JP2016206378A - Coloring composition, coloring cured film, and solid state imaging element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition having excellent color reproducibility and suitable for forming a red pixel hardly affecting a transmission region of a green pixel.SOLUTION: A coloring composition for a color filter is a coloring composition containing (A) a colorant, (B) binder resin, and (C) a polymerizable compound, and contains a compound represented by the formula (1) as (A) the colorant.SELECTED DRAWING: None

Description

  The present invention relates to a colored composition, a colored cured film, and a solid-state imaging device, and more specifically, a colored composition used for forming a colored cured film used in a solid-state imaging device, and the colored composition. The present invention relates to a colored cured film and a solid-state imaging device including the colored cured film.

  A solid-state imaging device such as a CCD or CMOS generally disposes colors by disposing B (blue), G (green), and R (red) pixels on the light receiving element. As an ideal spectral characteristic of a pixel, it is required that transmittance in a wavelength region of colors other than the color of the pixel is reduced and that color separation is excellent. For example, in the case of a red pixel, a red pixel with reduced transmittance in the blue to green wavelength region is required.

  In general, toning is performed using two or more types of pigments in order to obtain color characteristics required in each pixel. For example, in a red pixel, C.I. I. Pigment red 177, C.I. I. Pigment red 242, C.I. I. Pigment Red 254 or the like is used (for example, see Patent Documents 1 to 3).

JP 9-325209 A Japanese Patent Laid-Open No. 11-14824 JP 2000-89025 A

  In recent years, for color filters used in solid-state imaging devices, there is an increasing demand for pixel thinning in order to increase the amount of light reaching the light receiving portion in order to improve light sensitivity.

 In addition, in a color filter used for a solid-state imaging device, in order to obtain good color reproducibility, it is also required that the rising from the absorption region to the transmission region in the transmission curve is gradual with respect to the pixel.

  In order to meet such demands for thinning, the concentration of pigments is being studied, but there are increasing demands for color characteristics for color filters, such as further thinning pixels and improving color separation. Below, it is becoming difficult to meet the demand even if the conventional technique of simply increasing the concentration of the pigment is applied.

  Further, according to the study by the present inventors, it has been found that it is difficult to produce a red pixel that achieves both color reproducibility and color separation only by using a conventionally used pigment for forming a red pixel. That is, C.I. I. When Pigment Red 254 is used, it is difficult to produce a red pixel having good color reproducibility because the transition from the absorption region to the transmission region is steep in the transmission curve, and the transmittance in the wavelength region of 520 nm to 540 nm is difficult. Is slightly higher, which affects the transmission region of the green pixel. On the other hand, C.I. I. When Pigment Red 177 is used, the rise from the absorption region to the transmission region in the transmission curve is C.I. I. Although it is more gradual than Pigment Red 254, the transmittance in the wavelength region of 480 nm to 520 nm is increased, which affects the transmission region of the green pixel. Further, C.I. I. When CI Pigment Red 242 is used, the transmittance in the green wavelength region is low, but the transition from the absorption region to the transmission region in the transmission curve is C.I. I. Since it is on the short wavelength side compared to Pigment Red 254, the color separation from the green pixel is affected. Here, “color separation” refers to having spectral characteristics that do not easily affect the transmission region of a green pixel.

  As described above, it is difficult to form a red pixel that achieves both good color reproducibility and color separation when the conventional red pigment is used alone or in combination with other pigments as the main pigment. Met.

  Therefore, the subject of this invention is providing the coloring composition suitable for formation of a red pixel which has favorable color reproducibility and is hard to affect the permeation | transmission area | region of a green pixel. Furthermore, the subject of this invention is providing the solid-state image sensor which comprises the red pixel formed using the said coloring composition, and this red pixel.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by using a pigment having a specific structure.

  That is, this invention is a coloring composition containing (A) a coloring agent, (B) binder resin, and (C) polymeric compound, Comprising: (A) The compound represented by following formula (1) as a coloring agent The coloring composition for color filters containing this is provided.

[In Formula (1),
R represents a monovalent organic group,
X ¹ and X ² each independently represent a hydrogen atom or a metal atom. ]
The present invention also provides a colored cured film of a color filter containing a compound represented by the formula (1), and a solid-state imaging device comprising the colored cured film. The “colored cured film” as used herein means each color pixel, protective film, black matrix, spacer, insulating film, etc. used in a display element or solid-state imaging element.

  By using the coloring composition of the present invention, it is possible to form a red pixel having good color reproducibility and hardly affecting the transmission region of the green pixel.

  Therefore, the colored composition of the present invention can be used very suitably for the production of a solid-state imaging device such as a CMOS image sensor.

