JP5029119B2 - Light-shielding resin composition, color filter, and liquid crystal display device - Google Patents

Description

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

  A color filter usually forms black pixels (hereinafter sometimes referred to as “black matrix”) on the surface of a transparent substrate such as glass or plastic sheet, and subsequently, three or more types of red, green, blue, etc. The different colored pixels are sequentially formed in a color pattern such as a stripe shape or a mosaic shape.

  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 superposition is several μm to several tens of μm, and it is manufactured by a fine processing technique with high dimensional accuracy.

  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, a pigment dispersion method for forming a color filter image by applying a colored resin composition containing a color material on a transparent substrate and repeating image exposure, development, and curing as necessary is formed. The color filter pixel is widely adopted because it has high accuracy such as position and film thickness, is excellent in durability such as light resistance and heat resistance, and has few defects such as pinholes.

  As described above, since the fine processing technology with high dimensional accuracy is required for the production of the color filter, the color resin composition to be used requires strict developability, resolution, and adhesion. In particular, in the production of a black matrix, since it is formed of a light-shielding resin composition, higher performance developability, resolution, and adhesion are required, and red formed in a subsequent process is superimposed. Thin film formability is also required so that the flatness of green and blue colored pixels is not impaired. In response to such demands, for example, a technique for improving sensitivity by improving a photopolymerization initiator and realizing high-performance developability, resolution, and adhesion in a black matrix is disclosed (Patent Document 1).

On the other hand, when a black matrix is formed by the light-shielding resin composition, it may be adjacent to the liquid crystal in the liquid crystal display device, and a highly conductive substance such as a metal ion derived from the light-shielding resin composition for forming the black matrix. It is known that when the liquid crystal 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 this problem, a technique for reducing the total content of sodium atoms and sodium ions in the colored pixels and the black matrix to a certain range, and a photosensitivity for forming a black matrix in which the amount of monovalent metal cation is less than a certain value. A composition (Patent Document 2) and a color filter (Patent Document 3) using a black matrix using carbon black whose total content of Na and Ca is reduced to a certain value or less as a light shielding material are disclosed.
JP 2005-128483 A JP 7-271020 A Japanese Patent Laid-Open No. 9-71733

  However, in the above prior art, the technique for reducing the metal ion content is aimed at preventing a decrease in the voltage holding ratio of the liquid crystal, and only the above technique achieves developability, resolution and adhesion. It was not possible. In addition, the improvement of the photopolymerization initiator in the prior art described above has an insufficient aspect in terms of improving the strict developability, resolution, adhesion, particularly linearity and adhesion.

  By the way, as carbon black used for the light-shielding resin composition as in the present invention, those having a relatively small structure are preferable. 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 a lot of potassium ions. According to the study by the present inventors, the potassium ions in the light-shielding resin composition are the substrates of the pixels formed using the light-shielding resin composition. It has been found that it becomes a factor that inhibits adhesion, resolution, and strict developability.

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

  As a result of intensive studies to solve the above problems, the present inventors have (A) binder resin, (B) monomer, (C) photopolymerization initiator, and (D) specific average particle diameter and DBP oil absorption amount. A black matrix formed using a light-shielding resin composition containing carbon black and having a reduced potassium ion content is excellent in developability, resolution, adhesion, particularly linearity, and adhesion. The inventors have found that an effect that cannot be expected from the technology is obtained, and have completed the present invention.

That is, the gist of the present invention is (A) binder resin, (B) monomer, (C) photopolymerization initiator, basic polymer dispersant, and (D) DBP oil absorption when the average particle size is 8 nm or more and 65 nm or less. In the light-shielding resin composition, wherein carbon black is 90 ml / 100 g or less and the content of potassium ions is 20 ppm or less with respect to the total solid content.

  Another gist of the present invention resides in a color filter having a pixel formed using this light-shielding resin composition.

  Another gist of the present invention resides in a liquid crystal display device including the color filter.

  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, and adhesion, thereby providing a high-quality color filter and liquid crystal display. A device can be provided.

  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 the embodiments of the present invention, and the present invention does not exceed the gist thereof. It is not limited to the contents of.

[1] Light-shielding resin composition The light-shielding resin composition of the present invention comprises (A) a binder resin, (B) a monomer, (C) a photopolymerization initiator, and (D) an average particle size of 8 nm to 65 nm. Carbon black having a DBP oil absorption of 90 ml / 100 g or less is an essential component, and if necessary, additives other than the above components are blended. Further, it is essential that the content of potassium ions is 20 ppm or less with respect to the total solid content.

  The use of the light-shielding resin composition of the present invention is not particularly limited, but it is 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 this specification, “(meth) acryl”, “(meth) acrylate” and the like mean “acryl and / or methacryl”, “acrylate and / or methacrylate” and the like, for example, “(meth) “Acrylic acid” is intended to mean “acrylic acid and / or methacrylic acid”.

  In the section [1], “total solid content” refers to all components of the light-shielding resin composition of the present invention other than the solvent components described later.

[1-1] (A) Binder Resin As the (A) binder resin used in the light-shielding resin composition of the present invention, an epoxy acrylate resin having a carboxyl group is preferably used.

  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 portion to the epoxy resin, and further reacting with a polybasic acid anhydride. Is synthesized. Such a reaction product has substantially no epoxy group in terms of chemical structure and is not limited to “acrylate”, but epoxy resin is a raw material, and “acrylate” is a representative example. It is named like this according to common usage.

  As an epoxy resin used as a raw material, for example, bisphenol A type epoxy resin (for example, “Epicoat 828”, “Epicoat 1001”, “Epicoat 1002”, “Epicoat 1004”, etc., manufactured by Yuka Shell Epoxy Co., Ltd.), bisphenol A type epoxy resin Epoxy resin obtained by the reaction of alcoholic hydroxyl group and epichlorohydrin (for example, “NER-1302” (epoxy equivalent 323, softening point 76 ° C.) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F-type resin (for example, oily shell epoxy) "Epicoat 807", "EP-4001", "EP-4002", "EP-4004 etc.") manufactured by the company, epoxy resin obtained by reaction of alcoholic hydroxyl group of bisphenol F type epoxy resin and epichlorohydrin (for example, Japan “NER-74” manufactured by Kayaku Co., Ltd. 6 ”(epoxy equivalent 350, softening point 66 ° C.)), bisphenol S type epoxy resin, biphenyl glycidyl ether (eg“ YX-4000 ”manufactured by Yuka Shell Epoxy), phenol novolac type epoxy resin (eg Nippon Kayaku) “EPPN-201” manufactured by Yakuhin, “EP-152”, “EP-154” manufactured by Yuka Shell Epoxy, “DEN-438” manufactured by Dow Chemical Co.), (o, m, p-) cresol Novolac-type epoxy resin (for example, “EOCN-102S”, “EOCN-1020”, “EOCN-104S” manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanurate (for example, “TEPIC” manufactured by Nissan Chemical Co., Ltd.), Tris Phenolmethane type epoxy resin (for example, “EPPN-501”, “EPN-502”, “Nippon Kayaku Co., Ltd.” PPN-503 ”), fluorene epoxy resin (for example, cardo epoxy resin“ ESF-300 ”manufactured by Nippon Steel Chemical Co., Ltd.), alicyclic epoxy resin (“ Celoxide 2021P ”,“ Celoxide EHPE ”manufactured by Daicel Chemical Industries, Ltd.) ), Dicyclopentadiene type epoxy resin obtained by glycidylation of phenol resin by reaction of dicyclopentadiene and phenol (for example, “XD-1000” manufactured by Nippon Kayaku Co., Ltd., “EXA-7200” manufactured by Dainippon Ink, Japan “NC-3000” and “NC-7300” manufactured by Kayaku Co., Ltd.) and epoxy resins represented by the following structural formula (see Japanese Patent No. 2878486) can be suitably used.

