WO2007125864A1

WO2007125864A1 - Light blocking resin composition, color filter, and liquid crystal display

Info

Publication number: WO2007125864A1
Application number: PCT/JP2007/058737
Authority: WO
Inventors: Toshiya Naruto; Junji Mizukami
Original assignee: Mitsubishi Chemical Corporation
Priority date: 2006-04-28
Filing date: 2007-04-23
Publication date: 2007-11-08
Also published as: KR101439085B1; JP2007316620A; CN101313032B; TW200808887A; TWI431053B; CN101313032A; JP5029119B2; KR20090005262A

Abstract

Disclosed is a light blocking resin composition which enables to form a black matrix excellent in developability, resolution and adhesion, especially in linearity and adhesion. The light blocking resin composition contains a binder resin, a monomer, a photopolymerization initiator and a carbon black having an average particle diameter of not less than 8 nm but not more than 65 nm and a DBP oil absorption of not more than 90 ml/100 g. In addition, this light blocking resin composition contains not more than 20 ppm of potassium ions relative to the total solid content. Also disclosed are a color filter having a pixel formed by using this light blocking resin composition, and a liquid crystal display comprising such a color filter.

Description

Specification

Light-shielding resin composition, color filter, and liquid crystal display device

Field of Invention

[0001] The present invention relates to a light-shielding resin composition, a color filter, and a liquid crystal display device. Specifically, it is a light-shielding oil that can form black pixels with excellent linearity and adhesion, suitable for the production of optical power filters used in color televisions, liquid crystal display devices, solid-state imaging devices, cameras, etc. The present invention relates to a composition, a color filter using the light-shielding resin composition, and a liquid crystal display device including the color filter.

Background of the Invention

[0002] Color filters usually form black pixels (hereinafter sometimes referred to as "black matrix") on the surface of a transparent substrate such as glass or plastic sheet, and then red, green, blue, etc. These three or more different colored pixels are sequentially formed in a striped or mosaic color pattern.

[0003] The pattern size varies depending on the use of the color filter and each color, but is usually about 5 to 700 μm. Further, the positional accuracy of the overlay is several μm to several tens of μm, and it is manufactured with high dimensional accuracy and a fine processing technique.

[0004] Typical methods for producing a color filter include a dyeing method, a printing method, a pigment dispersion method, and an electrodeposition method. Among these, in particular, the pigment dispersion method in which a colored resin composition containing a color material is applied on a transparent substrate and image exposure, development, and curing as necessary is repeated to form a color filter image is a formation method. The position of the color filter pixel, the accuracy of the film thickness, etc. are high. It has excellent durability such as light resistance and heat resistance, and has few defects such as pinholes, so it is widely used.

[0005] The production of color filters requires a fine processing technique with high dimensional accuracy as described above, and therefore, the colored resin composition used requires strict developability, resolution, and adhesion. It is done. In particular, in the production of a black matrix, since it is formed from a light-shielding resin composition, higher performance developability, resolution, and adhesion are required, and red is formed in a subsequent process. Thin film formation is also necessary so that the flatness of colored pixels of green and blue is not impaired. It is demanded. For example, a technology that improves sensitivity by improving the photopolymerization initiator and achieves high-performance developability, resolution, and adhesion in the black matrix is disclosed! Patent Document 1).

[0006] On the other hand, when a black matrix is formed by the light-shielding resin composition, there is a possibility that it is adjacent to the liquid crystal in the liquid crystal display device, and metal ions derived from the light-shielding resin composition for forming the black matrix. It is known that when a good conductive material such as the above flows out to the liquid crystal side, the voltage holding ratio of the liquid crystal is lowered and the life of the liquid crystal display device is shortened. To solve the problem, a technology to reduce the total content of sodium atoms and sodium ions in the colored pixels and black matrix to a certain range, and formation of a black matrix in which the amount of monovalent metal cations is below a certain value And a color filter (Patent Document 3) using a black matrix with a light shielding material of carbon black in which the total content of Na and Ca is reduced to a certain value or less are disclosed. Speak.

Patent Document 1: Japanese Unexamined Patent Application Publication No. 2005-128483

Patent Document 2: Japanese Patent Laid-Open No. 7-271020

Patent Document 3: Japanese Patent Laid-Open No. 9-71733

[0007] The above-described conventional technique for reducing the metal ion content is intended to prevent a decrease in the voltage holding ratio of the liquid crystal, and only with the above technique, developability, resolution, and adhesion can be achieved. I could n’t do anything. In addition, the improvement of the photopolymerization initiator in the prior art described above has been insufficient in terms of improving the strict developability, resolution, adhesion, particularly linearity and adhesion.

[0008] The carbon black used in the light-shielding resin composition preferably has a relatively small structure. Such carbon black is produced, for example, by burning heavy oil in a system to which an inorganic compound containing potassium element is added. The obtained carbon black contains potassium ions. However, according to the study by the present inventors, potassium ions in the light-shielding resin composition are obtained from the pixels formed using the light-shielding resin composition. It has been found that it becomes a factor that impedes adhesion to the substrate, resolution, and strict developability.

Summary of the Invention [0009] The present invention has been made in view of the above-described conventional situation, and is a light-shielding property capable of forming a black matrix excellent in developability, resolution, adhesion, particularly linearity and adhesion. An object of the present invention is to provide a resin composition, a color filter using the light-shielding resin composition, and a liquid crystal display device including the color filter.

The light-shielding resin composition of the first aspect is a light-shielding resin composition containing a binder resin, a monomer, a photopolymerization initiator, and carbon black, and the carbon black has an average particle size of 8 nm or more. 65 nm or less, the DBP oil absorption of carbon black is 90 mlZlO Og or less, and the potassium ion content of the light-shielding resin composition is 20 ppm or less based on the total solid content. is there.

The color filter of the second aspect has a pixel formed using the light-shielding resin composition of the first aspect.

The liquid crystal display device according to the third aspect includes the color filter according to the second aspect.

Detailed description

[0010] The inventors of the present invention have disclosed a light-shielding film containing a noda resin, a monomer, a photopolymerization initiator, and carbon black having a specific average particle size and DBP oil absorption, and having a reduced potassium ion content. It has been found that the black matrix formed using the oil composition has an unprecedented effect that the conventional technical ability is excellent in developability, resolution, adhesion, especially linearity and adhesion. .

[0011] According to the light-shielding resin composition of the present invention, it is possible to form a black matrix that is excellent in developability, resolution, adhesion, particularly linearity, adhesion, and thereby high quality. A color filter and a liquid crystal display device can be provided.

[0012] Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention exceeds the gist thereof. As long as it is not limited to these contents.

[0013] [1] Shading resin composition

The light-shielding resin composition of the present invention comprises, as essential components, binder resin, monomer, photopolymerization initiator, and power bon black having an average particle size of 8 nm to 65 nm and a DBP oil absorption of 90 mlZ 1 OOg or less. If necessary, other additives other than the above components It is a blended one. It is essential that the potassium ion content is 20 ppm or less based on the total solid content.

[0014] The use of the light-shielding resin composition of the present invention is not particularly limited, but is particularly preferably used as a composition for the purpose of forming black pixels (black matrix) of color filters.

Hereinafter, each component contained in the light-shielding resin composition of the present invention will be described.

In the present specification, “(meth) acryl”, “(meth) acrylate”, etc. mean “acryl and Z or methacryl”, “acrylate and Z or metatalate”, and the like. For example, “(meth) acrylic acid” means “acrylic acid and Z or methacrylic acid”.

[0017] In the section [1], "total solids" refers to all components of the light-shielding resin composition of the present invention other than the solvent components described later.

[0018] [1 1] Binder resin

As the binder resin used in the light-shielding resin composition of the present invention, it is preferable to use an epoxy acrylate resin having a carboxyl group.

[0019] The epoxy acrylate resin is obtained by adding an α, β unsaturated monocarboxylic acid or an α, β unsaturated monocarboxylic acid ester having a carboxyl group to the ester moiety to the epoxy resin, and further adding a polybasic acid anhydride. It is synthesized by reacting. Such a reaction product has substantially no epoxy group due to its chemical structure, and is not limited to “attalylate”, but epoxy resin is a raw material, and “attalylate” is a representative example. Therefore, it is named like this according to common usage.

[0020] The epoxy resin used as a raw material is, for example, bisphenol type epoxy resin (for example, “Epicoat 828”, “Epicoat 1001”, “Epicoat 1002”, “Epicoat 1004” manufactured by Yuka Shell Epoxy Co., Ltd.) , Epoxy resin obtained by reaction of alcoholic hydroxyl group of bisphenol A type epoxy resin with epichlorohydrin (for example “NE R-1302J (epoxy equivalent 323, softening point 76 ° C made by Nippon Kayaku Co., Ltd.) )), Bisphenol F type resin (for example, “Epicoat 807”, “EP—4001,” “EP—4002,” “EP 4004, etc.” manufactured by Yuka Shell Epoxy Co., Ltd.), Bisphenol F type epoxy resin Epoxy resin obtained by the reaction of alcoholic hydroxyl group and epichlorohydrin (eg “NER-7406” manufactured by Nippon Kayaku Co., Ltd.) (Epoxy equivalent 350, softening point 66 ° C)), bisphenol S type epoxy resin, biphenyl daricidyl ether (for example, “YX-4000” manufactured by Yuka Shell Epoxy Co., Ltd.), phenol nopolak type epoxy resin (for example, , ΓΕΡΡΝ-201, manufactured by Nippon Kayaku Co., Ltd., “」 -152 ”,“ ΕΡ-154 ”manufactured by Yuka Shellepoxy,“ DEN-438 ”manufactured by Dow Chemical Co., Ltd.), (o, m, ρ —) Cresolol novolac-type epoxy resin (eg “EOCN-10 2S”, “EOCN-1020”, “EOCN-104S” manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanurate (eg Nissan Chemical) "TEPK"), trisphenol methane type epoxy resin (for example, "EPPN-501", "EPN-502", "EPPN-503" manufactured by Nippon Kayaku Co., Ltd.), fluorene epoxy resin (for example, , Nippon Steel Chemical Co., Ltd.'s power-based epoxy resin "ESF-300"), Cyclic epoxy resin (“Celoxide 2021P”, “Celoxide® E” manufactured by Daicel Chemical Industries, Ltd.), dicyclopentagen type epoxy resin obtained by glycidylation of phenol resin by reaction of dicyclopentagen and phenol ( For example, “XD-1000” manufactured by Nippon Gaiyaku Co., Ltd., “EXA-7200” manufactured by Dai Nippon Ink Co., Ltd., “NC-3000”, “NC-7300” manufactured by Nippon Kayaku Co., Ltd.), and the following structural formula (See Japanese Patent No. 2878486), etc. can be suitably used.

[0021] [Chemical 1]

[0022] These may be used alone or in combination of two or more.

[0023] Another example of the epoxy resin is a copolymerized epoxy resin. Examples of the copolymerized epoxy resin include glycidyl (meth) acrylate, (meth) attalyloylmethyl cyclohexene oxide, burcyclohexene oxide and the like (hereinafter referred to as “the first component of copolymerized epoxy resin). ) And other monofunctional ethylenically unsaturated group-containing compounds (hereinafter referred to as “second component of copolymer epoxy resin”), for example, methyl (meth) atari , Ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, styrene, phenoxychetyl (meth) acrylate , Benzyl (meth) acrylate, _a -methylstyrene, glycerol mono (meth) acrylate, and one or more compounds selected by the compound represented by the following general formula (1). And copolymers.