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 this invention makes it essential to contain the compound represented by the said Formula (1) as (A) coloring agent. 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 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, such as a halogen atom, hydroxyl group, cyano group, formyl group, carboxy group, nitro group, amino group, dialkylamino group, diarylamino group. Groups, alkoxy groups, aryloxy groups, alkoxycarbonyl groups, alkylthio groups, arylthio groups, trialkylsilyl groups, mercapto groups, allyl groups, alkylsulfonyl groups, alkylsulfamoyl groups, and the like.
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 compound 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.

  In the colored composition of the present invention, the content ratio of the compound represented by the formula (1) is more than 0% by mass and preferably 80% by mass or less, more preferably 20 to 70% by mass with respect to the total colorant. 30-65 mass% is still more preferable.

Usually, the compound represented by the formula (1) can be used as a red colorant, but the colored composition of the present invention further contains a red colorant other than the compound represented by the formula (1). May be. Such other red colorants include red pigments and red dyes. 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 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, it is preferable to include at least one selected from anthraquinone pigments and diketopyrrolopyrrole pigments as other red colorants. As an anthraquinone pigment, C.I. I. Pigment red 177, C.I. I. Pigment red 179, C.I. I. Pigment Red 224 is preferred, and C.I. I. Pigment Red 179 is more preferable.
The diketopyrrolopyrrole pigment is a compound represented by the following formula (2).

[In Formula (2), Y < ¹ > and Y < ² > show a hydrogen atom, a halogen atom, or an aryl group mutually independently. ]
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, C.I. I. Pigment Red 272, and a pigment where Y ¹ = Y ² = bromine atom in the formula (2) can be mentioned. I. Pigment red 254, C.I. I. Pigment Red 264, a pigment where Y ¹ = Y ² = bromine atom in formula (2) is preferred.

  In the colored composition of the present invention, the content of the red colorant other than the compound represented by the formula (1) is preferably 0 to 50% by mass and more preferably 25 to 45% by mass with respect to the total colorant. preferable.

  Other red colorants other than the compound represented by Formula (1) can be used alone or in admixture of two or more.

  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, examples of yellow colorants 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 coloring composition of the present invention contains a yellow colorant, the content ratio of the yellow colorant is preferably more than 0% by mass and 55% by mass or less, more preferably 20-50% by mass with respect to the total colorant. Preferably, it is more preferably 25 to 45% by mass.

  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.

  In the present invention, the compound represented by the formula (1) and other pigments that are optionally mixed are purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. Can also be used. 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.

  Moreover, in this invention, at least 1 sort (s) chosen from a well-known dispersing agent and a dispersing aid can also be contained with the compound represented by Formula (1), and the other coloring agent mixed arbitrarily.

  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 rate of a coloring agent is 70 mass% or less normally in solid content of a coloring composition. The colored composition of the present invention is used for forming a colored cured film of a color filter. However, if the content of the colorant is too high, color dispersion such as pigment dispersibility, storage stability, curability, developability, etc. In some cases, the characteristics generally required for a colored cured film for a filter cannot be ensured. The colored composition of the present invention is preferably used for color filter applications in that it can form a red pixel that achieves both good color reproducibility and color separation even if the content of the colorant is not high. it can. That is, even when the content ratio of (A) the colorant is 60% by mass or less, further 55% by mass or less, further 50% by mass or less, and further 48% by mass or less, both good color reproducibility and color separation are achieved. On the other hand, it is possible to satisfy characteristics generally required for a colored cured film for a color filter, such as pigment dispersibility, storage stability, curability, and developability. In addition, the lower limit of the content ratio of the colorant (A) is usually 5% by mass or more, 30% by mass or more, and further 40% by mass or more, having good color reproducibility and transmitting green pixels. This is preferable in that a red pixel that hardly affects the region can be formed. 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.
Furthermore, as the binder resin (B) in the present invention, in addition to the resin having the acidic functional group, the co-polymerization of a monomer containing an unsaturated monomer having at least one selected from an ethylene oxide chain and a propylene oxide chain Coalescence is also preferred. Examples of the unsaturated monomer include polyethylene glycol (polymerization degree 2 to 10) methyl ether (meth) acrylate and polypropylene glycol (polymerization degree 2 to 10) methyl exemplified in the description of the unsaturated monomer (b2). Examples include ether (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, paracumylphenol ethylene oxide-modified (meth) acrylate, and the like. be able to.

  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, alkali developability, the storage stability of a coloring composition, and a pattern shape 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 setting it as such an aspect, sclerosis | hardenability and alkali developability can be improved more and generation | occurrence | production of background dirt, film residue, etc. on the board | substrate of an unexposed part 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). Commercially available O-acyloxime compounds include NCI-831, NCI-930 (above, manufactured by ADEKA Corporation), DFI-020, DFI-091 (above, manufactured by Daito Chemix Corporation), OXE-03, OXE- 04 (above, manufactured by BASF) or 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.
-(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.