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

  Another example of the epoxy resin is a copolymer type epoxy resin. Examples of the copolymerization type epoxy resin include glycidyl (meth) acrylate, (meth) acryloylmethylcyclohexene oxide, vinylcyclohexene oxide and the like (hereinafter referred to as “first component of copolymerization type epoxy resin”) and one other than these. Functional ethylenically unsaturated group-containing compound (hereinafter referred to as “second component of copolymerization type epoxy resin”), for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxy Ethyl acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, styrene, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, α-methylstyrene, glycerin mono (meth) acrylate, the following general formula (1 Or a compound represented by One or more members selected, reacting the city include a copolymer obtained by.

（式（１）中、Ｒ^６１は水素またはエチル基、Ｒ^６２は水素または炭素数１〜６のアルキル基を示し、ｒは２〜１０の整数である。

(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.

  Examples of the compound of the general formula (1) include polyethylene glycol mono (meth) acrylates such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, and tetraethylene glycol mono (meth) acrylate; methoxydiethylene glycol mono ( Examples thereof include alkoxy polyethylene glycol (meth) acrylates such as meth) acrylate, methoxytriethylene glycol mono (meth) acrylate, and methoxytetraethylene glycol mono (meth) acrylate.

  As for the weight average molecular weight (Mw) of polyethylene conversion measured by GPC of the said copolymerization type epoxy resin, about 1000-200000 is preferable. The amount of the first component of the copolymerization type epoxy resin used is preferably 10% by weight or more, particularly preferably 20% by weight or more, preferably 70% by weight based on the second component of the copolymerization type epoxy resin. % By weight or less, particularly preferably 50% by weight or less.

  As such a copolymer type epoxy resin, specifically, “CP-15”, “CP-30”, “CP-50”, “CP-20SA”, “CP-510SA” manufactured by NOF Corporation, “CP-50S”, “CP-50M”, “CP-20MA” and the like are exemplified.

  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. If the weight average molecular weight is less than the above range, there are many cases where a problem occurs in the film forming property. Conversely, if the resin exceeds the above range, gelation easily occurs during the addition reaction of α, β-unsaturated monocarboxylic acid. May become difficult.

  Examples of the α, β-unsaturated monocarboxylic acid include itaconic acid, crotonic acid, cinnamic acid, acrylic acid, and methacrylic acid. Acrylic acid and methacrylic acid are preferable, and acrylic acid is particularly rich in reactivity. Therefore, it is preferable.

  The α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester portion includes acrylic acid-2-succinoyloxyethyl, acrylic acid-2-malenoyloxyethyl, acrylic acid-2-phthaloyloxyethyl, Acrylic acid-2-hexahydrophthaloyloxyethyl, methacrylic acid-2-succinoyloxyethyl, methacrylic acid-2-malenoyloxyethyl, methacrylic acid-2-phthaloyloxyethyl, methacrylic acid-2-hexahydrophthalo Yloxyethyl, crotonic acid-2-succinoyloxyethyl, and the like. Preferred are acrylic acid-2-malenoyloxyethyl acrylate and 2-phthaloyloxyethyl acrylate, and particularly acrylic acid-2-maleic acid. Noyloxyethyl is preferred. These may be used alone or in combination of two or more.

  A known method can be used for the addition reaction of α, β-unsaturated monocarboxylic acid or an ester thereof and an epoxy resin, for example, by reacting at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst. Can be implemented. Here, as the esterification catalyst, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine; quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, dodecyltrimethylammonium chloride, and the like can be used.

  The amount of α, 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 1.1, relative to 1 equivalent of the epoxy group of the raw material epoxy resin. Equivalent range. When the amount of α, β-unsaturated monocarboxylic acid or ester thereof used is small, the amount of unsaturated groups introduced is insufficient, and the subsequent reaction with polybasic acid anhydrides 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. In either case, there is a tendency for the curing properties to deteriorate.

  The polybasic acid anhydride to be further added to the epoxy resin to which the α, β-unsaturated carboxylic acid or ester thereof is added includes maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, Hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic dianhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, biphenyltetra Carboxylic acid dianhydride and the like, preferably maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, Biphenyltetracarboxylic dianhydride Particularly preferred compounds are tetrahydrophthalic anhydride and biphenyltetracarboxylic dianhydride. These may be used alone or in combination of two or more.

A known method can also be used for the addition reaction of polybasic acid anhydride, and it can be carried out by continuing the reaction under the same conditions as the addition reaction of α, β-unsaturated carboxylic acid or ester thereof.
The addition amount of the polybasic acid anhydride is preferably such that the acid value of the resulting epoxy acrylate resin is in the range of 10 to 150 mg-KOH / g, more preferably in the range of 20 to 140 mg-KOH / g. 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.

Other examples of the epoxy acrylate resin having a carboxyl group include a naphthalene-containing resin described in JP-A-6-49174; JP-A 2003-89716, JP-A 2003-165830, JP-A 2005-325331, JP-A 2001-354735. Examples of the fluorene-containing resin described in the gazette include resins described in JP-A No. 2005-126684, JP-A No. 2005-55814, JP-A No. 2004-295084, and the like.
Moreover, the commercially available epoxy acrylate resin which has a carboxyl group can also be used, and "ACA-200M" by Daicel Corporation etc. can be mentioned as a commercial item, for example.

  As the (A) binder resin, for example, an acrylic binder described in JP-A-2005-154708 can also be used.

  The ratio of (A) 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, and usually 50% by weight. Hereinafter, it is preferably 40% by weight or less, more preferably 30% by weight or less. If the ratio of the binder resin is too small, image formation becomes unstable, and it becomes difficult to control the shape, and the durability to chemicals may be deteriorated. Moreover, when there is too much, light-shielding property cannot be improved.

[1-2] (B) Monomer The monomer (B) used in the light-shielding resin composition of the present invention is not particularly limited as long as it contains a low-molecular compound that is photopolymerizable and polymerizable. , A polyfunctional monomer having a functional group is preferable, and an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”) is more preferable. Moreover, the monomer may have an acid group.

  The ethylenic compound is a compound having an ethylenic double bond 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. is there. The term “monomer” in the present invention means a concept relative to a so-called polymer substance, and in addition to “monomer” in a narrow sense, “dimer”, “trimer”, “oligomer”. Means a concept that also includes

  Examples of the ethylenic compound having an acid group include an unsaturated carboxylic acid, an ester of an unsaturated carboxylic acid and a monohydroxy compound, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, an aromatic polyhydroxy compound and an unsaturated compound. Esters obtained by esterification with unsaturated carboxylic acid, unsaturated carboxylic acid and polyvalent carboxylic acid, and polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds, and polyisocyanate compounds Examples thereof include an ethylenic compound having a urethane skeleton obtained by reacting a (meth) acryloyl-containing hydroxy compound.

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

  Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol ethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, penta Acrylic esters such as erythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate and the like can be mentioned. In addition, the acrylic acid part of these acrylates is a methacrylic acid ester substituted for a methacrylic acid part, an itaconic acid ester substituted for an itaconic acid part, a crotonic acid ester substituted for a crotonic acid part, or a maleic acid substituted for a maleic acid part Examples include esters.

  Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.

  The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance but may be 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 pentaerythritol, acrylic acid, adipic acid, butanediol and glycerin. And the like.

  Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic rings such as cyclohexane diisocyanate and isophorone diisocyanate. Formula diisocyanate; aromatic diisocyanate such as toluene diisocyanate and diphenylmethane diisocyanate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyloxymethyl) propane, 3-hydroxy (1 , 1,1-Trimethacryloyloxymethyl) propane and other (meth) acryloyl group-containing hydroxy compounds And the like.

  Other examples of the ethylenic compound used in the present invention include acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate.

  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, this can be used as it is. The acid group may be introduced by reacting the group with a non-aromatic carboxylic acid 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, succinic anhydride, anhydrous Maleic acid is mentioned.

  In the present invention, the monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.

  Of the epoxy acrylate resins described in the epoxy acrylate, those having no carboxyl group can also be used as monomers.

  These monomers may be used alone, but since it is difficult to use a single compound in production, two or more kinds may be used in combination. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.

  A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g. If the acid value of the polyfunctional monomer is too low, the development and dissolution characteristics may be lowered. If the acid value is too high, the production and handling becomes difficult and the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel is deteriorated. Tend. Accordingly, 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 should be adjusted so as to fall within the above range. is important.

  In the present invention, more preferred polyfunctional monomers having an acid group are mainly dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinic acid ester of dipentaerythritol pentaacrylate which are commercially available as TO1382 manufactured by Toagosei Co., Ltd. It is a mixture as a component. This polyfunctional monomer can also be used in combination with other polyfunctional monomers.

  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, as a ratio to the color material containing carbon black. 5 to 200% by weight, preferably 10 to 100% by weight, more preferably 15 to 80% by weight. The blending ratio of the polyfunctional monomer is appropriately adjusted according to the type of the color material containing carbon black of the light-shielding resin composition and the acid value of the polyfunctional monomer used.

  In addition, you may use a monofunctional monomer for a part among the polyfunctional monomers mentioned above as needed. In this case, examples of the monofunctional monomer include those described in JP-A-7-325400.

  Specifically, for example, isobutyl (meth) acrylate, t-butyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, Benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, phenoxy polyethylene glycol ( (Meth) acrylate, methoxypropylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, mono 2- (meth) acryloyloxyethyl phthalate, mono-2- (meth) acryloyloxypropyl phthalate, mono-2- (meth) acryloyloxypropyl tetrahydrophthalate, morpholinoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, Tetrafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorododecyl (meth) acrylate, trimethylsiloxyethyl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexane Diol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate Tripropylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, glycerin methacrylate acrylate, bisphenol A, EO adduct di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, trimethylolpropane EO adduct tri (meth) acrylate, glycerin EO adduct tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, dipentaerythritol hexa (meth) acrylate, novolak Modified (meth) acrylic acid of epoxy, modified (meth) acrylic acid and anhydride of novolak epoxy, N-vinylpyrrolidone, N-bi Examples include nilcaprolactam, (meth) acrylated isocyanurate, dipentaerythritol monohydroxypenta (meth) acrylate, urethane (meth) acrylate, and unsaturated polyester (meth) acrylate.

[1-3] (C) Photopolymerization initiator system (C) The photopolymerization initiator contained in the light-shielding resin composition of the present invention is usually an accelerator and a sensitizing dye added as necessary. It is used as a mixture (photopolymerization initiator system) with an additive. The photopolymerization initiator system 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.

  Examples of the photopolymerization initiator constituting the photopolymerization initiator system component include metallocene compounds including titanocene compounds described in JP-A Nos. 59-152396 and 61-151197, and JP-A-10 Hexaarylbiimidazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acids Examples include radical activators such as esters, α-aminoalkylphenone compounds, oxime ester initiators described in JP-A Nos. 2000-80068 and 2006-36750, and the like.

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

  2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 Halomethylated triazine derivatives such as -ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine;

  2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′-benzofuryl) vinyl] -1,3,4-oxa Diazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5 monofuryl-1,3 Halomethylated oxadiazole derivatives such as 4-oxadiazole;

  2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole dimer, 2- ( 2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenylimidazole dimer, (4'-methoxyphenyl) -4,5 -Imidazole derivatives such as diphenylimidazole dimer;

  Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;

  Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone;

  Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone;

  2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p -Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 '-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl Acetophenone derivatives such as-(p-butylphenyl) ketone;

  Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone;

  benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate;

  Acridine derivatives such as 9-phenylacridine, 9- (p-methoxyphenyl) acridine;

  Phenazine derivatives such as 9,10-dimethylbenzphenazine;

  Anthrone derivatives such as benzanthrone;

  Di-cyclopentadienyl-Ti-di-chloride, di-cyclopentagenyl-Ti-bis-phenyl, di-cyclopentagenyl-Ti-bis-2,3,4,5,6-pentafluorophenyl -1-yl, di-cyclopentagenyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentagenyl-Ti-bis-2,4,6-tri Fluorophen-1-yl, di-cyclopentagenyl-Ti-2,6-dipuruolophen-1-yl, di-cyclopentagenyl-Ti-2,4-di-fluorophen-1-yl, Di-methylcyclopentagenyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentagenyl-Ti-bis-2,6-di-fluoropheny -1 Yl, di - cyclopentadienyl -Ti-2,6-di - fluoro-3- (pill-1-yl) - titanocene derivatives such as 1-yl;

  2-Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylamino Propiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone Α-aminoalkylphenone compounds such as

  1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 An oxime ester compound such as -yl] -1- (O-acetyloxime).

  As this oxime ester compound, compounds exemplified below can be particularly preferably used.

These may be used alone or in combination of two or more.
In addition, as (C) photoinitiator in this invention, an oxime ester type compound is especially preferable.

  Examples of the accelerator constituting the photopolymerization initiator system component include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, and 2-mercaptobenzoxazole. A mercapto compound having a heterocyclic ring such as 2-mercaptobenzimidazole or an aliphatic polyfunctional mercapto compound is used.

  These photopolymerization initiators and accelerators may be used alone or in combination of two or more.

  Specific examples of the photopolymerization initiator component include dialkylacetophenone-based compounds described on pages 16 to 26 of "Fine Chemical" (March 1, 1991, vol. 20, No. 4). Benzoin, thioxanthone derivatives, and the like, as well as hexaarylbiimidazole series, S-trihalomethyltriazine series, and JP-A-4-221958 described in JP-A-58-403023 and JP-B-45-37377. And a combination of a titanocene and a xanthene dye, an addition-polymerizable ethylenic saturated double bond-containing compound having an amino group or a urethane group, and the like described in JP-A-4-219756 and the like. .

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

  If necessary, a sensitizing dye corresponding to the wavelength of the image exposure light source can be added to the photopolymerization initiator system component for the purpose of increasing the sensitivity. These sensitizing dyes include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, coumarin dyes having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335, and 3-ketocoumarin compounds described in Kaihei 3-239703 and 5-289335, pyromethene dyes described in JP-A-6-19240, and others, JP-A 47-2528, 54-155292, JP 45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-6988, JP-A-57-168088. No. 5, JP-A-5-107761, JP-A-5-210240, and JP-A-4-288818. Mention may be made of a dye or the like having a skeleton.