[0024] [Chemical 2]

In the formula (1), R ⁶¹ represents hydrogen or an ethyl group, R ⁶² represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and r is an integer of 2 to 10.

[0025] The compound of the general formula (1) includes, for example, polyethylene glycol mono (meta) such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene dallicol mono (meth) acrylate. ) Atarylate; Alkoxypolyethylene dallic (meth) acrylate, such as methoxydiethylene glycol mono (meth) acrylate, methoxytriethylene glycol mono (meth) acrylate, methoxytetraethylene glycol mono (meth) acrylate, etc. It is done.

[0026] The weight-average molecular weight (Mw) in terms of polyethylene measured by GPC of the copolymerized epoxy resin is preferably about 1000 to 200,000. The amount of the first component of the copolymerized epoxy resin used is preferably 10% by weight or more, particularly preferably 20% by weight or more, preferably with respect to the second component of the copolymerized epoxy resin. Is less than 70% by weight, particularly preferably less than 50% by weight.

[0027] Specific examples of such copolymer type epoxy resins include "CP-15", "CP-30", "CP-50", "CP-20SA", "CP" manufactured by Nippon Oil & Fats Co., Ltd. — 510SA ”,“ CP-50S ”,“ CP-50M ”,“ CP-20MA ”and the like.

[0028] The molecular weight of the raw material epoxy resin is usually in the range of 200 to 200,000, preferably 300 to 100,000 as the weight average molecular weight in terms of polystyrene measured by GPC. On the contrary, if the weight average molecular weight is less than the above range, a problem may occur in the film forming property. In the case of a resin having a viscosity exceeding 50%, gelling is likely to occur during the addition reaction of α and β unsaturated monocarboxylic acids, and the production may be difficult.

[0029] Examples of the a, β-unsaturated monocarboxylic acid include itaconic acid, crotonic acid, cinnamic acid, acrylic acid, methacrylic acid, and the like, preferably acrylic acid and methacrylic acid, and particularly attalic acid is reacted. It is preferred because of its rich nature.

[0030] The α, j8-unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety includes 2-succinoyloxychetyl acrylate, 2-maleyloxychityl acrylate, 2-phthaloyl acrylate. Xichetyl, 2-hexahydrophthaloyloxetyl acrylate, 2-succinoyloxychetyl methacrylate, 2-maleyloxychetyl methacrylate, 2-phthaloyloxychetyl methacrylate, Examples include 2-methylhexallylmethacrylate 2-hexahydrophthaloyloxetyl, crotonic acid 2-succinoyloxyethyl, etc., preferably 2-acryloylethyl acrylate and 2-phthaloyl acrylate. It is chichetil, particularly 2-maleyloxychhetyl acrylate. These may be used alone or in combination of two or more.

[0031] The addition reaction of a, j8-unsaturated monocarboxylic acid or its ester and epoxy resin can be carried out using a known method, for example, at a temperature of 50 to 150 ° C in the presence of an esterification catalyst. It can implement by making it react. Here, as the ester catalyst, tertiary amine such as triethylamine, trimethylamine, benzyldimethylamine, benzyljetylamine, etc .; tetramethylammonium chloride, tetraethylammonium chloride, dodecyltrimethylammonium chloride, etc. Grade ammonium salt can be used.

[0032] The amount of the a, β-unsaturated monocarboxylic acid or ester thereof used is preferably in the range of 0.5 to 1.2 equivalents, more preferably 0.7 to 1 equivalent of epoxy group of the raw material epoxy resin. -1.1 equivalent range. If the amount of a, j8-unsaturated monocarboxylic acid or its ester is small, the amount of unsaturated group introduced is insufficient, and the subsequent reaction with polybasic acid anhydride is also insufficient. Also, it is not advantageous that a large amount of epoxy groups remain. On the other hand, if the amount used is large, α, β unsaturated monocarboxylic acid or ester thereof remains as an unreacted product. Exist. In the case of V deviation, the curing characteristics tend to deteriorate.

[0033] Polybasic acid anhydrides to be further added to epoxy resin attached with a, j8-unsaturated carboxylic acid or ester thereof include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride , Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic dianhydride, methyl hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, chlorend Acid, methyltetrahydrophthalic anhydride, biphenyltetracarboxylic dianhydride, etc., preferably maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, anhydrous Oxahydrophthalic acid, pyromellitic anhydride, trimellitic anhydride, biphenyltetracarboxylic acid Particularly preferred compounds are dianhydrides, tetrahydrophthalic anhydride and biphenyltetracarboxylic dianhydride. These may be used alone or in combination of two or more.

[0034] A known method can also be used for the addition reaction of polybasic acid anhydride, and the reaction is continued under the same conditions as the addition reaction of α, β-unsaturated carboxylic acid or ester thereof. be able to.

The addition amount of the polybasic acid anhydride is preferably an amount such that the acid value of the resulting epoxy attalylate resin is in the range of 10 to 15 Omg-KOHZg, and more preferably in the range of 20 to 140 mg-KOHZg. If the acid value of the resin is too small, the alkali developability is poor, and if the acid value of the resin is too large, the curing performance tends to be inferior.

[0035] Other examples of epoxy acrylate resins having a carboxyl group include naphthalene-containing resins described in JP-A-6-49174; JP-A 2003-89716, JP-A 2003-165830, JP-A 2005-325331. Examples thereof include fluorene-containing coagulants described in JP-A No. 2001-354735; JP-A 2005-126674, JP-A 2005-55814, JP-A 2004-295084, and the like.

In addition, commercially available epoxy acrylate resins having a carboxyl group can be used, and examples of commercially available products include “ACA-200M” manufactured by Daicel Corporation.

[0036] As the noda resin, acrylic binders described in, for example, JP-A-2005-154708 can also be used. [0037] The ratio of the binder resin to the total solid content in the light-shielding resin composition of the present invention is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more. Usually, it is 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less. If the ratio of the noda resin is too small, the image formation becomes unstable and the shape is not controlled, and the durability to chemicals may be deteriorated. If the amount is too large, the light shielding property cannot be improved.

[0038] [1 2] Monomer

The monomer used in the light-shielding resin composition of the present invention is not particularly limited as long as it is a photopolymerizable and contains a polymerizable low molecular weight compound, but is a polyfunctional monomer having a functional group. A compound capable of addition polymerization (hereinafter referred to as “ethylenic compound”) having at least one ethylenic double bond is more preferable. The monomer may have an acid group.

[0039] The ethylenic compound is an ethylenic compound that undergoes addition polymerization and cures by the action of a photopolymerization initiator described later when the light-shielding resin composition of the present invention is irradiated with actinic rays. It is a compound having a double bond. The “monomer” in the present invention means a concept opposite to a so-called high molecular substance, and in addition to “monomer” in a narrow sense, “dimer”, “trimer”, “oligomer”. ”Means a concept including“

[0040] Examples of the ethylenic compound having an acid group include unsaturated carboxylic acid, ester of unsaturated carboxylic acid and monohydroxy compound, aliphatic polyhydroxy compound and unsaturated force rubonic acid. Esters, aromatic polyhydroxy compounds and unsaturated carboxylic acids, unsaturated carboxylic acids and polyvalent carboxylic acids, and the aforementioned aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds, etc. An ethylenic compound having a urethane skeleton obtained by reacting an ester or polyisocyanate compound obtained by an ester reaction with a polyvalent hydroxy compound and a (meth) atallyloyl-containing hydroxy compound. Examples include compounds.

[0041] Examples of the unsaturated carboxylic acid include (meth) acrylic acid, itaconic acid, ilotonic acid, maleic acid and the like.

[0042] Examples of the ester of an aliphatic polyhydroxyl compound and an unsaturated carboxylic acid include ethylene diol diatalate, triethylene glycol diatalate, trimethylol propane tri Atalylate, trimethylolethane tritalylate, pentaerythritol diatalylate, pentaerythritol triatalylate, pentaerythritol tetratalariate, dipentaerythritol tetratalylate, dipentaerythritol pentaatalylate, dipentaerythritol hexatalylate, glycerol Acrylate esters such as acrylate. In addition, the acrylic acid part of these acrylates was replaced with a methacrylic acid ester substituted for the methacrylic acid part, an itaconic acid ester substituted for the itaconic acid part, a crotonic acid ester substituted for the crotonic acid part, or a maleic acid part. Maleic acid esters are listed.

[0043] Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include: Hyde mouth quinone diatalylate, Hyde mouth quinone dimetatalylate, Resorcin ditalarate, Resorcin dimetatalylate, Pyrogallol tritalylate Etc.

[0044] The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound may not necessarily be a single substance but a mixture. Typical examples are condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and penterythritol, acrylic acid, adipic acid, butanediol. And glycerin condensates.

[0045] Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) atallyloyl group-containing hydroxy compound include hexamethylene diisocyanate, trimethylhexamethyate. Aliphatic diisocyanates such as diisocyanate; cycloaliphatic diisocyanates such as cyclohexane diisocyanate, isophorone diisocyanate; aromatic diisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, etc. —Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triatalylooxymethyl) propane, 3-hydroxy (1,1,1-trimethacryloyloxymethyl) propane, etc. Of (meth) atallyloyl group-containing hydroxy compounds It is.

[0046] Other examples of the ethylenic compound used in the present invention include acrylamides such as ethylene bisacrylamide; allylic esters such as diallyl phthalate; Bulle group-containing compounds such as are also useful.

[0047] In the present invention, the monomer is a polyfunctional monomer and may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Therefore, if the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, the above-described ethylenic property is required in order to be able to use this as it is. It is also possible to introduce an acid group by reacting the hydroxyl group of the compound with a non-aromatic carboxylic anhydride. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, and succinic anhydride. Examples include acid and maleic anhydride.

In the present invention, the monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an unreacted hydroxy group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group by reacting a non-aromatic carboxylic acid anhydride with a sil group is particularly preferred. In this ester, the aliphatic polyhydroxy compound is pentaerythritol and z or Dipentaerythritol.

[0049] Of the epoxy acrylate resins described in the epoxy acrylate, those having a carboxyl group can also be used as monomers.

[0050] These monomers may be used alone, but since it is difficult to use a single compound for production, two or more of them may be used in combination. If necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination.

[0051] A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOHZg, and particularly preferably 5 to 30 mg-KOHZg. If the acid value of the polyfunctional monomer is too low, the development and dissolution characteristics may be lowered, and if it is too high, the production and handling will be difficult, and the photopolymerization performance will be degraded, and the curability such as the surface smoothness of the pixels will be inferior. Tend . Therefore, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer are within the above range. It is important to adjust.

[0052] In the present invention, a more preferred polyfunctional monomer having an acid group is T manufactured by Toagosei Co., Ltd. It is a mixture of dipentaerythritol hexatalylate, dipentaerythritol pentaatarylate, and dipentaerythritol pentaatalylate, which is commercially available as 01382, based on succinic acid ester. This polyfunctional monomer can also be used in combination with other polyfunctional monomers.

[0053] The blending ratio of these polyfunctional monomers is usually 1 to 80% by weight, preferably 5 to 70% by weight, based on the total solid content of the light-shielding resin composition of the present invention. The ratio to the material is 5 to 200% by weight, preferably 10 to: LOO% by weight, more preferably 15 to 80% by weight. The blending ratio of the polyfunctional monomer is appropriately adjusted according to the type of color material containing carbon black in the light-shielding resin composition and the acid value of the polyfunctional monomer used.