  Of these organic solvents, one or more selected from (poly) alkylene glycol monoalkyl ether acetate, ketoalcohol and ketone are preferred from the viewpoints of solubility, pigment dispersibility, coatability and the like.

  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, the (A) colorant containing the compound represented by the formula (1) is used in (E) a solvent, in the presence of a dispersant, and optionally (B) a part of the binder resin, for example, a bead mill, a roll mill, etc. Is mixed and dispersed while being pulverized to obtain a colorant dispersion, and then the colorant dispersion is mixed with (C) a polymerizable compound, and (B) a binder resin, and (D) photopolymerization, if necessary. A method in which an initiator, an additional (E) solvent and other components are added and mixed is preferable.
Colored cured film and method for forming the same The colored cured film of the present invention contains the compound represented by the formula (1) and can be formed using the colored composition of the present invention. Examples of the colored cured film of the present invention include a red cured film (red pixel), a protective film, a black matrix, a spacer, and an insulating film used for color filters constituting display elements and solid-state imaging elements. It is preferable to use for the red cured film used for the color filter which comprises an element and a solid-state image sensor.

  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 using a sexually colored 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.

The color filter including the colored cured film of the present invention thus formed is extremely useful for a color liquid crystal display element, a color image pickup tube element, a color sensor, an organic EL display element, electronic paper, a solid-state image pickup element and the like.
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 3 parts by mass of 2,2′-azobisisobutyronitrile and 100 parts by mass of propylene glycol monomethyl ether acetate (hereinafter also referred to as “PGMEA”), followed by N-phenyl. 12 parts by weight of maleimide, 10 parts by weight of styrene, 20 parts by weight of methacrylic acid, 15 parts by weight of 2-hydroxyethyl methacrylate, 29 parts by weight of 2-ethylhexyl methacrylate, 14 parts by weight of benzyl methacrylate and pentaerythritol tetrakis (3-mercaptopropionate) 5 parts by mass (manufactured by Sakai Chemical Industry Co., Ltd.) was charged and purged 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 polymerization was further performed for 1 hour.

  After cooling to room temperature, PGMEA was added so that the solid content concentration was 40% by mass to obtain a binder resin solution (solid content concentration 33.3% by mass). The obtained binder resin (B-1) had Mw of 9,700 and Mn of 5,700. This binder resin solution is referred to as “binder resin (B-1) solution”.

Synthesis example 2
In Synthesis Example 1, a binder resin was prepared in the same manner as in Synthesis Example 1 except that 20 parts by mass of methoxypolyethylene glycol monomethacrylate (trade name PME-200, manufactured by NOF Corporation) was used instead of 20 parts by mass of methacrylic acid. Synthesized. Let the obtained binder resin solution be a "binder resin (B-2) solution."

<Preparation of colorant dispersion>
Preparation Example 1
As a coloring agent, C.I. I. Pigment Red 57: 1 is 7.15 parts by mass and C.I. I. 3.85 parts by mass of Pigment Yellow 185, 2.90 parts by mass (in terms of solid content) of BYK-LPN21116 (produced by BYK Corporation) as a dispersant, and 2.90 of binder resin (B-1) as a binder resin. Colored by mixing and dispersing for 12 hours in a bead mill using 0.80 parts by mass of compound b (sulfonic acid derivative of quinophthalone) as a dispersion aid and 82.40 parts by mass of PGMEA as a solvent. An agent dispersion (A) was prepared.

Preparation Examples 2-9
In Preparation Example 1, colorant dispersions (B) to (I) were prepared by changing the type and amount of each component as shown in Table 1.

In Table 1, each component is as follows.
R57: 1: C.I. I. Pigment Red 57: 1
R264: C.I. I. Pigment Red 264
R254: C.I. I. Pigment Red 254
Compound (2-1): Compound R179 in the above formula (2) where Y ¹ = Y ² = bromine atom: C.I. I. Pigment Red 179
Y139: C.I. I. Pigment Yellow 139
Y185: C.I. I. Pigment Yellow 185
LPN21116: BYK-LPN21116 ((Meth) acrylic dispersant, manufactured by BYK (BYK)))
Compound b: sulfonic acid derivative of quinophthalone

<Preparation of composition for forming underlying film>
Preparation Example 10
After the atmosphere in the flask was replaced with nitrogen, 200 parts by mass of a methyl-3-methoxypropionate solution in which 0.6 parts by mass of 2,2′-azobisisobutyronitrile was dissolved was charged. Subsequently, 37.5 parts by mass of tert-butyl methacrylate and 62.5 parts by mass of glycidyl methacrylate were charged, stirred, and heated at 70 ° C. for 6 hours. After cooling, a resin solution containing a polymer was obtained.