  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′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone. Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) Benzothiazole, 2- (p-di Tilaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, ( p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine, etc. P-dialkylaminophenyl group-containing compounds. Of these, 4,4'-dialkylaminobenzophenone is most preferred. A sensitizing dye may also be used individually by 1 type, and 2 or more types may be mixed and used for it.

  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, more preferably 0 to 0% in the total solid content in the light-shielding resin composition. 10% by weight.

[1-4] (D) Carbon Black The light-shielding resin composition of the present invention contains carbon black having an average particle size of 8 nm to 65 nm and a DBP oil absorption of 90 ml / 100 g or less as an essential component.
By using carbon black having an average particle size in the above range, the OD value (Optical Density: optical density) becomes 3.0 to 5.0, and in addition to high developability, resolution, and adhesion, contrast is also achieved. A high color filter can be provided. Further, by using carbon black having a DBP oil absorption amount of 90 ml / 100 g or less and a relatively small oil absorption amount, the developability, resolution, and adhesion can be further improved.

  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 thinning will be difficult, and if it is too small, it will be difficult to ensure dispersion stability.

The average particle diameter of carbon black in the present invention means a number average particle diameter.
In general, carbon black has an average particle size of several tens of thousands of photographs taken with an electron microscope and is photographed in several fields of view, and a particle image analysis in which about 2000 to 3000 particles of these photographs are measured by an image processing apparatus. It is calculated by.

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

  In order to set the average particle size and oil absorption amount of carbon black within the above ranges, for example, when carbon black is produced by burning heavy oil, a method of adding an inorganic compound containing potassium element into the system is adopted. I can do it.

  In this case, examples of the inorganic compound containing potassium element used for the production of carbon black include inorganic salts such as hydroxides, chlorides, sulfates, carbonates, organic acid salts including fatty acids, and metal alkyls. Organic metal compounds. Of these, potassium hydroxide and potassium chloride are particularly preferably used. These inorganic compounds containing potassium element may be used alone or in combination of two or more.

  These inorganic compounds containing potassium element should be added in such an amount that the concentration of potassium element in the atmosphere in the carbon black production process is usually 100 to 5000 ppm, more preferably 100 to 3000 ppm, to produce carbon black. .

  A specific example of a method for producing carbon black to which an inorganic compound containing potassium element is added is the method described in JP-A-8-41377.

The surface of the carbon black used in the present invention preferably has a pH of 5 or less, particularly 4 or less. When the pH of the surface of the carbon black exceeds 5, since the dispersant is difficult to adhere, 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 carbon black surface is measured by dispersing the carbon black powder in water and measuring the aqueous pH of the dispersion.

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

Mitsubishi Chemical Corporation: 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, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, OIL7B, OIL9B, OIL11B, OIL30B, OIL31

Degussa: Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Special Black 4, Color Black FW1, Color Black FW2, C lor Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170

Cabot Corporation: Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130 , VULCAN XC72R, ELFTEX-8

Koronbiyan Carbon Co., Ltd.: RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN760, RAVEN780RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1060U, RAVEN1080U, RAVEN1100URAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U , RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN575 , RAVEN7000

  The ratio of 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, and particularly preferably 40 to 70%. % By weight. When the content ratio of carbon black is too small, the coloring power becomes low, the film thickness becomes too thick with respect to the color density, and adversely affects the gap control and the like when forming a liquid crystal cell. On the other hand, if the content ratio of carbon black is too large, dispersion stability deteriorates and there is a risk that problems such as reaggregation and thickening occur.

[1-5] Other Color Material Components The light-shielding resin composition of the present invention may contain other color material components to the extent that the effects of the present invention are not impaired in addition to the carbon black.

  As other coloring materials, dyes and pigments can be used, but pigments are preferable 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 μm or less, preferably 0.1 μm or less.

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

  Examples of black pigments that can be used alone include acetylene black, lamp black, bone black, graphite, iron black (iron oxide black pigment), aniline black, cyanine black, and titanium black.

  For example, as titanium black, a method of heating and reducing a mixture of titanium dioxide and metal titanium in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), ultrafine dioxide obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at a high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069, Japanese Patent Laid-Open No. No. 61-201610), a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and reduced at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610), and the like. However, it is not limited to these.

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

  In addition, organic pigments of three colors of red, green, and blue can be mixed and used as a black pigment, and barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, and the like can also be used.

  Color materials that can be mixed for preparing a black pigment include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170), Safranin OK70: 100 (50240), Erioglaucine X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimler First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. (The numbers in parentheses above mean the color index (CI)).

  Further, other pigments that can be used in combination are C.I. I. For example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Examples thereof include brown pigments 23, 25, and 26.

  Furthermore, other known pigments of various colors such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment 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. It is. Specific examples of pigments that can be used are shown below by pigment numbers. In addition, “CI” described below means a color index (CI).

  Examples of red pigments include C.I. I. 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, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 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, 267 268, 269, 270, 271, 272, 273, 274, 275, 276. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.

  Examples of blue pigments include C.I. I. Pigment Blue 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. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment blue 15: 6.

  Examples of green pigments include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. And CI Pigment Green 7 and 36.

Examples of yellow pigments include C.I. I. 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, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208. it can. Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.

  Examples of orange pigments include C.I. I. Pigment Orange 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. Of these, C.I. I. And CI pigment oranges 38 and 71.

  Examples of purple pigments include C.I. I. 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. Of these, C.I. I. Pigment violet 19, 23, more preferably C.I. I. And CI Pigment Violet 23.

  Examples of dyes that can be used as other colorants include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

  Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

  Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.

  Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

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

[1-6] Dispersant The light-shielding resin composition of the present invention contains a dispersant because fine dispersion of a pigment such as carbon black and stabilization of the dispersion state are important for quality stability. It is desirable to do.

  Examples of the dispersant include surfactants such as nonions, cations, and anions, and polymer dispersants. Among these, polymer dispersants are preferable, and primary, secondary, or tertiary amino groups, and pyridine are particularly preferable. , Polymer dispersants having basic functional groups such as nitrogen-containing heterocycles such as pyrimidine and pyrazine (in the present invention, polymer dispersants having such basic functional groups are referred to as “basic polymer dispersants”) Is advantageously used.

  Examples of the basic polymer dispersant include urethane-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, acrylic dispersants, and the like, but urethane-based dispersants are preferable, for example, polyisocyanate compounds, Examples thereof include a polymer dispersant obtained by reacting a compound having one or two hydroxyl groups in the same molecule with a compound having active hydrogen and a tertiary amino group in the same molecule.

  Examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aromatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ω, ω Alicyclic diisocyanates such as '-diisocyanate dimethylcyclohexane, xylylene diisocyanate, α, α, α', α'-tetramethyl Aliphatic diisocyanates having aromatic rings such as luxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate , Triisocyanates such as bicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate, and trimers thereof, water adducts, and polyol adducts thereof. Preferred as the polyisocyanate are trimers of organic diisocyanate, and most preferred are trimerene of tolylene diisocyanate and trimer of isophorone diisocyanate. These polyisocyanate compounds may be used alone or in combination of two or more.

  The polyisocyanate trimer can be produced by using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc. Examples include a method of obtaining a desired isocyanurate group-containing polyisocyanate by performing partial trimerization, stopping the trimerization by adding a catalyst poison, and then removing unreacted polyisocyanate by solvent extraction and thin-film distillation. .

  Examples of compounds having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, and the like, and one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms. And mixtures of two or more of these.

  Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these.