[0054] If necessary, a monofunctional monomer may be used instead of a part of the above-described polyfunctional monomer. In this case, examples of the monofunctional monomer include those described in JP-A-7-325400.

[0055] Specifically, for example, isobutyl (meth) acrylate, t-butyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, to the mouth Xylyl (meth) acrylate, Isobornyl (meth) acrylate, Benzyl (meth) acrylate, 2-Methoxyethyl (meth) acrylate, 3-Methoxypropyl (meth) acrylate, Ethyl carbitol (Meta) Atalylate, phenoxychetyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy propylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2 —Hydroxypropyl (meth) atalylate, Mono 1— T) Ataliloyloxyshethyl phthalate, Mono 1— (Meth) Atalyloxypropyl phthalate, Mono 1— (Meth) Atyloxypropyl tetrahydrophthalate, Morpholinetyl (Meth) Atari Rate, Trifluoroethyl (meth) acrylate, Tetrafluoropropyl (meth) acrylate, Octafluoropentyl (meth) acrylate, Heptadecafluorododecyl (meth) acrylate, Trimethyl tyrosylkistil (meth) ate , 1,4-Butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) Atalylate, tetraethylene glycol di (meth) Atallate, tripropylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, glycerine metatalyl acrylate, bisphenol A, EO adduct di (meth) acrylate, trimethylolpropane tri (meta) ) Atalylate, Pentaerythritol Tri (meth) Atalylate, Pentaerythritol Tetra (meth) Atalylate, Trimethylol Propane EO Adduct Tri (Meth) Atalylate, Glycerin EO Adduct Tri (Meth) Atallate, Tris (Metal ) Ataliloyloxetyl phosphate, dipentaerythritol hexa (meth) acrylate, (meth) acrylic acid modification of novolac epoxy, (meth) acrylic acid and acid anhydride modification of novolac epoxy, N—Bulpyrrolidone, N— Interview le force Puroratatamu, (meth) acrylated Isoshianureto, dipentaerythritol monohydroxy penta (meth) § click Relate, urethane (meth) Atari rate, unsaturated polyester (meth) Atari rate and the like.

[0056] [1 3] Photopolymerization initiator

The photopolymerization initiator contained in the light-shielding resin composition of the present invention is usually a mixture (photopolymerization initiator composition) of an accelerator and an additive such as a sensitizing dye added as necessary. Can be used. The photopolymerization initiator is a component having a function of generating a polymerization active radical by directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction.

[0057] Examples of the photopolymerization initiator include meta-octane compounds containing titanocene compounds described in JP-A-59-152396 and JP-A-61-151197, 39 Hexalylbiimidazole derivatives, halomethyl-s-triazine derivatives, N-phenylglycine, etc. N-aryl-a-amino acids, N-aryl-a-amino acid salts, N-aryl-a-amino acid esters And oxime ester initiators described in JP-A 2000-80068, JP-A 2006-36750, and the like.

[0058] Specific examples of the photopolymerization initiator that can be used in the present invention are listed below.

[0059] 2- (4-Methoxyphenyl) 4,6 bis (trichloromethyl) s triazine, 2- (4-methoxynaphthyl) 4,6-bis (trichloromethyl) s triazine, 2- (4-ethoxy naphthyl) ) -4,6 bis (trichloromethyl) -s triazine, 2- (4 ethoxycarbo-naphthalyl) -4,6-bis (trichloromethyl) -s triazine, etc. Derivatives;

[0060] 2 Trichloromethyl-5- (2'-benzofuryl)-1, 3, 4-oxoxadiazole, 2-Trichloromethyl 5- 5- [j8 (2'-benzofuryl) bul] 1 1, 3, 4-Oxazazol 1, 2-trichloromethyl 5- (j8- (2 '-(6 benzofuryl) butyl)) 1, 1, 3, 4-oxadiazonole, 2 trichloromethinole 5-furinole 1, 3, 4 Halomethylated oxaziazole derivatives such as oxaziazo monoure;

[0061] 2— (2 '— Black Mouth-Fuel) 1, 4, 5 Diphenol-Limidasol Dimer, 2— (2' — Black Mouth-Fuel) — 4, 5 Bis (3 '— Methoxy-Fuel) ) Imidazole dimer, 2- (2 '-fluorophenol)-4,5 diphenol imidazole dimer, 2- (2'-methoxyphenol) 4, 5 diphenol imidazole dimer, (4′-methoxyphenol) —imidazole derivatives such as 4,5 diphenylimidazole dimer;

[0062] Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenol ether, benzoin isobutyl ether, and benzoin isopropyl ether;

[0063] Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethyl anthraquinone, 2-t butyl anthraquinone, and 1-mouth anthraquinone;

[0064] Benzophenones such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methenolebenzophenone, 2-clobenbenzophenone, 4-bromobenzophenone, 2 Derivatives;

[0065] 2,2 Dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy 2-methylphenylpronone << 1-, 1-hydroxy-1- Methylethyl mono (ρ-isopropylphenol) ketone, 1-Hydroxy 1 mono (ρ dodecylphenol) ketone, 2-Methyl- (4 '(methylthio) phenol) 2-Morpholino 1-propanone, 1, 1 1, acetophenone derivatives such as 1-trichloromethyl mono (ρ butylphenol) ketone;

[0066] Thioxanthone derivatives such as thixanthone, 2 ethylthioxanthone, 2 isopropyl thixanthone, 2 chlorothioxanthone, 2,4 dimethylthioxanthone, 2,4 jetylthioxanthone, 2,4 diisopropylthioxanthone;

[0067] Benzo such as ρ dimethylamino benzoate, ρ ethylamino benzoate Acid ester derivatives;

[0068] 9 Aphalidine derivatives such as 9- (p-methoxyphenol) ataridine; [0069] 9, 10 Phenylazine derivatives such as dimethylbenzphenazine;

[0070] Anthrone derivatives such as benzanthrone;

[0071] Dicyclopentadiene Ti-dimonochloride, dicyclopentadiene Ti—bis-monophenyl, di-cyclopentagenyl Ti-bis-1, 2, 4, 4, 5, 6 pentafluorophenyl 1 —Yl, dicyclopentagenyl Ti—bis-1,2,3,5,6-tetrafluorophenyl 1—yl, dicyclopentadienyl Ti—bis1,2,4,6 Trifluoropheny 1 —Yel, Dicyclopentadienyl Ti— 2, 6—Jepur Orofeny — 1—Yel, Dicyclopentagenyl Ti—2, 4 Difluorofluorophenyl 1—Yel, G Methylcyclopentadiene Ti-Bis 2, 3, 4, 5, 6 Pentafluorophenyl 1 yl, Dimethylcyclopentadiene Ti-Bis 2, 6 Difluorophenyl 1-inore, Dicyclopentageninore Ti 2, 6 Jif Noroleo 3 (Pinolei 1 Yil) titanocene derivatives such as Hue-1il;

[0072] 2-Methyl-1 [4 (Methylthio) phenol] 2 Morpholinopropane 1-one, 2-Benzyl-1-2-Dimethylamino-1- 1- (4-Morpholinol) 1-butanone 1, 2-Benzyl -2-dimethylamino 1- (4 morpholinophenol) butane 1-one, 4 dimethylaminoethyl benzoate, 4 dimethylaminoisoamyl benzoate, 4 — jetylaminoacetophenone, 4 dimethylaminopropi Ofenone, 2-ethyl hexyl 1,4 dimethylaminobenzoate, 2,5 bis (4 ethylaminobenzal) cyclohexanone, 7-jetylamino-3- (4-jetylaminobenzoyl) coumarin, 4 (jetylamino) _a-§ aminoalkyl Hue-based compound of chalcone and the like;

[0073] 1, 2—Octanedione, 1— [4— (Ferulthio) phenol] — 2— (O Benzyloxime), Ethanone, 1— [9 Ethyl 6— (2-Methylbenzoyl) 9H—Carbazol [Lu 3-yl] 1) Oxime ester compounds such as 1 (O-acetyloxyme).

[0074] As the oxime ester-based compound, compounds exemplified below are particularly preferably used.

[0075] [Chemical 3] Tsuyoshi [9 00]

These may be used alone or in combination of two or more.

In addition, as a photoinitiator in this invention, an oxime ester type compound is especially preferable. [0078] Examples of the accelerator constituting the photopolymerization initiator composition include N, N dialkylaminobenzoic acid alkyl esters such as N, N dimethylaminobenzoic acid ethyl ester, 2 mercaptobenzozothiazole, 2-mercaptobenzoxazole. Mercapto compounds having a heterocyclic ring such as 2-mercaptobenzoimidazole or aliphatic polyfunctional mercapto compounds are used.

[0079] These photopolymerization initiators and accelerators may be used singly or in combination of two or more.

[0080] As a specific photopolymerization initiator composition, for example, "Fine Chemical" (1991, March 1 issue, vol. 20, No. 4), pages 16-26 In addition to the diolenoquinoline phenone series, benzoin, thixanthone derivatives, etc., as described in JP-A-58-403023, JP-B-45-37377, etc. Addition polymerization having a titanocene and a xanthene dye, an amino group or a urethane group described in biimidazole series, S-trinouromethyltriazine series, JP-A-4-221958, JP-A-4-219756, etc. And a system combining ethylenic saturated double bond-containing compounds.

[0081] The blending ratio of the photopolymerization initiator composition is usually 0.1 to 40% by weight, preferably 0.5 to 30% by weight in the total solid content in the light-shielding resin composition of the present invention. It is. If the blending ratio is extremely low, the sensitivity to the exposure light may be reduced. Conversely, if the blending ratio is extremely high, the solubility of the unexposed portion in the developing solution is lowered, and development failure may be induced.

[0082] If necessary, a sensitizing dye corresponding to the wavelength of the image exposure light source can be added to the photopolymerization initiator composition for the purpose of increasing the sensitivity. Examples of these sensitizing dyes include xanthene dyes described in JP-A-4 221958 and JP-A-4-219756, and coumarin dyes having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335. Kaihei 3 239703, 3-ketocoumariny compound described in 5-289335, pyromethene dye described in JP 6-19240 A, and others, JP 47-2528, 54-155292, Kosho 45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-69, JP-A-57. — 1680 Examples thereof include dyes having a dialkylaminobenzene skeleton described in JP-A No. 88, JP-A-5-107761, JP-A-5-210240, and JP-A-4-288818.

[0083] Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4, 4'-dimethylaminobenzophenone, 4,4'-jetilaminobenzofoenone, 2aminobenzofenone, 4-aminominobenzofoenone, 4,4'-aminoaminobenzofenone, 3,3'-diaminobe. Benzophenone compounds such as nzophenone and 3, 4-diaminobenzophenone; 2- (p dimethylaminophenol) benzoxazole, 2- (p dimethylaminophenol) benzoxazole, 2- (p Dimethylaminophenol) benzo [4,5] benzoxazole, 2- (p dimethylaminophenol) benzo [6,7] benzoxazole, 2,5 bis (p jetylaminophenol) 1, 3, 4-Oxazole, 2- (p-dimethylaminophenol) benzothiazole, 2- (p-demethylaminophenol) benzothiazole, 2- (p dimethylaminophenol) ) Imidazole, 2- (ρ jetylaminophenol) benzimidazole, 2,5 bis (p-jetylaminophenol) 1,3,4-thiadiazole, (p dimethylaminophenol) pyridine, ( (p dimethylaminophenol) pyridine, (p dimethylaminophenol) quinoline, (p dimethylaminophenol) quinoline, (p dimethylaminophenol) pyrimidine, (p cetylaminophenol) P) P-dialkylaminophenol-containing compounds such as pyrimidine. Of these, 4,4′-dialkylaminobenzophenone is most preferred. Sensitizing dyes may also be used alone or in combination of two or more.