  Next, after diluting 33.3 parts by mass (containing 10 parts of the polymer) of this resin solution, 31.9 parts by mass of methyl-3-methoxypropionate, and 3.4 parts by mass of propylene glycol monomethyl ether. , 0.3 parts by mass of trimellitic acid, 0.5 parts by mass of 3-glycidoxypropyltrimethoxysilane, and 0.005 parts by mass of the trade name “FC-4432” (manufactured by Sumitomo 3M Limited) Then, a composition for forming a base film was prepared.

<Preparation and evaluation of coloring composition>
Example 1
53.18 parts by weight of the colorant dispersion (A), 2.23 parts by weight of the binder resin (B-1) solution as the binder resin, and Kayrad DPEA-12 (produced by Nippon Kayaku Co., Ltd. 2.28 parts by mass of pentaerythritol hexaacrylate), 0.61 parts by mass of NCI-930 (manufactured by ADEKA Corporation) as a photopolymerization initiator, and Ftergent FTX-218 (manufactured by Neos Corporation) as a fluorosurfactant A colored composition (RS-1) having a solid content concentration of 13% by mass was prepared by mixing 0.30 part by mass of a 1% by mass PGMEA solution and 41.39 parts by mass of PGMEA as a solvent. In addition, the coloring agent density | concentration in coloring composition (RS-1) is 45 mass%.

Evaluation of transmittance A colored composition (RS-1) 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 3. However, the transmittance | permeability of Table 3 is a value compared with a glass substrate.

Evaluation method Measurement point 1: Transmittance at 400 nm. If it is 15% or less, purple light can be efficiently shielded. 10% or less is more preferable, and 7% or less is still more preferable.
Measurement point 2: transmittance at 450 nm. If it is 10% or less, purple to blue light can be efficiently shielded. 5% or less is more preferable, and 3% or less is still more preferable.
Measurement point 3: transmittance at 530 nm. If it is 10% or less, green light can be efficiently shielded. 8% or less is more preferable.
Measurement point 4: transmittance at 630 nm. If it is 80% or more, red light can be efficiently transmitted. 85% or more is more preferable.

  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 that hardly affects the transmission region of the green pixel, that is, has 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 Pattern Shape and Residue Using an automatic coating and developing apparatus (clean track manufactured by Tokyo Electron Ltd., trade name “MARK-Vz”) on a silicon wafer, the composition for forming an underlying film is formed by spin coating. After coating, baking was performed at 230 ° C. for 300 seconds to form a base film having a thickness of 0.6 μm.

A colored composition (RS-1) was applied onto the undercoat film 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-1) was evaluated by observing the silicon wafer with an electron microscope. The evaluation criteria are as follows, and the results are shown in Table 3.

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 2-8 and Comparative Examples 1-3
In Example 1, the kind and quantity of each component were changed as shown in Table 2, and colored compositions (RS-2) to (RS-11) were prepared. All of the colored compositions (RS-2) to (RS-11) have a solid content concentration of 13% by mass.

  Next, evaluation was performed in the same manner as in Example 1 except that the colored compositions (RS-2) to (RS-11) were used instead of the colored composition (RS-1). The evaluation results are shown in Table 3.

In Table 2, each component is as follows.
C-1: Kayalad DPEA-12 (Nippon Kayaku Co., Ltd., ethylene oxide modified dipentaerythritol hexaacrylate)
D-1: NCI-930 (manufactured by ADEKA Corporation)
D-2: IRGACURE OXE-04 (manufactured by BASF)
F-1: 1 mass% PGMEA solution of footgent FTX-218 (manufactured by Neos Co., Ltd.)

In Table 3, “the content ratio of the colorant” is the content ratio of the colorant (A) relative to the solid content of the color composition, and “the ratio of each colorant” is the total colorant in the color composition. It is a content rate of each coloring agent with respect to.

Claims (7)

A coloring composition containing (A) a colorant, (B) a binder resin, and (C) a polymerizable compound,
(A) A colored composition for a color filter comprising a compound represented by the following formula (1) as a colorant.

[In Formula (1),
R represents a monovalent organic group,
X ¹ and X ² each independently represent a hydrogen atom or a metal atom. ]   The coloring composition according to claim 1, wherein R is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. (A) The coloring composition of Claim 1 or 2 whose content rate of a coloring agent is 5 mass% or more and 70 mass% or less in solid content of a coloring composition. Furthermore, the coloring composition of any one of Claims 1-3 containing a yellow coloring agent. Furthermore, the coloring composition of any one of Claims 1-4 containing other red coloring agents other than the compound represented by Formula (1). A colored cured film for a color filter comprising a compound represented by the following formula (1).

[In Formula (1),
R represents an aliphatic hydrocarbon group;
X ¹ and X ² each independently represent a hydrogen atom or a metal atom. ] A solid-state imaging device comprising the colored cured film according to claim 6.