  Polyether diols are those obtained by homo- or copolymerization of alkylene oxide, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and The mixture of 2 or more types of those is mentioned.

  Polyether ester diols include those obtained by reacting a mixture of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides, or reacting polyester glycols with alkylene oxides, such as poly (poly And oxytetramethylene) adipate.

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

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 glycol, 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-pentane Diol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol, 1,9- Nonanediol and other aliphatic glycols, bishydroxymethylcyclohexane and other alicyclic glycols, xylylene glycol and bishydroxyethoxybenzene and other aromatic glycols, N-methyldiethanolamine and other N-alkyl dialkanolamines and the like) Those obtained by condensation, such as polyethylene adipate, polybutylene adipate, Rihexamethylene adipate, polyethylene / propylene adipate, etc., or polylactone diol or polylactone monool obtained by using the above diol or monohydric alcohol having 1 to 25 carbon atoms as an initiator, such as polycaprolactone glycol, polymethylvalero Examples include lactones and mixtures of two or more thereof. Most preferred as the polyester glycol is polycaprolactone glycol or polycaprolactone starting with an alcohol having 1 to 25 carbon atoms.

  Examples of polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate. Examples of polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. Is mentioned.

  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.

  In a compound having an active hydrogen and a tertiary amino group in the same molecule, the active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom may be a functional group such as a hydroxyl group, an amino group or a thiol group. The hydrogen atom in group is mentioned, Among these, the hydrogen atom of an amino group, especially a primary amino group is preferable. The tertiary amino group is not particularly limited. Moreover, as a tertiary amino group, the amino group which has a C1-C4 alkyl group, or a heterocyclic structure, More specifically, an imidazole ring or a triazole ring is mentioned.

  Examples of compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N, N- Dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N-dibutylethylenediamine N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1,4- Examples include butanediamine.

  In addition, the tertiary amino group is an N-containing heterocycle, such as pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzo Examples thereof include N-containing hetero 5-membered rings such as thiazole ring and benzothiadiazole ring, N-containing hetero 6-membered rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, and isoquinoline ring. Preferred as these N-containing heterocycles are an imidazole ring or a triazole ring.

  Specific examples of these compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. Further, specific examples of the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1 , 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 , 4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like.

  Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole Is preferred.

  A preferable blending ratio of the dispersant raw material is 10 to 200 parts by weight, preferably 20 to 200 parts by weight of 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. 190 parts by weight, more preferably 30 to 180 parts by weight, and the compound having an active hydrogen and a tertiary amino group in the same molecule is 0.2 to 25 parts by weight, preferably 0.3 to 24 parts by weight.

  The reaction is carried out according to a known method for producing a polyurethane resin. As a solvent for performing the reaction, usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve, benzene, toluene, xylene, Hydrocarbons such as hexane, diacetone alcohol, isopropanol, sec-butanol, tert-butanol, etc., alcohols having a relatively large molecular weight around the hydroxyl group, such as alcohols other than primary alcohols, methylene chloride, chloroform 1 type, or 2 or more types, such as chlorides, such as tetrahydrofuran, ethers, such as diethyl ether, aprotic polar solvents, such as dimethylformamide, N-methylpyrrolidone, and dimethyl sulfoxide, are used.

  In the above reaction, a urethanization reaction catalyst is usually used. Examples of the urethanization reaction catalyst used include, for example, tin series such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, stannous octoate, iron series such as iron acetylacetonate and ferric chloride, triethylamine, 1 type, or 2 or more types, such as tertiary amine type | system | groups, such as a triethylenediamine, are mentioned.

  In addition, it is preferable to control the introduction amount of the compound having an active hydrogen and a tertiary amino group in the same molecule in the range of 1 to 100 mg-KOH / g 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 obtained by neutralizing and titrating a basic amino group with an acid, and representing the acid value in mg of KOH. When the amine value is less than the above range, the dispersing ability tends to be lowered, and when it exceeds the above range, developability tends to be lowered.

  In the case where an isocyanate group remains in the polymer dispersant produced by the above reaction, it is preferable to modify the remaining isocyanate group with an alcohol or an amino compound because the stability with time of the product becomes high.

The weight average molecular weight of such a basic polymer dispersant is usually 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 50,000. 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 inferior and the reaction is difficult to control.
In addition, a weight average molecular weight is measured by polystyrene conversion by GPC (gel permeation chromatography).

  As the basic polymer dispersant, commercially available ones can also be used. For example, under the trade name, BY161 DB161, DB162, DB163, DB164, DB166, DB182, EFKA 4046, Lubrizol. Examples include Solid Spur 38500, Solid Spur 20000, Solid Spur 24000, Solid Spur 27000, Solid Spur 28000, and the like.

  These dispersing agents may be used individually by 1 type, and may mix and use 2 or more types.

  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, more preferably 0.5% by weight or more. The amount is usually 10% by weight or less, preferably 6% by weight or less, and more preferably 5% by weight or less. If the content of the dispersant is too small, the dispersion stability is deteriorated, 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.

[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.

  Examples of pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, Examples thereof include derivatives such as dioxazine pigments. As substituents of pigment derivatives, sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. can be directly in the pigment skeleton or alkyl groups, aryl groups, complex groups. Examples thereof include those bonded via a ring group and the like, preferably a sulfonamide group and 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 pigment sulfonic acid. And sulfonic acid derivatives of dioxazine pigments.

  The addition amount of the pigment derivative is usually 0.01 to 4% by weight, preferably 0.05 to 3% by weight or less, more preferably 0.1 to 2%, based on the total solid content of the light-shielding resin composition of the present invention. % By weight. If the addition amount of the pigment derivative is small, the dispersion stability is deteriorated, and problems such as reaggregation and thickening may occur. On the contrary, if the amount is too large, the contribution to the dispersion stability is saturated, and on the contrary, the color purity may be lowered.

[1-8] Organic Carboxylic Acid, Organic Carboxylic Anhydride The light-shielding resin composition of the present invention may further contain an organic carboxylic acid and / or an organic carboxylic acid anhydride in addition to the above components.

[1-8-1] Organic carboxylic acid Examples of the organic carboxylic acid include aliphatic carboxylic acids and / or aromatic carboxylic acids. Specific examples of the aliphatic carboxylic acid include monoacids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid, glycolic acid, acrylic acid, and methacrylic acid. Carboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethyl Examples thereof include dicarboxylic acids such as succinic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, and fumaric acid, and tricarboxylic acids such as tricarbaryl acid, aconitic acid, and camphoric acid. Specific examples of the aromatic carboxylic acid include benzoic acid, toluic acid, cumic acid, hemelic acid, mesitylene acid, phthalic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, and merophanic acid. , Pyromellitic acid, phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, umbelic acid, etc. Examples thereof include carboxylic acids in which a carboxyl group is directly bonded to a group, and carboxylic acids in which a carboxyl group is bonded from a phenyl group through a carbon bond.

  Among the organic carboxylic acids, monocarboxylic acids and dicarboxylic acids are preferable, and malonic acid, glutaric acid, and glycolic acid are more preferable, and malonic acid is particularly preferable.

  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 background stains is insufficient. If the molecular weight is too small, the addition amount may be reduced or process contamination may occur due to sublimation or volatilization.