[0084] The blending ratio of the sensitizing dye in the light-shielding resin composition of the present invention is usually 0 to 20% by weight, preferably 0 to 15% by weight, based on the total solid content in the light-shielding resin composition. More preferably 0

~ 10% by weight.

[0085] [1 4] Carbon black

The light-shielding resin composition of the present invention contains carbon black having an average particle diameter of 8 nm or more and 65 nm or less and a DBP oil absorption of 90 mlZ100 g or less as an essential component.

By using carbon black with an average particle size in the above range, the OD value (Optical Density: optical density) is 3.0 to 5.0, in addition to high developability, resolution and adhesion. In addition, a color filter with high contrast can be provided. Further, by using carbon black having a DBP oil absorption of 90 mlZlOOg or less and a relatively small oil absorption, the developability, resolution and adhesion can be further improved.

[0086] The lower limit of the average particle diameter of carbon black is preferably 17 nm, more preferably 21 nm, and the upper limit is preferably 40 nm, more preferably 32 nm or less. If the average particle size of carbon black is too large, the OD value will be low and thin film will be difficult, and if it is too small, it will be difficult to ensure dispersion stability.

[0087] The average particle size of carbon black in the present invention means the number average particle size.

In general, the average particle diameter of carbon black is taken by several fields of view of photographs taken at tens of thousands of times by electron microscope observation, and particle image analysis is performed by measuring about 2000 to 3000 particles of these photographs with an image processing device. Desired.

[0088] The carbon black used in the present invention has a DBP oil absorption of usually 90 mlZlOOg or less, preferably 75 ml / 100 g or less, and usually 40 mlZl00g or more, preferably 50 ml / lOOg or more.

[0089] In order to make the carbon black average particle size and the oil absorption amount within the above range, for example, when producing carbon black by burning heavy oil, a method of adding an inorganic compound containing potassium element into the system, etc. Can be adopted.

[0090] In this case, examples of the inorganic compound containing potassium element used for the production of carbon black include inorganic salts such as hydroxide, chloride, sulfate, carbonate, and organic acid salts including fatty acids. And organometallic compounds such as metal alkyls. Of these, potassium hydroxide and potassium salt are particularly preferably used. These inorganic compounds containing potassium element may be used singly or in combination of two or more.

[0091] These inorganic compounds containing potassium element are added in such an amount that the concentration of cadmium element in the atmosphere in the carbon black production process is usually 100 to 5000 ppm, more preferably <100 to 3000 ppm. It is good to manufacture.

[0092] Specific examples of a method for producing carbon black to which an inorganic compound containing potassium element is added include the method described in JP-A-8-41377.

[0093] The pH of the surface of the carbon black used in the present invention is 5 or less, particularly 4 or less. And are preferred. When the pH of the surface of the carbon black exceeds 5, it is difficult for the dispersant to adhere to the surface, so that the dispersibility may be insufficient. The lower the pH of the carbon black surface, the better, but the lower limit is usually 2 or more.

The pH of the surface of carbon black is measured by dispersing carbon black powder in water and measuring the aqueous pH of the dispersion.

[0094] Examples of the carbon black used in the present invention include the following carbon black.

[0095] Made by Mitsubishi Kaisha: MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1 000, # 2200, # 2300, # 2350, # 2400, # 2600, # 3050, # 3150, # 325 0, # 3600, # 3750, # 3950, # 4000, OIL7B, OIL9B, OIL11B, OIL30B, OIL31

[0096] Degussa: Printex3, Printex30P, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Prin tex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V , PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlackl00, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S 160, Color Bla ck S170

[0097] Manufactured by Cabot: Monarchl20, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, MonarchlOOO, MonarchllOO, Monarchl300, Monarchl400, Monarch4630, REGAL99, REGAL99R, REGAL415, RE GAL415R 、 REGAL250, REGAL250RREGAL REGAL660R, BLACK PEARLS480, PEARLS 130, VULCAN XC72R ゝ ELFTEX-8

[0098] Colombian Carbon Corporation: RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN760, RAVEN 780RAVEN850, RAVE N890H, RAVEN1000, RAVEN1020, RAVEN1060U, RAVEN1080U, R AVEN 11 OOURAVEN 1040, RAVEN1060U, RAVEN1080U, RAVEN117 0, VEN1080U, RAVEN117 0 , RAVEN2000, RAVEN2 500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVE N7000

[0099] The ratio of the carbon black to the total solid content in the light-shielding resin composition of the present invention is usually 1 to 90% by weight, preferably 5 to 80% by weight, more preferably 10 to 70% by weight, particularly preferably. Is 40 to 70% by weight. If the carbon black content is too small, the coloring power will be low, the film thickness will be too thick for the color density, and this will adversely affect the gap control during liquid crystal cell. On the other hand, if the content of carbon black is too large, the dispersion stability deteriorates and there is a risk of problems such as re-aggregation and thickening.

[0100] [1 5] Other colorant ingredients

The light-shielding resin composition of the present invention may contain other colorant components to the extent that the effects of the present invention are not impaired in addition to the carbon black.

[0101] As other colorants, dyes and pigments can be used, but pigments are preferred from the viewpoint of heat resistance, light resistance, and the like. The pigment is preferably used dispersed in an average particle size of 0.5 / z m or less, preferably 0.1 μm or less.

[0102] As the pigment, a black pigment may be used by mixing a color material such as red, green, or blue, which may be used alone. These pigments can be appropriately selected from inorganic or organic pigments.

[0103] Examples of black pigments that can be used alone include acetylene black, lamp black, bone black, graphite, iron black (acid-iron iron black pigment), alin black, cyanine black, and titanium black. It is done.

[0104] For example, titanium black can be obtained by heating and reducing a mixture of titanium dioxide and metallic titanium in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), and by high-temperature hydrolysis of tetrasalt titanium. To reduce the obtained ultrafine titanium dioxide in a reducing atmosphere containing hydrogen ( JP-A-57-205322), high-temperature reduction of titanium dioxide or titanium hydroxide in the presence of ammonia (JP-A-60-65069, JP-A-61-201610), Examples thereof include a method in which a vanadium compound is attached to titanium dioxide dihydrate or titanium hydroxide hydroxide and reduced at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610). It ’s not limited to these! /

[0105] Examples of commercially available titanium black include Titanium Black 10S, 12S 13R 13M 13M-C, etc., manufactured by Mitsubishi Materials Corporation.

[0106] In addition, organic pigments of three colors, red, green, and blue, can be mixed and used as black pigments. Barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron, chromium oxide, etc. can be used. Tochidaru.

[0107] Color materials that can be mixed to prepare a black pigment include Victoria Pure Blue (42595), Auramin 0 (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170), Safranin OK70: 100 (50240), Ellioglaucin X (42080), No. 120Z Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzine Yellow 4T—564D ( 21095), Shimla First Red 4015 (12355), Lionol Red 7B 4401 (15850), Firth Gen Blue TGR—L (74160), Dionol Blue SM (2 6150), Lionol Blue ES (Vigment Blue 15: 6 ), Lionogen Red GD (Vigment Red 168), Lionol Green 2YS (Vigment Green 36), etc. (The numbers in parentheses above are Color index (C. I.) means).

[0108] Further, other pigments that can be used in combination are represented by CI numbers. For example, CI yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 1 53, 154, 166, CI orange pigment 36, 43, 51, 55, 59, 61, CI red pigment 9, 9 7, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 2 26, 227, 228, 240, CI Neolet Pigment 19, 23, 29, 30, 37, 40, 50, CI Blue Pigment 15, 15: 1, 15: 4, 22, 60, 64, CI green pigment 7, CI brown pigment 23, 25, 26 and the like.

[0109] Further, other known blue pigments, green pigments, red pigments, yellow pigments, purple pigments, oranges, Various color pigments such as range pigments, brown pigments, and black pigments can be used. In addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene, various inorganic pigments can be used. Is available. Specific examples of pigments that can be used are shown below as pigment numbers. The following “CI” means the color index (CI).

[0110] CI pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37 , 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53 : 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81 : 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144 , 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 20 0, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247 , 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 26 7 268 269 270 271 272 273 274 275 Of these, CI CI Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably ί CI Pigment Red 177, 209, 224, 254 are preferably used. I can list them.

[0111] Blue pigments include C. I. Pigment Benore 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15:

3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Among these, C.I. pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, and more preferably C.I. pigment blue 15: 6 can be mentioned.

[0112] Examples of green pigments include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 1 8, 19, 26, 36, 45, 48, 50, 51, 54, You can raise 55 and have the power S. Among these, CI pigment green 7 and 36 are preferable. [0113] CI pigment yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81 , 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133 , 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154

, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 16 9, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 1 89, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 20 2, 203, 204, 205, 206, 207, 208 Speaking power is able to S. Among these, CI pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 is preferable, and CI pigment yellow 83, 138, 139, 150, 180 is more preferable. Force S is possible.

[0114] CI pigment range 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 Among these, C.I. Pigment Orange 38 and 71 are preferable.

[0115] Purple pigments include CI pigment violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Among these, C.I. pigment violet 19, 23 is preferable, and C.I. pigment violet 23 is more preferable.

[0116] Other dyes that can be used as colorants include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinonimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes. Etc.

[0117] Examples of azo dyes include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Benolet 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12 , CI direct orange 26, CI direct green 28, CI direct green 59, CI reac Tib Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, CI Mordant Black 7 and the like.

[0118] Examples of anthraquinone dyes include CI Bat Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue 56 CI Days Purse Blue 60 etc.

In addition, as phthalocyanine dyes, for example, CI pad blue 5 isotropic quinone imine dyes, for example, CI basic blue 3, CI basic blue 9, etc., as quinoline dyes, for example, CI solvent yellow 33 CI Acid Yellow 3, CI Disperse Yellow 64 Isotropic Nitro dyes include, for example, CI Acid Yellow 1, CI Acid Orange 3, CI Disperse Yellow 42, and the like.

[0120] The ratio of the other coloring material to the total solid content in the light-shielding rosin composition of the present invention is usually 0 to 8% by weight, preferably 0 to 4% by weight, more preferably 0 to 2% by weight. It is. If the content of the coloring material is too large, the dispersion stability deteriorates and there is a risk of problems such as reaggregation and thickening.

[0121] [1 6] Dispersant

In the light-shielding resin composition of the present invention, since it is important for quality stability to finely disperse a pigment such as carbon black and stabilize the dispersion state, it is desirable to add a dispersant.

[0122] Examples of the dispersant include surfactants such as non-one, cation, and ar-on, and polymer dispersants. Among them, polymer dispersants are particularly preferred, especially the first and second grades. Or a polymer dispersant having a basic functional group such as a tertiary amino group, nitrogen-containing heterocycle such as pyridine, pyrimidine, pyrazine, etc. (in the present invention, a high molecular weight dispersant having such a basic functional group). The molecular dispersant is referred to as “basic polymer dispersant.”) Is advantageously used.

[0123] Basic polymer dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, Examples include urethane-based dispersants and acrylic dispersants. Urethane-based dispersants are preferred, for example, polyisocyanate compounds and compounds having one or two hydroxyl groups in the same molecule. And a polymer dispersant obtained by reacting an active hydrogen with a compound having a tertiary amino group in the same molecule.

