% or less, blue to green light can be efficiently shielded. It is more preferable if it is 8% or less.
Measurement point 3: transmittance at 570 nm. If it is 5% or less, green to yellow light can be efficiently shielded.
Measurement point 4: transmittance at 630 nm. If it is 80% or more, red light can be efficiently transmitted. It is more preferable if it is 85% or more.

  If it is a red cured film that satisfies all the evaluation criteria at the measurement points 1 to 4, it can be said that it is a red cured film for a solid-state imaging device with good color separation. Moreover, if it is a red cured film which satisfy | fills the more preferable evaluation criteria in the measurement points 1-4, it can be said that especially color separation property is favorable.

Evaluation of Resolution A colored composition (RS-101) was applied on a silicon wafer by a spin coating method, and then heated at 100 ° C. for 180 seconds to form a coating film. Exposure was performed by reduced projection exposure (manufactured by Nikon Corporation, NSR-2005i10D, exposure amount of 1,000 mJ / cm ² at a wavelength of 365 nm) through a mask. Next, the coating film was developed by bringing it into contact with an aqueous solution containing 0.05% by mass of tetramethylammonium hydroxide for 15 seconds. Next, the silicon wafer having the developed coating film was heated on a hot plate at 200 ° C. for 300 seconds to obtain a silicon wafer having a square colored cured film having a side of 3 μm.

  The resolution of the colored composition (RS-101) was evaluated by observing the silicon wafer with an electron microscope. The evaluation criteria are as follows, and the results are shown in Table 7.

Evaluation criteria ○: The cross-sectional shape of the pattern is rectangular, and no residue is observed between the patterns.
(Triangle | delta): The cross-sectional shape of a pattern is not a rectangle, or a residue is recognized between patterns.
X: The cross-sectional shape of a pattern is not a rectangle, and a residue is recognized between patterns.

Examples 102-104 and Comparative Examples 101-104
In Example 101, the type and amount of each component were changed as shown in Table 6 to prepare colored compositions (RS-102) to (RS-108). All of the colored compositions (RS-102) to (RS-107) have a solid content concentration of 13% by mass and a colorant concentration of 50% by mass. The coloring composition (RS-108) has a solid content concentration of 13% by mass and a colorant concentration of 55% by mass.
Subsequently, evaluation was performed in the same manner as in Example 101 except that the colored compositions (RS-102) to (RS-108) were used instead of the colored composition (RS-101). Table 7 shows the evaluation results.

In Table 6, each component is as follows.
C-2: Kayalad DPEA-12 (Nippon Kayaku Co., Ltd., ethylene oxide modified dipentaerythritol hexaacrylate)
D-3: 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime) (Irgacure OXE01, manufactured by Ciba Specialty Chemicals Co., Ltd.)
F-2: 1% by mass propylene glycol monomethyl ether acetate solution of MegaFac F-554 (manufactured by DIC Corporation)

Claims (11)

A coloring composition containing (A) a colorant, (B) a binder resin, and (C) a polymerizable compound,
(A) The colorant is C.I. I. Pigment violet 19 and a red colorant; I. The coloring composition whose content rate of pigment violet 19 exceeds 0 mass% with respect to all the coloring agents, and is less than 30 mass%. The coloring composition according to claim 1, which is for forming a red cured film of a color filter used in a solid-state imaging device. The coloring composition of Claim 1 or 2 in which a red coloring agent contains at least 1 sort (s) chosen from the pigment represented by following formula (1), and a diketopyrrolopyrrole pigment.

[In Formula (1),
R represents a hydrogen atom or a monovalent organic group,
X ¹ and X ² each independently represent a hydrogen atom or a metal atom. ] C. I. Pigment Violet 19 and the red colorant are contained in C.I. I. The coloring composition according to any one of claims 1 to 3, wherein Pigment Violet 19: Red Colorant = 1:99 to 50:50. Furthermore, the coloring composition of any one of Claims 1-4 containing a yellow coloring agent.   The colored composition according to claim 1, which is for forming a red cured film of a color filter used in a display element. The coloring composition according to claim 6, wherein the red colorant contains at least one selected from a red pigment having an azo bond and a diketopyrrolopyrrole pigment. A red pigment having an azo bond is C.I. I. Pigment red 166, C.I. I. Pigment red 208, C.I. I. Pigment red 214 and C.I. I. The coloring composition according to claim 7, which is at least one selected from the group consisting of CI Pigment Red 242.   C. I. Pigment violet 19 and a red colorant; I. A colored cured film in which the content ratio of Pigment Violet 19 is more than 0% by mass and less than 30% by mass with respect to all colorants. A solid-state imaging device comprising the colored cured film according to claim 9. A display device comprising the colored cured film according to claim 9.