[1-8-2] Organic carboxylic acid anhydride Examples of the organic carboxylic acid anhydride include aliphatic carboxylic acid anhydrides and / or aromatic carboxylic acid anhydrides. Includes acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, glutaric anhydride, 1,2-cyclohexenedicarboxylic anhydride, n -Aliphatic carboxylic acid anhydrides such as octadecyl succinic acid and anhydrous 5-norbornene-2,3-dicarboxylic acid. Specific examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride.

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

  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 organic carboxylic acid anhydride is too large, the effect of improving background stains is insufficient, and if it is too small, there is a risk of reducing the amount of addition or process contamination due to sublimation or volatilization.

  One of these organic carboxylic acids and / or organic carboxylic acid anhydrides may be used alone, or two or more thereof may be mixed and used.

  The addition amount of these organic carboxylic acids and / or organic carboxylic acid anhydrides is usually 0.01% by weight or more, preferably 0.03% by weight or more, based on the total solid content of the light-shielding resin composition of the present invention. Preferably it is 0.05 weight% or more, Usually, 10 weight% or less, Preferably it is 5 weight% or less, More preferably, it is 3 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 are deteriorated, and undissolved peeling pieces may be generated.

[1-9] Other Solid Content The light-shielding resin composition of the present invention can further contain a solid content 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.

[1-9-1] Surfactant As the surfactant, one or more of various types such as anionic, cationic, nonionic, and amphoteric surfactants can be used. It is preferable to use a nonionic surfactant from the viewpoint that

  The addition amount of the surfactant is usually 0.001 to 10% by weight, preferably 0.005 to 1% by weight, and more preferably 0.01 to 10% by weight with respect to the total solid content in the light-shielding resin composition of the present invention. 0.5% by weight, most preferably 0.03-0.3% 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 too large, the smoothness and uniformity of the coating film cannot be expressed and other characteristics may be deteriorated. .

[1-9-2] Thermal polymerization inhibitor Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol, and the like. Or 2 or more types 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.

[1-9-3] Plasticizer Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like. 1 type (s) or 2 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.

[1-9-4] Others 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.

[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 (A) a binder resin, (B) a monomer, (C) a photopolymerization initiator, (D) carbon black and the other colorants described above, a dispersant, and further It has the function of adjusting viscosity by dissolving or dispersing other components blended as necessary.

As the solvent, it is preferable to select a solvent that 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.

  Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, methoxymethyl Glycol monoalkyl ethers such as pentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether;

  Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;

  Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, dipropylene glycol Glycol alkyl ether acetates such as monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate;

  Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;

  Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone;

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

  aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;

  Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

  Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;

  Amyl formate, ethyl formate, 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-methoxy Linear or cyclic esters such as propyl propionate, butyl 3-methoxypropionate, γ-butyrolactone;

  Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

  Halogenated hydrocarbons such as butyl chloride and amyl chloride;

  Ether ketones such as methoxymethylpentanone;

  Nitriles such as acetonitrile and benzonitrile;

  Solvents corresponding to the above include mineral spirit, Valsol # 2, Apco # 18 Solvent, Apco Thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, diglyme and other commercial products.

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

  The content of the solvent in the light-shielding resin composition of the present invention is not particularly limited, but is usually 99% by weight or less, usually 50% by weight or more, preferably 55% by weight or more, and more preferably 60% by weight. % Or more. If the proportion of the solvent is too large, the solid content of the binder resin, the monomer, the color material such as carbon black, the dispersing agent, etc. is too small, which is inappropriate for forming the light-shielding resin composition. On the other hand, when the ratio of the solvent is too small, the viscosity becomes high and is not suitable for coating.

[1-11] Potassium ion content In the light-shielding resin composition of the present invention, it is essential that the potassium ion content is 20 ppm or less based on the total solid content. The potassium ion content is preferably 18 ppm or less, more preferably 10 ppm or less, based on the total solid content of the light-shielding resin composition.

  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 the content of potassium ion in the light-shielding resin composition is too large, developability, resolution, adhesion, particularly linearity and adhesion cannot be sufficiently ensured.

In order to set the content of potassium ions in the above range, for example, in the case of carbon black obtained by the method of adding potassium element in Section [1-4], there is a method of removing it by washing or the like.
When removing by washing with water, it is important to make carbon black and water contact efficiently. Specifically, a method of adding pure water to carbon black and kneading or stirring the mixture many times while changing the water using a device such as a homomixer, a twin screw kneader, or a normal stirrer can be mentioned. The total amount of water used is preferably 500 mL or more, more preferably 1000 mL or more per 100 g of carbon black.

  The potassium ion content in the light-shielding resin composition is, for example, by adding 9 mL of pure water to 0.2 g (as a solid content) of the light-shielding resin composition and extracting it in an ultrasonic bath for 30 minutes, followed by ultracentrifugation. (50,000 rpm × 1 hr), and the supernatant can be measured by ion chromatography.

[2] Method for producing light-shielding resin composition The light-shielding resin composition of the present invention comprises, for example, as follows, first, (D) carbon black, a solvent, and, if necessary, a dispersant and other components. A black pigment dispersion can be produced by dispersing and mixing, and (A) binder resin, (B) monomer, (C) photopolymerization initiator, etc. can be added to and mixed with this black pigment dispersion. The manufacturing method of the light-shielding resin composition of the invention is not limited to this method.

[2-1] Method for Producing Black Pigment Dispersion Liquid 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 form a liquid black pigment. A dispersion is obtained. 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, or 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 color filter The light shielding ability of the substrate is improved.

  When the pigment is subjected to a dispersion treatment, the above binder resin or dispersion aid may be used in combination as appropriate. For example, when a 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 zirconia beads. The temperature for 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 dispersion time varies depending on the composition of the black pigment dispersion (pigment, solvent, dispersant, etc.), the size of the sand grinder apparatus, etc., and therefore needs to be adjusted as appropriate.

  In this case, the standard of dispersion is to control the gloss of the black pigment dispersion so that the 20-degree specular gloss in JIS Z8741 is in the range of 100 to 200. When the gloss of the black pigment dispersion is low, the dispersion treatment is not sufficient and rough pigment particles often remain, which is insufficient in terms of developability, adhesion, resolution, and the like. In addition, when the dispersion treatment is performed until the gloss value exceeds the above range, a large number of ultrafine particles are generated, and the dispersion stability tends to be impaired.

  As described above, the black pigment dispersion produced in this way is added with (A) a binder resin when the pigment is dispersed, and the (A) binder resin of the light-shielding resin composition of the present invention is added. A part thereof may be included, and by including such a binder resin, the dispersion stability at the time of producing a black pigment dispersion can be enhanced.

  In this case, the amount of the (A) binder resin added is preferably 5 to 100% by weight, particularly 10 to 80% by weight, based on the pigment in the black pigment dispersion. (A) If the addition amount of the binder resin is too small, the effect of increasing the dispersion stability is insufficient, and if it is too large, the density of the color material such as carbon black is lowered, so that sufficient light shielding properties cannot be obtained.

The solid content concentration in the black pigment dispersion is usually about 10 to 20% by weight. The concentration of potassium ions and / or potassium atoms is usually 100 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 a black pigment dispersion obtained by the above process and other components necessary as components of the light-shielding resin composition. Are added and mixed to prepare a uniform solution. In this case, a dispersion treatment using a liquid in which all the components to be blended as the light-shielding resin composition are mixed at the same time is not preferable because a highly reactive component may be denatured due to heat generated at the time of dispersion. In addition, since fine dust is often mixed in the liquid in the manufacturing process, it is desirable to filter the obtained light-shielding resin composition with a filter or the like.