[0124] Examples of the above polyisocyanate compounds include para-phenolic diisocyanate, 2,4 tolylene diisocyanate, 2,6 tolylene diisocyanate, 4, 4 ' Aromatic diisocyanates such as rumethane diisocyanate, naphthalene 1,5 diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2, 4, 4 trimethylhexamethylene diisocyanate , Aliphatic diisocyanates such as dimer acid diisocyanate, isophorone diisocyanate, 4, 4'-methylenebis (cyclohexyl isocyanate), ω, ω '— diisocyanate dimethylcyclohexane, etc. , Xylylene diisocyanate, a, a, a ', a'-tetramethylxylylene diiso Aliphatic diisocyanates having an aromatic ring such as cyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate 1-4-isocyanate methyloctane, 1, 3 , 6 Triisocyanates such as hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanate phenol), tris (isocyanate phenol) thiophosphate, and trimers thereof , Water adducts, and these polyol adducts. Preferred as the polyisocyanate are trimers of organic diisocyanate, and most preferred are trimer of tolylene diisocyanate and trimer of isophorone diisocyanate. These polyisocyanate compounds may be used alone or in combination of two or more.

[0125] The polyisocyanate trimer is produced by using a suitable trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. After partial trimerization of the isocyanate group of cyanate was stopped and the trimer was stopped by adding catalyst poison, unreacted polyisocyanate was removed by solvent extraction and thin-film distillation. And a method for obtaining the desired isocyanurate group-containing polyisocyanate.

[0126] The compound having one or two hydroxyl groups in the same molecule includes polyether glycol Lupoli, Poplarie Este Lug Grilicor, Lunar, Polypoli Carbobonate Toglylico Corle, Poplario Olef Fining Grilicor, etc. The hydroxyl group at the terminal end of the chemical compound of these is an aralkoxyl group having 11 to 2255 carbon atoms and having been aralkoxylated. However, and more and more than 22 types of mixed compounds are listed. .

[0127] As for Poplarie-Etter Lug Gryricoeur, Poplarie-Etélélé Giorgiaur, Pope-Polylier Ete-Terre-Estel-Lugegi-Oleur, and many more There are more than 22 kinds of mixed mixtures. .

[0128] As for poplarie ether rugidiool, it can be obtained by alone or co-polymerizing aralkylkilenlenoxydoxide alone. For example, poplarie ethylylene glycocorol, poplar lip propyripe licoric corn poplar Alligatorium, poplario oxytite tetra la methicilleren gurico korul,, Poplario oxychet hexanthame melylen licorice,, Poplario oxysio A mixture of more than 22 of these and more can be enumerated. .

[0129] As for POPOLLIRIE ETTERRUL EST STELLU DIGIOORLE, it is also possible to use AETERELLU group-containing diGiorle or other mixed darling cocools. The power to react the object with didicacarbobonic acid or their anhydrous water, or the polypolyester. For example, it can be obtained by reacting guaricocorol with aralkylkilenlenoxyxidide.

[0130] Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms. It is a compound.

[0131] Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycolole, diethylene glycol, triethylene glycol). , Propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3 butanediol, 1,4 butanediol, 2,3 butanediol, 3-methyl-1,5 pentanediol, neopentyl Glycol, 2-methyl-1,3 propanediol, 2-methyl-2-propyl 1,3 propanediol, 2-butyl

2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4 trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexane Diol, 2,5 Dimethyl-2,5 Hexanediol, 1,8 otatamethylene glycol, 2-methyl-1,8 otatamethylene Recall, aliphatic glycols such as 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, N- such as N-methyljetanolamine Alkyl dialkanolamine, etc.), such as polyethylene adipate, polyethylene adipate, polyhexamethylene adipate, polyethylene Z-propylene adipate, etc., or the above diols or monovalent valences of 1 to 25 carbon atoms Examples thereof include polylatatonediol or polylatathone monool obtained by using alcohol as an initiator V, such as polystrength prolatatone glycol, polymethylvalerolatatone, and mixtures of two or more thereof. The most preferred polyester glycol is poly-strength prolatatone glycol or poly-strength prolatatone starting with alcohol having 1 to 25 carbon atoms.

[0132] Polycarbonate glycol includes poly (1,6-hexylene) carbonate, poly (3-methyl-1,5-pentylene) carbonate, etc. Polyolefin glycol includes polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol Etc.

[0133] The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.

[0134] In a compound having an active hydrogen and a tertiary amino group in the same molecule, an active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a nitrogen atom includes a hydroxyl group, an amino group. A hydrogen atom in a functional group such as a thiol group or a thiol group, among which a hydrogen atom of an amino group, particularly a primary amino group is preferred. The tertiary amino group is not particularly limited. The tertiary amino group includes an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, and more specifically, an imidazole ring or a triazole ring.

[0135] Examples of compounds having an active hydrogen and a tertiary amino group in the same molecule are N, N-dimethyl-1,3 propanediamine, N, N jetyl-1,3 propanediamine, N, N dipropinoleyl 1,3 propanediamine N, N Dibutinoleol 1,3 Propanediamine, N, N Dimethylethylenediamine, N, N Jetylethylenediamine, N, N Dipropylethylenediamine, N, N-Dibutylethylenediamine, N, N Dimethyl-1,4 butanediamine, N, N Jetinore 1,4 butanediamin, N, N Dipropinore 1,4-butanediamine, N, N-dibutyl-1,4-butanediamine and the like.

[0136] Further, as the tertiary amino group is an N-containing heterocycle, a pyrazole ring, an imidazole ring

, Triazole ring, tetrazole ring, indole ring, force rubazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazol ring, benzothiadiazole ring, etc. N-containing hetero ring, pyridine Ring, pyridazine ring

N-containing hetero 6-membered ring such as pyrimidine ring, triazine ring, quinoline ring, atalidine ring, isoquinoline ring, and the like. Preferred as these N-containing heterocycles are an imidazole ring or a triazole ring.

[0137] Specific examples of these compounds having an imidazole ring and an amino group are as follows:

Examples include 3-aminopropyl) imidazole, histidine, 2-aminoimidazole, and 1- (2-aminoethyl) imidazole. Further, specific examples of a compound having a triazole ring and an amino group include 3-amino-1, 2, 4-triazole, 5- (2-amino-1,5).

1) —Huenore 1H—1, 2, 4—Triazore, 4—Amino 4H—1

, 2, 4—Triazole— 3, 5—Diol, 3—Amino— 5—Fel— 1H— 1, 3, 4— Triazol, Ignore, ₅ —Amino—, ₄ —Diphenylenore, ₂ , ₃ — Triazo, Ichinole, ₃ — Amino

-Benzyl 1H-2, 4-triazole and the like.

[0138] Among them, N, N-dimethyl-1,3-propanediol, N, N-jetyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole Is preferred.

[0139] A preferable blending ratio of the dispersant raw material is a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by weight of the polyisocyanate compound. ~ 200 parts by weight, preferably 20 to 190 parts by weight, more preferably 30 to 180 parts by weight, and the compound having active hydrogen and tertiary amino group in the same molecule is 0.2 to 25 parts by weight, preferably 0. 3 to 24 parts by weight.

[0140] The reaction is carried out according to a known method of producing polyurethane resin. Solvents used for the reaction are usually ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone, and esters such as ethyl acetate, butyl acetate, and cetosolve acetate. , Hydrocarbons such as benzene, toluene, xylene, hexane, Diacetone alcohol, isopropanol, sec-butanol, tert-butanol and other alcohols having a relatively high molecular weight substituent around the hydroxyl group, such as alcohols other than primary alcohol, methylene chloride, black mouth form, etc. One kind or two or more kinds of ethers such as chloride, tetrahydrofuran, jetyl ether and the like, and aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone and dimethylsulfoxide are used.

[0141] In the above reaction, a urethanization reaction catalyst is usually used. Examples of the urethanization reaction catalyst used include tin-based compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diformateate, stanasoctoate, iron acetylethylacetonate, and ferric chloride. One type or two or more types of tertiary amines such as iron, triethylamine and triethylenediamine are listed.

[0142] The introduction amount of the compound having active hydrogen and tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mg-KOHZg in terms of the amine value after the reaction. The amine value is more preferably in the range of 5 to 95 mg-KOH / g. Here, the amine value is a value expressed in mg of KOH corresponding to the acid value after neutralizing titration of a basic amino group with an acid. If the amine value is less than the above range, the dispersing ability tends to be lowered, and if it exceeds the above range, the developability tends to be lowered.

[0143] In the case where the isocyanate group remains in the polymer dispersant produced by the above reaction, further modification of the remaining isocyanate group with an alcoholamine compound is preferable because the stability with time of the product becomes high. Better ,.

[0144] The weight average molecular weight of such a basic polymer dispersant is usually 1,000 to 200,000, preferably <is 2,000 to 100,000, more preferably <is 3,000 to 50,000. Range. When the weight average molecular weight is less than 1,000, the dispersibility and dispersion stability are poor, and when it exceeds 200,000, the solubility is lowered, and the dispersibility is poor and the reaction is difficult to control.

The weight average molecular weight is measured in terms of polystyrene by GPC (gel permeation chromatography).

[0145] As the basic polymer dispersant, commercially available ones can also be used. For example, by the trade name, BY161 DB161, DB162, DB163, DB164, DB166, DB182, EFKA 4046, Norrebri Norre Solis Nose 38500, Solisnose 20000, Solisnose 24000, Solisnose 27000, Solisnose 28000, etc.

[0146] These dispersants may be used singly or in combination of two or more.

[0147] The ratio of these dispersants to the total solid content in the light-shielding resin composition of the present invention is usually 0.05% by weight or more, preferably 0.1% by weight or more, and more preferably 0.5% by weight. %, Usually 10% by weight or less, preferably 6% by weight or less, more preferably 5% by weight or less. If the content of the dispersant is too small, the dispersion stability deteriorates, and problems such as reaggregation and thickening may occur. On the other hand, if the amount is too large, the ratio of the pigment is relatively reduced, so that the coloring power may be lowered or the sensitivity may be lowered in the crosslinking by exposure.

[0148] [1 7] Dispersion aid

The light-shielding resin composition of the present invention may also contain a dispersion aid in addition to the dispersant.

Examples of the dispersion aid include pigment derivatives.

[0149] Examples of the pigment derivative include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, di-xazine, anthraquinone, indanthrene, perylene, perinone, Examples include derivatives such as diketopyrrolopyrrole and dioxazine pigments. As substituents of pigment derivatives, sulfonic acid groups, sulfonamide groups and their quaternary salts, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. are directly in the pigment skeleton or alkyl groups, aryl groups. And a group bonded through a heterocyclic group, preferably a sulfonamide group, a quaternary salt thereof, and a sulfonic acid group, and more preferably a sulfonic acid group. In addition, a plurality of these substituents may be substituted on one pigment skeleton, or a mixture of compounds having different numbers of substitutions. Specific examples of pigment derivatives include azo pigment sulfonic acid derivatives, phthalocyanine pigment sulfonic acid derivatives, quinophthalone pigment sulfonic acid derivatives, anthraquinone pigment sulfonic acid derivatives, quinacridone pigment sulfonic acid derivatives, and diketopyrrolopyrrole pigments. Examples thereof include sulfonic acid derivatives and sulfonic acid derivatives of dioxazine pigments.

