KR20140130224A - Carbon black dispersant for black matrix - Google Patents

Abstract

Provided is a carbon black dispersion capable of forming a fine line pattern excellent in adhesion with high light shielding and high resistance when used in a resist composition for a black matrix of a color filter. (I): wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁵ represents a hydrogen atom or a methyl group, A represents -CO-, -SO ₂ -, -C (CF ₃ ) ₂ -, -Si (CH ₃ ) ₂ -, -CH ₂ -, -C (CH ₃ ) ₂ -, -O-, 9,9-fluorenyl group or a direct bond, X represents a tetravalent carboxylic acid residue, Y ¹ and Y ² each independently represent a hydrogen atom or -OC-Z - (COOH) _m (wherein Z represents a divalent or trivalent carboxylic acid residue and m represents a number of 1 to 2), and n represents an integer of 1 to 20) Acrylate is a carbon black dispersion for a black matrix containing water.

Description

Carbon Black Dispersion for Black Matrix {CARBON BLACK DISPERSANT FOR BLACK MATRIX}

The present invention relates to a carbon black dispersion used in a resist composition for a black matrix of a color filter. To a carbon black dispersion capable of forming a fine line pattern excellent in adhesion with high light shielding and high resistance in a black matrix of a color filter.

Recently, color liquid crystal display devices have been used in all fields such as liquid crystal TVs, liquid crystal monitors, and color liquid crystal cellular phones. The color filter is one of the important members that determines the visibility of the color liquid crystal display device. It is required to further improve the visibility and to further enhance the black matrix in order to obtain a clearer image, so that a pigment such as carbon black is added to the photosensitive resin composition It is added in a larger amount than in the prior art.

However, when the content of the pigment is increased, light in the ultraviolet ray region is hardly reaching the deep portion of the coating film, especially in the case of forming a color filter, and the adhesion of the pattern is poor due to the hardening failure in the photocurable composition, There arises a problem that loss of sharpness of the shrinkage occurs. Therefore, a high sensitivity photopolymerization initiator and an acrylic monomer having a high degree of polymerization have been used so as not to cause a hardening failure even when a high concentration of pigment is contained. However, in the present technology, it is realistic that sensitization to a photopolymerization initiator or acrylic monomer is different from the limit There is a problem that sufficient sensitivity, adhesion and storage stability for forming a good pattern in the high-concentration pigment region can not be obtained.

When carbon black is used as the pigment, since the carbon black has conductivity, the resistance value of the black matrix obtained by raising the carbon black concentration in the resin in order to increase the light shielding property is lowered so that the distance between the transparent electrode on the color filter and the black matrix yarn or the counter electrode And there is a problem that the image defect is easily caused.

Therefore, the inventors of the present invention have proposed a resist composition for a color filter using a carbon black pigment dispersion in which specific epoxy (meth) acrylate acid moieties are covaried together with a dispersant using water as an alkali-soluble resin used in pigment dispersion (Refer to Patent Document 1). According to the resist composition, high adhesion to a high sensitivity and excellent storage stability can be attained in a region including a high-concentration pigment achieving high light shielding.

Patent Document 1: JP-A-2008-9401

However, even with the resist composition, it is still difficult to achieve both high shielding and high resistance in the fine line pattern. For example, when a large amount of carbon black is added for improving the light shielding property, What was not obtained, but the resistance did not reach the required level remained as a problem.

The present invention has been made in view of the above problems, and it is an object of the present invention to provide a carbon black dispersion capable of achieving high adhesion performance and storage stability while maintaining high light shielding and high resistance in the resist composition, There is.

The above object of the present invention is achieved by the following means.

(1) That is, the present invention is a carbon black dispersion for black matrix comprising carbon black, a photo-curable resin or a thermosetting resin dispersed in a solvent, wherein the carbon black comprises a dye-coated carbon black having a surface coated with a dye , The photocurable resin or the thermosetting resin is a resin obtained by reacting a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols with (meth) acrylic acid with (a) a dicarboxylic acid or its anhydride and (b) a tetracarboxylic acid (I), which is obtained by reacting an acid dianhydride or its acid dianhydride so that the molar ratio of (a) to (b) is 1: 10 to 10:

[Chemical Formula 1]

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ⁵ is a hydrogen atom or a methyl group, , -SO ₂ -, -C (CF ₃ ) ₂ -, -Si (CH ₃ ) ₂ -, -CH ₂ -, -C (CH ₃ ) ₂ -, -O-, 9,9- It denotes a straight bond, X is a tetravalent carboxylic acid moiety, Y ¹ and Y ² is a hydrogen atom or a -OC-Z- (COOH) _m (end, Z is a divalent or trivalent residue of carbon acid, each independently (Wherein m represents a number of 1 to 2), and n represents an integer of 1 to 20, is a carbon black dispersion for a black matrix containing an epoxy (meth) acrylate acid moiety.