[3] Production of Color Filter Next, a specific example of the production method of the color filter of the present invention will be described.

  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.

The light-shielding resin composition of the present invention is particularly used as a coating liquid for forming a black matrix for a color filter.
Coating, heating and drying, image exposure, development, and thermosetting processes for black resist on the transparent substrate and for red, green, and blue color resists on the resin black matrix forming surface formed on the transparent substrate, respectively. To form a pixel image of each color.

[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. Examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, epoxy resins, unsaturated polyester resins, and poly (meth). Examples thereof include thermosetting resin sheets such as acrylic resins, and various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance.

  For transparent substrates and black matrix forming substrates, to improve surface properties such as adhesion, corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as silane coupling agents and urethane resins, as necessary May be performed.

  The thickness of the transparent substrate is usually 0.05 to 10 mm, preferably 0.1 to 7 mm. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01-10 micrometers normally, Preferably it is the range of 0.05-5 micrometers.

[3-2] Formation of Pixel [3-2-1] Formation of Coating Film In forming the black matrix, the light-shielding resin composition of the present invention is applied on a transparent substrate, dried, and then formed. A photomask is overlaid on the surface, and image exposure, development, and thermal curing or photocuring are performed as necessary through the photomask. In forming the pixel, a colored composition containing one color material 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 image exposure, development, and heat curing or photocuring as necessary are performed through this photomask to form a pixel image, thereby creating 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.

  Application of the light-shielding resin composition and the coloring composition can be performed by a spinner method, a wire bar method, a flow coating 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 has no influence from mist adhering to the spin coating method. To preferred.

  If the thickness of the coating film is too thick, pattern development becomes difficult and it may be difficult to adjust the gap in the liquid crystal cell forming process. Expression may be impossible. The thickness of the coating film is usually preferably in the range of 0.2 to 20 μm as the film thickness after drying, more preferably in the range of 0.5 to 10 μm, and still more preferably in the range of 0.8 to 5 μm. It is a range.

[3-2-2] Drying of coating film The coating film formed by coating a light-shielding resin composition or a colored composition on a transparent substrate is dried by using a hot plate, an IR oven, or a convection oven. Is preferred. 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 kind of the solvent component in the light-shielding resin composition or the colored composition, the performance of the dryer to be used, and the like. The drying time is usually selected in the range of 15 to 5 minutes at a temperature of 40 to 80 ° C., preferably 30 to 50 to 70 ° C., depending on the type of solvent component, the performance of the dryer used, and the like. It is selected in the range of seconds to 3 minutes.

  The reheat drying temperature condition is 50 to 200 ° C higher than the predrying temperature, 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 is, the better the adhesion of the coating film to the transparent substrate is. 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.

[3-2-3] Exposure Step Image exposure is performed by superposing a negative matrix pattern on a dried coating film of a light-shielding resin composition or a colored composition, and using this mask pattern, an ultraviolet or visible light source Irradiation is performed. 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 a decrease in sensitivity of the coating film due to oxygen.

  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, a carbon arc, a fluorescent lamp. And lamp light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, and semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

[3-2-4] Development Step After the image exposure, development can be performed 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.

  Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate , Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethyl Ami, mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), coli And organic alkaline compounds such as. These alkaline compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinate esters, amphoteric surfactants such as alkylbetaines, amino acids, etc. They may be used alone or in combination of two or more.

  Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. These organic solvents may be used individually by 1 type, may be used in mixture of 2 or more types, and may be used 1 type or 2 types or more together with water.

  There are no particular limitations on the conditions for the development treatment, and usually the development temperature is in the range of 10 to 50 ° C., especially 15 to 45 ° C., particularly preferably 20 to 40 ° C. The development methods are immersion development, spray development, brush Any of a developing method, an ultrasonic developing method and the like can be used.

[3-2-5] Thermosetting treatment The developed color filter substrate is usually subjected to thermosetting treatment or photocuring treatment, preferably thermosetting treatment.

  As for the thermosetting treatment conditions, the temperature is selected in the range of 100 to 280 ° C, preferably in the range of 150 to 250 ° C, and the time is selected in the range of 5 to 60 minutes.

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

[3-2-6] Formation of transparent electrode The color filter according to the present invention forms a transparent electrode such as ITO on an image as it is, and is used as a part of a component such as a color display or a liquid crystal display device. However, 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.

  Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed.

[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.

  In the liquid crystal display device of the present invention, an alignment film is usually formed on the color filter of the present invention, spacers are dispersed on the alignment film, and then bonded to a counter substrate to form a liquid crystal cell. The liquid crystal is injected into the cell and connected to the counter electrode.

  As the alignment film, a resin film such as polyimide is suitable. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, 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 irradiation with ultraviolet rays or a rubbing cloth to process the surface state so that the tilt of the liquid crystal can be adjusted.

  A spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer of 2 to 8 μm is usually preferable. A photo spacer (PS) of a transparent resin film can be formed on the color filter substrate by photolithography, and this can be used instead of the spacer.

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

  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 μm. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by ultraviolet (UV) irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.

The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of reduced pressure in the liquid crystal cell is usually 1 × 10 ⁻² to 1 × 10 ⁻⁷ Pa, preferably 1 × 10 ⁻³ to 1 × 10 ⁻⁶ Pa. Moreover, it is preferable to heat a liquid crystal cell at the time of pressure reduction, and heating temperature is 30-100 degreeC normally, More preferably, it is 50-90 degreeC. The warming hold during decompression is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal. The liquid crystal cell into which the liquid crystal is injected has a liquid crystal display device (panel) completed by sealing the liquid crystal injection port by curing the UV curable resin.

  The type of liquid crystal is not particularly limited, and conventionally known liquid crystals such as aromatic, aliphatic, and polycyclic compounds are used, and any of lyotropic liquid crystals, thermotropic liquid crystals, and the like may be used. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of them may be used.

  EXAMPLES 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.

[Synthesis example]
Synthesis Example 1 (Preparation of polymer dispersant solution)
32 g of tolylene diisocyanate trimer (Mittech GP750A manufactured by Mitsubishi Chemical Co., Ltd., resin solid content 50% by weight, butyl acetate solution) and 0.02 g of dibutyltin dilaurate as a catalyst in 47 g of propylene glycol monomethyl ether acetate (PGMEA) Diluted and dissolved. Under stirring, the number average molecular weight 1,000 polyethylene glycol ("Uniox M-1000" manufactured by NOF Corporation) having one end of a methoxy group and polypropylene having a number average molecular weight of 1,000. A mixture of 9.6 g of glycol (“SANNICS PP-1000” manufactured by Sanyo Chemical Industries, Ltd.) was dropped, and the mixture was further reacted at 70 ° C. for 3 hours. Next, 1 g of N, N-dimethylamino-1,3-propanediamine was added, and the mixture was further reacted at 40 ° C. for 1 hour. The amine value of the solution containing the polymer dispersant thus obtained was determined by neutralization titration to be 14 mg-KOH / g. The resin content was 40% by weight as determined by the dry-up method (at 150 ° C. for 30 minutes, the solvent was removed on a hot plate and the resin concentration was calculated from the weight change).