[0150] The added amount of the pigment derivative is usually 0.01 to 4% by weight, preferably 0.05 to 3% by weight or less, more preferably 0 to the total solid content of the light-shielding resin composition of the present invention. . 1-2% by weight is there. If the amount of the pigment derivative added is small, dispersion stability deteriorates and problems such as reaggregation and thickening may occur. On the other hand, if the amount is too large, the contribution to dispersion stability is saturated, and on the contrary, the color purity may be lowered.

[0151] [18] Organic carboxylic acid, organic carboxylic anhydride

In addition to the above components, the light-shielding resin composition of the present invention may further contain an organic carboxylic acid and Z or an organic carboxylic acid anhydride.

[0152] [1 8— 1] Organic carboxylic acid

Organic carboxylic acids include aliphatic carboxylic acids and Z or aromatic carboxylic acids. Specific examples of the aliphatic carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, jetyl acetic acid, enanthic acid, strong prillic acid, glycolic acid, acrylic acid, and methacrylic acid. Monocarboxylic acid such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, Examples thereof include dicarboxylic acids such as tetramethylsuccinic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, and fumaric acid, and tricarboxylic acids such as tricarnolic acid, aconitic acid, and camphoric acid. Specific examples of aromatic carboxylic acids include benzoic acid, toluic acid, cumic acid, hemelic acid, mesitylene acid, phthalic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, and melophane. Acid, pyromellitic acid, phenacetic acid, hydroacetropic acid, hydrocacinic acid, mandelic acid, succinic acid, atropic acid, kaynic acid, methyl kainate, benzyl cinnamate, cinnamylidene acetic acid, tamalic acid And carboxylic acids in which a carboxyl group is directly bonded to a phenyl group such as umbelic acid, and carboxylic acids in which a carboxyl group is bonded through a carbon atom having a phenyl group.

[0153] Among the above organic carboxylic acids, malonic acid, particularly preferred are malonic acid, glutaric acid and glycolic acid, among which monocarboxylic acid and dicarboxylic acid are preferred.

[0154] The molecular weight of the organic carboxylic acid is usually 1000 or less, and usually 50 or more. If the molecular weight of the organic carboxylic acid is too large, the effect of improving the soiling is insufficient, and if it is too small, the amount added may be reduced due to sublimation or volatilization, or process contamination may occur. [0155] [1 8-2] Organic carboxylic acid anhydride

Examples of organic carboxylic acid anhydrides include aliphatic carboxylic acid anhydrides and Z or aromatic carboxylic acid anhydrides. Specific examples of aliphatic carboxylic acid anhydrides include acetic anhydride, anhydrous trichlorodiacetic acid, and trifluoroacetic anhydride. Acetic acid, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, glutaric anhydride, 1,2 cyclohexenedicarboxylic anhydride, n-octadecyl succinic anhydride, 5 norborn anhydride And aliphatic carboxylic acid anhydrides such as Nene-2,3 dicarboxylic acid. Specific examples of aromatic rubonic acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride.

[0156] Among the organic carboxylic acid anhydrides, maleic anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, and citraconic anhydride are more preferable.

[0157] The molecular weight of the organic carboxylic acid anhydride is usually 800 or less, preferably 600 or less, more preferably 500 or less, and usually 50 or more. If the molecular weight of the above organic carboxylic acid anhydride is too large, the effect of improving soil stains will be insufficient, and if it is too small, there is a risk of reducing the amount of additives and process contamination due to sublimation and volatilization.

[0158] These organic carboxylic acids and Z or organic carboxylic acid anhydrides may be used singly or as a mixture of two or more.

[0159] The amount of addition of these organic carboxylic acid and Z or organic carboxylic anhydride is usually 0.01% by weight or more, preferably 0 in the total solid content of the light-shielding resin composition of the present invention. .03% by weight or more, more preferably 0.05% by weight or more, and usually 10% by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less. If the addition amount is too small, a sufficient addition effect cannot be obtained. If the addition amount is too large, surface smoothness and sensitivity may be deteriorated, and undissolved peeling pieces may be generated.

[0160] [1 9] Other solids

The light-shielding rosin composition of the present invention can further contain solids other than the above components as necessary. Examples of such components include surfactants, thermal polymerization inhibitors, plasticizers, storage stabilizers, surface protective agents, adhesion improvers, development improvers and the like.

[0161] [1 9 1] Surfactant As the surfactant, one or more of various types such as ionic, cationic, nonionic, and amphoteric surfactants can be used, but the possibility of adversely affecting various properties is low. Therefore, it is preferable to use a nonionic surfactant.

[0162] The amount of the surfactant added is generally 0.001 to 10 weight ^_0/0 of the total solid content of the light-shielding榭脂composition of the present invention, preferably from 0.005 to 1 weight ^_0/0 More preferably, the content is 0.01 to 0.5% by weight, and most preferably 0.03 to 0.3% by weight. If the addition amount of the surfactant is less than the above range, the smoothness and uniformity of the coating film cannot be expressed, and if it is more, the smoothness and uniformity of the coating film cannot be expressed, and other characteristics are poor. There is a case to hesitate.

[0163] [1 9 2] Thermal polymerization inhibitor

As the thermal polymerization inhibitor, for example, one, two or more kinds such as rho, idroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like are used. The addition amount of the thermal polymerization inhibitor is preferably in the range of 0 to 3% by weight with respect to the total solid content of the light-shielding resin composition of the present invention.

[0164] [1 9 3] Plasticizer

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl dallicol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. Two or more types are used. The amount of these plasticizers added is preferably 10% by weight or less based on the total solid content of the light-shielding resin composition of the present invention.

[0165] [1 9 4] Other

In addition, a storage stabilizer, a surface protective agent, an adhesion improver, a development improver and the like can be added as necessary. The amount of these components added is preferably 20% by weight or less in total with respect to the total solid content of the light-shielding resin composition of the present invention.

[0166] [1 10] Solvent

The light-shielding resin composition of the present invention is generally prepared by dissolving or dispersing the above-described solid content in a solvent.

In the light-shielding resin composition of the present invention, the solvent comprises (i) a binder resin, (ii) a monomer, (C) a photopolymerization initiator, (D) carbon black and the above-mentioned other colorants, dispersants, and Further, it has a function of adjusting viscosity by dissolving or dispersing other components blended as necessary.

[0167] As the solvent, it is preferable to select a solvent which can dissolve or disperse each component constituting the composition and has a boiling point in the range of 100 to 200 ° C. More preferably, the solvent has a boiling point of 120 to 170 ° C.

Examples of such solvents include the following.

[0168] Ethylene Glycolanol Monomethinole Ether, Ethylene Glycolic Monomono Ethenole Ether, Ethylene Glyconore Monopropinoleetenore, Ethylene Glycolenomonomono Butenoreethenore, Ethylene Glycolenomonomono Butenoreetenore, Propylene Glyconore Monomethylenoateolene, Propylene glycolate tertbutinoleether, Diethyleneglycolanol monomethylol ether, Diethylene glycol monoethyl ether, Methoxymethyl pentanol, Propylene glycolenoleino ethinoleate, Dipropylene glycolate Glycol monoalkyl such as monoethylenoatenole, diplypropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether Ethers;

[0169] Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol jetyl ether, polyethylene glycol dimethyl ether, diethylene glycol jetyl ether, jetylene glycol dipropyl ether, diethylene glycol dibutyl ether;

[0170] Ethylene glycol monomethino ethenore acetate, ethylene glycol mono methino acrylate, teracetate, propylene glycol monomethyl ether acetate, propylene glyceno mono ethino enoate acetate, propylene glycol eno mono ethino enoate Glycol alkyl ether acetates such as acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, dipropylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate; [0171] jetyl ether, dipropyl Etheroles such as ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether ;

[0172] Acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl Ketones such as isoamyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone;

[0173] Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin;

[0174] Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-xane, hexene, isoprene, dipentene, dodecane;

[0175] Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

[0176] Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;

[0177] Amylformate, Ethylformate, Ethyl acetate, Butyl acetate, Propyl acetate, Amyl acetate, Ethylene glycol acetate, Ethyl propionate, Propyl propionate, Butyl butyrate, Isobutyl butyrate, Methyl isobutyrate, Ethyl caprylate, Butyl stearate Rate, Ethyl benzoate, Methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, Methyl 3-methoxypropionate, Ethyl 3-ethoxypropionate, Methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, 3 —Chain or cyclic esters such as propyl methoxypropionate, butyl 3-methoxypropionate, γ—butyroratatone;

[0178] Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

[0179] Halogenated hydrocarbons such as butyl chloride and milk mouthride;

[0180] Ether ketones such as methoxymethylpentanone;

[0181] -Tolyls such as acetonitrile and benzo-tolyl;

[0182] Solvents applicable to the above include mineral spirits, Valsol # 2, Apco # 18 Solvent, Apco thinner, Soal Solvent No. 1 and No. 2, Solvesso # 150, Shell TS28 Solvent, Calvi Such as Toll, Ethyl Carbitol, Butyl Carbitol, Methylcele Solv, Ethinorecero Sonoreb, Ethylcele Solvate, Diglyme The commercial item of a brand name is mentioned.

[0183] These solvents may be used alone or in combination of two or more.

[0184] The content of the solvent in the light-shielding resin composition of the present invention is not particularly limited. Power is usually 99% by weight or less, usually 50% by weight or more, preferably 55% by weight or more, and more preferably. Is more than 60% by weight. If the proportion of the solvent is too large, the solid content of the binder resin, monomer, carbon black and other coloring materials, and the dispersant is too small to be suitable for forming a light-shielding resin composition. On the other hand, if the proportion of the solvent is too small, the viscosity increases and it is not suitable for coating.

[0185] [1 11] Potassium ion content

The light-shielding rosin composition of the present invention must have a potassium ion content of 20 ppm or less based on the total solid content. The content of potassium ions is preferably 18 ppm or less, more preferably 10 ppm or less, based on the total solid content of the light-shielding resin composition.

[0186] The lower limit of the potassium ion content of the light-shielding resin composition of the present invention is preferably as small as possible, but is usually 0.1 ppm or more with respect to the total solid content. If there is too much content of force rhodium ion in the light-shielding resin composition, developability, resolution, adhesion, especially linearity and adhesion cannot be sufficiently secured.

[0187] In order to make the potassium ion content within the above range, for example, in the case of carbon black obtained by the method of adding a strong element in [14], this is removed by washing with water or the like. A method is mentioned.

When removing by washing with water, it is important to bring carbon black into contact with water efficiently. Specifically, pure water is added to carbon black, and kneading is repeated many times while changing the water using a device such as a homomixer, two-shaft-one dander, or a normal stirrer. The method of doing is mentioned. The amount of water used is preferably 500 mL or more per lOOg of carbon black, more preferably 10 mL or more.

[0188] The potassium ion content in the light-shielding resin composition is, for example, extracted by adding 30 ml of pure water to 0.2 g (as solid content) of the light-shielding resin composition and extracting in an ultrasonic bath for 30 minutes. Then, it can be measured by ultracentrifugation (50,000 rpm X lhr) and analyzing the supernatant by ion chromatography. [0189] [2] Method for producing light-shielding resin composition

The light-shielding resin composition of the present invention is produced, for example, as follows by first dispersing and mixing carbon black, a solvent, and, if necessary, a dispersant and other components to produce a black pigment dispersion. The black pigment dispersion can be produced by adding and mixing a binder resin, a monomer, a photopolymerization initiator, etc., but the method for producing the light-shielding resin composition of the present invention is not limited to this method. It ’s not something.