Synthesis example-2 (synthesis of binder resin)
“XD1000” manufactured by Nippon Kayaku Co., Ltd. (polyglycidyl ether of dicyclopentadiene / phenol polymer, weight average molecular weight 700, epoxy equivalent 252) 300 parts by weight, 87 parts by weight of acrylic acid, 0.2 parts by weight of p-methoxyphenol Part, 5 parts by weight of triphenylphosphine and 255 parts by weight of PGMEA were charged in a reaction vessel and stirred at 100 ° C. until the acid value became 3.0 mg-KOH / g. It took 9 hours for the acid value to reach the target (acid value 2.5 mg-KOH / g). Subsequently, 145 parts by weight of tetrahydrophthalic anhydride was further added and reacted at 120 ° C. for 4 hours to obtain a binder resin I solution having an acid value of 100 mg-KOH / g and a weight average molecular weight of 2600 in terms of polystyrene measured by GPC.

Synthesis Example 3 (Preparation of ink)
<Preparation of ink for example>
(Preparation of ink 1)
Carbon black for color (“MA-8” manufactured by Mitsubishi Chemical Co., Ltd., average particle size 24 μm, DBP oil absorption 58 ml / 100 g, surface pH 3.0) 100 g in a biaxial kneader with 500 ml of ultrapure water for 20 minutes The ultrapure water was removed by kneading and filtration. Ultrapure water was again added to the filtered carbon black and kneaded, and filtration was repeated four times. Finally, the carbon black filtered was dried and washed to obtain carbon black. 50 parts by weight of washed carbon black, 10 parts by weight of the polymer dispersant prepared in Synthesis Example-1 as a solid content, and carbon black and polymer dispersant so that the solid content concentration is 30% by weight Solution and PGMEA were added. The total weight of the dispersion was 50 g. This was thoroughly stirred with a stirrer and premixed.

  Next, the dispersion process was performed in the range of 25-45 degreeC with the paint shaker for 6 hours. As beads, 0.5 mmφ zirconia beads were used, and the same weight as the dispersion was added. After the completion of dispersion (20-degree specular gloss 170 in JIS Z8741), the beads and the dispersion were separated by a filter to prepare ink 1.

For this ink 1, 9 mL of pure water was added to 0.2 g of an ink sample, extracted for 30 minutes in an ultrasonic bath, ultracentrifugated (50,000 rpm × 1 hr), and the supernatant was subjected to ion chromatography analysis. The K ⁺ ion concentration (hereinafter the same) with respect to the total solid content was less than 5 ppm (below the detection limit).

(Preparation of ink 2)
Ink 2 was prepared in the same manner as ink 1 except that the number of cleaning, kneading and filtration operations with ultrapure water was set 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.

(Preparation of ink 3)
Ink 3 was prepared in the same manner as ink 1 except that the number of cleaning, kneading and filtration operations with ultrapure water was three. This ink 3 was subjected to ion chromatographic analysis in the same manner as ink 1, and the K ⁺ concentration was 6 ppm.

(Preparation of ink 4)
Ink 4 was prepared in the same manner as ink 1 except that the number of operations of washing, kneading, and filtration 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 comparative ink>
(Preparation of ink 5)
Ink 5 was prepared in the same manner as ink 1 except that no washing with ultrapure water was performed. When this ink 5 was subjected to ion chromatographic analysis in the same manner as ink 1, the K ⁺ concentration was 401 ppm.

  Note that the average particle diameter, DBP oil absorption, and surface pH of the carbon black used were the same as before the cleaning, kneading, and filtration treatment with ultrapure water.

[Examples 1 to 4 and Comparative Example 1]
(1) 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 by a stirrer. Prepared.

有機溶剤（ＰＧＭＥＡ）：３００ｇ
界面活性剤（住友３Ｍ社製「ＦＣ−４３０」フッ素系界面活性剤）：レジスト液中の濃度が１００ｐｐｍとなる量 <Combination ratio>
Ink prepared in Synthesis Example-3 (shown in Table 1): 50 g as a solid content
Binder resin I solution prepared in Synthesis Example-2: 30 g as a solid content
Monomer (ethylenic compound: dipentaerythritol hexaacrylate): 10 g
Basic polymer dispersant-containing solution prepared in Synthesis Example-1: 5 g as a solid content
Photopolymerization initiator (“CGI242” manufactured by Ciba Specialty Chemicals Co., Ltd.): 5 g

Organic solvent (PGMEA): 300g
Surfactant ("FC-430" fluorosurfactant manufactured by Sumitomo 3M Co.): An amount that makes the concentration in the resist solution 100 ppm

(2) Evaluation of resist solution Each black resist photosensitive solution prepared in (1) was applied to a glass substrate (“7059” manufactured by Corning) with a spin coater, and dried at 80 ° C. for 1 minute on a hot plate. The film thickness of the resist after drying was measured with a stylus type film thickness meter (“α-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 a sodium carbonate aqueous 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, and the results are shown in Table 1.

1. Sensitivity Displayed with an appropriate exposure amount (mj / cm ² ) capable of forming a mask pattern having a dimension of 20 μm as the dimension. That is, a resist with a small exposure amount has high sensitivity because an image can be formed with a low exposure amount.

2. Resolution The minimum resist pattern dimension that can be resolved at an exposure amount that faithfully reproduces a mask pattern having a dimension of 20 μm was observed with a microscope at a magnification of 200 times.
Minimum pattern dimension is 10μm or less: ◎
Minimum pattern dimension is more than 10μm and 15μm or less: ○
Minimum pattern dimension exceeds 15 μm: ×

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

Further, for each black resist photosensitive solution prepared in (1), the K ⁺ concentration was measured by the following method, the ratio to the total solid content in the resist photosensitive solution was determined, and the results are also shown in Table 1.
<K ⁺ concentration measurement method>
Add 9 mL of pure water to 0.2 g (as solid content) of black resist (light-shielding resin composition), extract in an ultrasonic bath for 30 minutes, then perform ultracentrifugation (50,000 rpm / 1 hr), and remove the supernatant. Analyzed by ion chromatography.

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, and adhesion, thereby providing a high-quality color filter and liquid crystal display. A device can be provided.
Therefore, the present invention has very high industrial applicability in the fields of light-shielding resin compositions, color filters, and liquid crystal display devices.

Claims (10)

(A) Binder resin, (B) monomer, (C) photopolymerization initiator, basic polymer dispersant, and (D) carbon having an average particle size of 8 nm to 65 nm and a DBP oil absorption of 90 ml / 100 g or less A light-shielding resin composition comprising black and having a potassium ion content of 20 ppm or less based on the total solid content.   The light-shielding resin composition according to claim 1, wherein the content of potassium ions is 10 ppm or less with respect to the total solid content. (D) The light-shielding resin composition according to claim 1 or 2, wherein the carbon black has a DBP oil absorption of 75 ml / 100 g or less.
Composition.   (D) The light-shielding resin composition according to any one of claims 1 to 3, wherein the content of carbon black is 10 to 70% by weight in the total solid content of the light-shielding resin composition.   (D) The light-shielding resin composition according to any one of claims 1 to 3, wherein the content of carbon black is 40 to 70% by weight in the total solid content of the light-shielding resin composition. (D) The light-shielding resin composition according to any one of claims 1 to 5 , wherein the surface of the carbon black has a pH of 5 or less. (A) The light-shielding resin composition according to any one of claims 1 to 6 , wherein the binder resin is an epoxy acrylate resin having a carboxyl group. (C) The light-shielding resin composition according to any one of claims 1 to 7 , wherein the photopolymerization initiator is an oxime ester compound. Color filter and having a pixel formed by using a light-shielding resin composition according to any one of claims 1 to 8. A liquid crystal display device comprising the color filter according to claim 9 .