[0190] [2-1] Method for producing black pigment dispersion

Carbon black, a solvent, and if necessary, a dispersant and other components are weighed in predetermined amounts, and in the dispersion treatment step, carbon black is dispersed to obtain a liquid black pigment dispersion. In this dispersion treatment step, a paint conditioner (paint shaker), a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer and the like can be used. Since the colorant containing carbon black is finely divided by this dispersion treatment, the light-shielding resin composition using the black pigment dispersion prepared in this way has improved coating properties, and the product The light shielding ability of the color filter substrate is improved.

[0191] When the pigment is subjected to a dispersion treatment, the binder resin or the dispersion aid may be used in combination as appropriate. For example, when the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads having a diameter of 0.1 to 8 mm or zircoyu beads. The temperature during the dispersion treatment is usually set in the range of 0 ° C to 100 ° C, preferably in the range of room temperature to 80 ° C. The appropriate dispersion time depends on the composition of the black pigment dispersion (pigment, solvent, dispersant, etc.), the size of the sand grinder apparatus, and the like, so it is necessary to adjust appropriately.

[0192] In this case, the standard of dispersion is to control the gloss of the black pigment dispersion so that the 20 ° specular gloss in JIS Z8741 is in the range of 100 to 200. In the case where the gloss of the black pigment dispersion is low, the dispersion treatment is not sufficient and rough, and pigment particles often remain, which is insufficient in terms of developability, adhesion, resolution, and the like. Further, when the dispersion treatment is carried out until the gloss value exceeds the above range, a large number of ultrafine particles are produced, so that the dispersion stability tends to be impaired. [0193] The black pigment dispersion produced in this way is added with a binder resin when dispersing the pigment as described above, and the binder resin resin of the light-shielding resin composition of the present invention is added. By including such noinda rosin which may be partially contained, it is possible to enhance the dispersion stability when producing a black pigment dispersion.

[0194] In this case, the amount of the binder resin added is preferably 5 to: LOO wt%, particularly 10 to 80 wt% with respect to the pigment in the black pigment dispersion. If the amount of the binder resin added is too small, the effect of increasing the dispersion stability is insufficient, and if it is too large, the concentration of the colorant such as carbon black is lowered, so that sufficient light shielding properties cannot be obtained.

[0195] The solid content concentration in the black pigment dispersion is usually about 10 to 20% by weight. The concentrations of potassium ions and Z or potassium atoms are usually 10 ppm or less, preferably 95 ppm or less, more preferably 50 ppm or less, based on the total solid content in the black pigment dispersion.

Here, “total solid content” refers to all components of the black pigment dispersion other than the solvent.

[2-2] Method for producing light-shielding resin composition (resist)

The light-shielding resin composition of the present invention is obtained by adding and mixing the black pigment dispersion obtained by the above process and other components necessary as components of the light-shielding resin composition into a uniform solution. Prepared. In this case, a dispersion treatment with a solution in which all the components to be blended as a light-shielding resin composition are mixed at the same time is not preferable because a highly reactive component may be modified due to heat generated during dispersion. In addition, since fine dust is often mixed in the liquid during the production process, it is desirable to filter the obtained light-shielding resin composition with a filter or the like.

[0197] [3] Manufacture of color filters

Next, a specific example of the color filter manufacturing method of the present invention will be described.

[0198] A color filter is usually manufactured by forming a black matrix on a transparent substrate and then sequentially forming pixel images of red, green, and blue colors.

[0199] The light-shielding resin composition of the present invention is particularly used as a coating liquid for forming a black matrix of a color filter.

Regarding black resists, red, green and blue color resists on transparent substrates. In this way, on the surface of the resin black matrix formed on the transparent substrate, a pixel image of each color is formed by applying, heating, drying, image exposure, developing and thermosetting, respectively.

[0200] [3-1] Transparent substrate (support)

The transparent substrate of the color filter is not particularly limited as long as it is transparent and has an appropriate strength. Materials include, for example, polyester resin such as polyethylene terephthalate, polyolefin resin such as polypropylene and polyethylene, thermoplastic resin sheet such as polycarbonate, polymethyl methacrylate, and polysulfone, epoxy resin, Examples include unsaturated polyester resin, thermosetting resin sheets such as poly (meth) acrylic resin, and various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance.

[0201] For transparent substrates and black matrix-formed substrates, various resin such as corona discharge treatment, ozone treatment, silane coupling agent, and urethane-based resin are used as necessary to improve surface properties such as adhesion. A thin film forming process or the like may be performed.

[0202] The thickness of the transparent substrate is usually in the range of 0.05 to: LOmm, preferably 0.1 to 7 mm.

When thin film forming treatment of various resins is performed, the film thickness is usually in the range of 0.01 to 10 m, preferably 0.05 to 5 m.

[0203] [3-2] Pixel formation

[3— 2— 1] Formation of coating film

In forming the black matrix, the light-shielding resin composition of the present invention is coated on a transparent substrate and dried, and then a photomask is overlaid on the formed coating film, and image exposure is performed through this photomask. Development, heat curing or photocuring as necessary. In forming pixels, a colored composition containing a color material of one of red, green, and blue is applied on a transparent substrate provided with a black matrix, dried, and then formed on the formed coating film. A photomask is overlaid, and a pixel image is formed through image exposure, development, and heat curing or photocuring as necessary through this photomask to form a colored layer of the pixel image. A color filter image can be formed by performing this operation for each of the three colored compositions of red, green, and blue. [0204] The shading resin composition and the coloring composition can be applied by a spinner method, a wire bar method, a flow coat method, a die coating method, a roll coating method, a spray coating method, or the like. In particular, the die coating method significantly reduces the amount of coating solution used and suppresses the generation of foreign substances that are completely free from the effects of mist adhering to the spin coating method. I like it.

[0205] If the thickness of the coating film is too thick, it will be difficult to develop a no-turn development, and it may be difficult to adjust the gap in the liquid crystal cell forming process, and if it is too thin, it will be difficult to increase the colorant density. Therefore, the desired color expression may not be possible. The thickness of the coating film is usually in the range of 0.2 to 20 111 as the film thickness after drying, more preferably in the range of 0.5 to 10 / ζ πι, and more Preference is given to a range of 0.8 to 5 m.

[0206] [3—2-2] Drying of coating film

Drying of the coating film formed by applying a light-shielding resin composition or coloring composition to a transparent substrate is preferably performed by a drying method using a hot plate, an IR oven, or a competition oven. Usually, after preliminary drying, two-stage drying is performed by heating again and drying. The conditions for the preliminary drying can be appropriately selected according to the type of the solvent component in the light-shielding resin composition or coloring composition, the performance of the dryer used, and the like. The drying time is usually selected in the range of 40 to 80 ° C and 15 seconds to 5 minutes, preferably 50 to 70 ° C, depending on the type of solvent component and the performance of the dryer used. In the range of 30 seconds to 3 minutes.

[0207] The temperature condition for the reheating drying is 50 to 200 ° C higher than the predrying temperature, and preferably 70 to 160 ° C, particularly preferably 70 to 130 ° C. The drying time is preferably 10 seconds to 10 minutes, and more preferably 15 seconds to 5 minutes, depending on the heating temperature. The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate. However, if the drying temperature is too high, the binder resin is decomposed, and thermal polymerization may be induced to cause development failure. The coating film may be dried by a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature.

[0208] [3—2-3] Exposure process

In image exposure, a negative matrix pattern is overlaid on the dried coating film of the light-shielding resin composition or coloring composition, and UV or visible light is passed through this mask pattern. Irradiate with a light source. At this time, if necessary, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the coating film in order to prevent the sensitivity of the coating film from being lowered by oxygen.

[0209] The light source used for image exposure is not particularly limited. 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, a low pressure mercury lamp, Examples include lamp light sources such as carbon arc and fluorescent lamps, and laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers. An optical filter can also be used when irradiating light of a specific wavelength.

[0210] [3—2-4] Development process

Development can be performed after the image exposure using an organic solvent or an aqueous solution containing a surfactant and an alkaline compound. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

[0211] Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, metasilicate. Inorganic alkaline compounds such as sodium, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, — Or triethanolamine, mono'di or trimethylami, mono-di or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenedimine, tetramethyl Ammonium hydroxide (TMAH), collagen And organic alkaline I 匕合 of such. These alkaline compounds may be used alone or as a mixture of two or more.

[0212] Examples of the surfactant include non-ionic interfaces such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and the like. Activators, alkyl benzene sulfonates, alkyl naphthalene sulfonates, Examples include cationic surfactants such as alkyl sulfates, alkyl sulfonates and sulfosuccinic acid ester salts, and amphoteric surfactants such as alkyl betaines and amino acids. These are used alone. You may mix and use 2 or more types.

[0213] Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butylcetosolve, phenylsolvesolve, propylene glycol, diacetone alcohol and the like. These organic solvents may be used alone or in combination of two or more, or one or more may be used in combination with water.

[0214] The development conditions are not particularly limited. Usually, the development temperature is in the range of 10 to 50 ° C, particularly 15 to 45 ° C, particularly preferably 20 to 40 ° C. The development method is immersion development. , Spray developing method, brush developing method, ultrasonic developing method and the like.

[0215] [3—2—5] Thermosetting treatment

The color filter substrate after development is usually subjected to heat curing treatment or light curing treatment, preferably heat curing treatment.

[0216] The thermosetting treatment conditions are selected such that the temperature ranges from 100 to 280 ° C, preferably from 150 to 250 ° C, and the time ranges from 5 to 60 minutes.

[0217] Through these series of steps, the pattern image formation for one color is completed. This process is repeated in sequence to pattern (black,) red, green, and blue to form a color filter. Note that the order of the three-color patterning of red, green, and blue is not limited to the order described above.

[0218] [3—2-6] Formation of transparent electrode

The color filter according to the present invention is used as a part of a component such as a color display or a liquid crystal display device by forming a transparent electrode such as ITO on the image as it is.

In order to improve surface smoothness and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary.

[0219] Further, in some applications such as the planar alignment type driving method (IPS mode), the transparent electrode may not be formed.

[0220] [4] Liquid crystal display device (panel) Next, a specific example of the manufacturing method of the liquid crystal display device (panel) of the present invention will be described.

[0221] In the liquid crystal display device of the present invention, an alignment film is usually formed on the color filter of the present invention, and after a spacer is dispersed on the alignment film, a liquid crystal cell is formed by bonding to a counter substrate. Then, liquid crystal is injected into the formed liquid crystal cell and connected to the counter electrode.

[0222] As the alignment film, a resin film such as polyimide is preferable. Gravure printing and Z or flexographic printing are usually used to form the alignment film, and the thickness of the alignment film is usually several tens of nm. The alignment film is cured by thermal baking, and then surface-treated by treatment with a UV-irradiated rubbing cloth to be processed into a surface state capable of adjusting the tilt of the liquid crystal.

[0223] As the spacer, a spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer of 2 to 8 m is usually preferable. A transparent resin film photospacer (PS) is formed on the color filter substrate by photolithography, and this is used in place of the spacer.

[0224] As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

[0225] The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 to 8 m. After bonding to the counter substrate, the portions other than the liquid crystal injection port are sealed with a sealing material such as epoxy resin. The sealing material is cured by ultraviolet (UV) irradiation and Z or heating, and the periphery of the liquid crystal cell is sealed.

[0226] The liquid crystal cell whose periphery is sealed is cut into panel units, and then the pressure is reduced in the vacuum chamber. After the liquid crystal inlet is immersed in the liquid crystal, the inside of the chamber leaks. Liquid crystal is injected into the liquid crystal cell. Decompression degree in the liquid crystal cell is usually a ^{1 X 10 _2 ~1 X 1 0} _7 Pa, preferably ^{^{1 X 10 _3 ~1 X 10 _6}} Pa. In addition, it is preferable to heat the liquid crystal cell at the time of depressurization, and the heating temperature is usually 30 to 100 ° C, more preferably 50 to 90 ° C. Heating during decompression is usually in the range of 10 to 60 minutes and then immersed in the liquid crystal. A liquid crystal cell filled with liquid crystal is completed by sealing the liquid crystal inlet with UV-cured resin cured.

[0227] There are no particular restrictions on the type of liquid crystal, such as aromatic, aliphatic, and polycyclic compounds. Known liquid crystal is used, and any of lyotropic liquid crystal, thermopick liquid crystal and the like may be used. Nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, etc. are known as thermo-mouth pick liquid crystal.

Example

[0228] Hereinafter, the present invention will be described more specifically with reference to synthesis examples, examples and comparative examples. However, the present invention is not limited to the description of the following examples unless it exceeds the gist. Absent.

[0229] [Synthesis example]

Synthesis Example 1 (Preparation of polymer dispersant solution)

Tolylene diisocyanate trimer (Mittech GP750A from Mitsubishi Chemical Co., Ltd., 50% by weight of rosin solids, butyl acetate solution) and 0.02g of dibutyltin dilaurate as a catalyst propylene glycol monomethyl ether acetate (PGMEA) Diluted with 47 g. Under stirring, this was mixed with a polyethylene glycol having a number average molecular weight of 1,000 at one end (“Oux M-1000” manufactured by NOF Corporation) and 14.4 g with a number average molecular weight of 1, 000 polypropylene glycol (“SANNICS PP-1000” manufactured by Sanyo Chemical Industries, Ltd.) 9.6 g of the mixture was added dropwise, and the mixture was further reacted at 70 ° C. for 3 hours. Next, N, N dimethylamino-1,3 propanediamine lg was added and reacted at 40 ° C. for an additional hour. The amine value of the solution containing the polymer dispersant thus obtained was determined by neutralization titration to be 14 mg-KOHZg. Further, the content of the resin was determined by the dry-up method (the solvent was removed on a hot plate at 150 ° C for 30 minutes, and the resin concentration was calculated from the weight change), and the content was 40% by weight.

Synthesis Example 2 (Synthesis of binder resin)

“XD1000” manufactured by Nippon Kayaku Co., Ltd. (polyglycidyl ether of dicyclopentagen phenol polymer, weight average molecular weight 700, epoxy equivalent 252) 300 parts by weight, acrylic acid 87 parts by weight, ρ-methoxyphenol 0.2 Part by weight, 5 parts by weight of triphenylphosphine, and 255 parts by weight of PGME A were charged in a reaction vessel, and stirred at 100 ° C until the acid value became 3. Omg-KOHZg. It took 9 hours for the acid value to reach the target (acid value 2.5 mg—KOH / g). Next, add 145 parts by weight of tetrahydrophthalic anhydride and react at 120 ° C for 4 hours. A binder resin I solution having an acid value of lOOmg—KOHZg, polystyrene-equivalent weight average molecular weight of 260, measured by GPC was obtained.

[0231] Synthesis Example 3 (Preparation of ink)

Preparation of ink 1

Carbon black for color (Mitsubishi Chemical “MA-8”, average particle size 24 μm, DBP oil absorption 58mlZlOOg, surface pH 3.0) lOOg in 2 shafts with ultrapure water 500ml The mixture was kneaded for 20 minutes, and ultrapure water was removed by filtration. Ultrapure water was added again to the filtered carbon black and kneaded, and filtration was repeated 4 times. Finally, the filtered carbon black was dried and washed to obtain a bonbon black. 50 parts by weight of washed carbon black, synthesis example—10 parts by weight of the polymer dispersant prepared in 1 as a solid, and carbon black and polymer dispersed so that the solids concentration is 30% by weight. Agent solution and PGMEA were added. The total weight of the dispersion was 50 g. This was stirred with a stirrer and premixed.

[0232] Next, a dispersion treatment was performed for 6 hours in the range of 25 to 45 ° C with a paint shaker. The beads used 0.5 mm diameter Zirco Your beads and had the same weight as the dispersion. After dispersion was completed (20-degree specular gloss 170 according to JIS Z8741), the beads and the dispersion were separated using a filter to prepare ink 1.

[0233] For this ink 1, add 0.2 mL of pure water to 0.2 g of the ink sample, extract in an ultrasonic bath for 30 minutes, then perform ultracentrifugation (50,000 rpm x lhr), and remove the supernatant. When the liquid was subjected to ion chromatography analysis, the K + ion concentration (hereinafter the same) with respect to the total solid content in the ink was less than 5 ppm (below the detection limit).

[0234] Preparation of Ink 2

Ink 2 was prepared in the same manner as Ink 1 except that the number of washing, kneading and filtration operations with ultrapure water was changed to two. When this ink 2 was subjected to ion chromatographic analysis in the same manner as ink 1, the K + concentration was 45 ppm.

[0235] Preparation of Ink 3

Wash with ultrapure water, kneading Ink 3 was prepared. When this ink 3 was subjected to ion chromatographic analysis in the same manner as ink 1, the K + concentration was 6 ppm.

[0236] Preparation of Ink 4

Ink 4 was prepared in the same manner as Ink 1 except that the number of washing, kneading and filtration operations with ultrapure water was one. When this ink 4 was subjected to ion chromatographic analysis in the same manner as ink 1, the K + concentration was 90 ppm.

Preparation of ink 5

Ink 5 was prepared in the same manner as ink 1 except that it was not washed with ultrapure water. This ink 5 was subjected to ion chromatographic analysis in the same manner as ink 1, and the K + concentration was 40 lppm.

[0238] The average particle size, DBP oil absorption, and surface pH of the carbon black used were the same as those before the cleaning, kneading, and filtration treatment with ultrapure water. .

[Examples 1 to 4 and Comparative Example 1]

i) Preparation of resist solution

Using the carbon black dispersion ink prepared in Synthesis Example 3, each component was added so as to have the following blending ratio, and stirred and dissolved with a stirrer to prepare a black resist photosensitive solution.

[0240] <Combination ratio>

Synthesis Example-Ink prepared in 3 (shown in Table 1): 50g as solid content

Synthesis example-2 Binder resin prepared in 2 Solution: 30g as solid content

Monomer (Ethylene Compound: Dipentaerythritol Hexatalylate): 10g Basic Polymer Dispersant-Containing Solution Prepared in Synthesis Example 1: 5g as Solids Photopolymerization Initiator (Ciba242, Ciba Specialty Chemicals) Compound shown in the following structural formula): 5g

[Chemical 5]

Organic solvent (PGMEA): 300g

Surfactant (Sumitomo 3M “FC-430” fluorosurfactant): Concentration force in resist solution SlOOppm

[0241] ii) Evaluation of resist solution

Each black resist sensitizing solution prepared in i) was applied to a glass substrate (“7059” manufactured by Cowing Co., Ltd.) with a spin coater and dried on a hot plate at 80 ° C. for 1 minute. The film thickness of the resist after drying was measured with a stylus type film thickness meter (“Hi-Step” manufactured by Tencor) and found to be 1 μm. Next, this sample was image-exposed through a mask while changing the exposure amount with a high-pressure mercury lamp. Then, a resist pattern was obtained by spray development at a temperature of 25 ° C. using an aqueous sodium carbonate solution having a concentration of 0.8% by weight.

The formed resist pattern was evaluated for sensitivity, resolving power, and light shielding property according to the following criteria. The results are shown in Table 1.

[0242] Sensitivity

The appropriate exposure (mjZcm ² ) that can form a mask pattern with a dimension of 20 μm is displayed. In other words, a resist with a small exposure amount has high sensitivity because an image can be formed with a low exposure amount.

[0243] Resolution

The minimum resist pattern size that can be resolved at an exposure that faithfully reproduces a mask pattern with a dimension of 20 μm was observed with a microscope at a magnification of 200 times.

Minimum pattern dimension is 10 m or less: ◎

Minimum pattern dimension exceeds 10 / z m and 15 / z m or less: 〇

Minimum pattern dimension exceeds 15 m: X

[0244] Light shielding

The optical density (OD) of the image area is measured with a Macbeth reflection densitometer (Kolmorgun TR927). It was measured. The OD value is a numerical value indicating the light shielding ability. The larger the numerical value, the higher the light shielding property.

[0245] Further, for each black resist photosensitive solution prepared in i), the K + concentration was measured by the following method to determine the ratio to the total solid content in the resist photosensitive solution, and the results are also shown in Table 1. did.

Add 9 mL of pure water to 0.2 g (as solid content) of black resist (light-shielding rosin composition), extract in an ultrasonic bath for 30 minutes, then perform ultracentrifugation (50,000 rpmZlhr), and ionize the supernatant. Analyzed by chromatography.

[0246] [Table 1]

Industrial applicability

[0247] According to the light-shielding resin composition of the present invention, it is possible to form a black matrix having excellent developability, resolution, adhesion, particularly linearity and adhesion, thereby achieving high quality. A color filter and a liquid crystal display device can be provided.

Therefore, the present invention has very high industrial applicability in the fields of light-shielding resin composition, color filter, and liquid crystal display device.

[0248] Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention.

This application is a Japanese patent application filed on April 28, 2006 (Japanese Patent Application No. 2006-1).

25635) and Japanese patent applications filed on April 20, 2007 (Japanese Patent Application No. 2007-11199)

Based on 1), which is incorporated by reference in its entirety.

Claims

The scope of the claims

[I] In a light-shielding resin composition containing Noinda resin, a monomer, a photopolymerization initiator, and carbon black,

The carbon black has an average particle size of 8 nm or more and 65 nm or less,

Carbon black has a DBP oil absorption of 90mlZlOOg or less,

The light-shielding resin composition, wherein the potassium ion content of the light-shielding resin composition is 20 ppm or less based on the total solid content.

[2] The light-shielding resin composition according to claim 1, wherein the potassium ion content is 10 ppm or less with respect to the total solid content.

[3] The light-shielding resin composition according to claim 1, wherein the carbon black has a DBP oil absorption of 75 mlZlOOg or less.

Composition.

[4] The light-shielding resin composition according to claim 1, wherein the content of carbon black is 10 to 70% by weight in the total solid content of the light-shielding resin composition.

[5] The light-shielding resin composition according to claim 1, wherein the content of carbon black is 40 to 70% by weight based on the total solid content of the light-shielding resin composition.

[6] The light-shielding resin composition according to claim 1, further comprising a basic polymer dispersant.

[7] The light-shielding resin composition according to claim 1, wherein the surface of the carbon black has a pH of 5 or less.

[8] The Noinda resin is an epoxy acrylate resin having a carboxyl group.

The light-shielding rosin composition according to 1.

[9] The light-shielding resin composition according to claim 1, wherein the photopolymerization initiator is an oxime ester compound.

[10] A color filter comprising a pixel formed using the light-shielding resin composition according to claim 1.

[II] A liquid crystal display device comprising the color filter according to claim 10.