(2) In the present invention, the dye-coated carbon black is the carbon black dispersion for a black matrix according to (1), wherein the content of the dye is 0.5 to 10 mass%.

(3) The present invention is also the carbon black dispersion for a black matrix according to (1) or (2), wherein the dye-coated carbon black is an anionic or nonionic dye.

(4) The present invention is also the carbon black dispersion for a black matrix according to any one of (1) to (3), wherein the dye-coated carbon black is a dye of a dark color series.

(5) In the present invention, the dye-coated carbon black is the carbon black dispersion for a black matrix according to any one of (1) to (4), wherein the dye is lacquered by a metal or a metal salt.

(6) The present invention is also the carbon black dispersion for black matrix according to (5), wherein the metal or metal salt is aluminum, magnesium, calcium, strontium, barium or manganese or a salt thereof.

(7) The present invention also relates to the carbon black for black matrix according to any one of (1) to (6), wherein the dye-coated carbon black is obtained by using carbon black having at least one acidic functional group on its surface. Is a dispersant.

(8) In the present invention, it is also preferable that the acidic functional group is at least one compound selected from the group consisting of hydroxyl group, oxo group, hydroperoxy group, carbonyl group, carboxyl group, peroxycarboxylic acid group, aldehyde group, ketone group, nitro group, Is a carbon black dispersion for a black matrix according to (7), wherein the carboxylic acid group is a carboxylic acid group, a sulfinic acid group, a sulfinic acid group, a thiocarboxylic acid group, a chlorosilyl group, a chloryl group, a perchloryl group, an iodo group or an iodoyl group.

(9) The present invention is also the carbon black dispersion for black matrix according to any one of (1) to (8), wherein the content of the dye-coated carbon black is 15 to 35 mass%.

(10) The present invention is also the carbon black dispersion for a black matrix according to any one of (1) to (9), wherein the amount of the epoxy (meth) acrylate acid part is 2 to 20 mass%.

Since the carbon black dispersion for a black matrix of the present invention comprises water and the specific epoxy (meth) acrylate acid part in which the dye-coated carbon black whose surface is coated with a dye is used in a resist composition for a black matrix, And a fine line pattern excellent in substrate adhesion can be formed. When this is applied to a color filter, a black matrix with high light shielding, high resistance and reliability can be produced.

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

The carbon black dispersion for black matrix of the present invention is obtained by dispersing carbon black, a photo-curable resin or a thermosetting resin in a solvent.

The carbon black used as the carbon black dispersion for a black matrix of the present invention includes a dye-coated carbon black whose surface is coated with a dye.

The kind of raw material carbon black used in the dye-coated carbon black of the present invention is not particularly limited, and known carbon black such as lamp black, acetylene black, thermal black, channel black, and furnace black can be used.

The raw material carbon black preferably has an average primary particle diameter of 5 to 60 nm, more preferably 10 to 50 nm, and particularly preferably 20 to 45 nm. Here, the average primary particle diameter refers to an additive average value of the primary particle diameters obtained by observing 1500 carbon black primary particles with an electron microscope. If the average primary particle diameter of the raw material carbon black is less than the above lower limit, it easily agglomerates to deteriorate the stability of the mill base and make it difficult to disperse a high concentration, while if exceeding the upper limit, the black matrix tends to cause a shape defect, Which is not preferable.

The raw material carbon black preferably has a DBP oil absorption (oil absorption amount) of 100 ml / 100 g or less. Here, the DBP oil absorption refers to the capacity of dibutyl phthalate (DBP) absorbed by 100 g of carbon black (JIS 6217). When the DBP oil absorption amount of the raw material carbon black exceeds the upper limit, the resistance value is lowered and the viscosity is increased, so that the coating property is deteriorated and the blackness is lowered, which is not preferable.

The raw material carbon black preferably has a pH value of 2 to 10, more preferably 5 to 9, and particularly preferably 4 to 8. Here, the pH value refers to a value obtained by measuring a mixture of carbon black and distilled water with a glass electrode pH meter (JIS6221). If the pH of the raw material carbon black is less than the above lower limit, the balance of the whole is broken and the stability becomes worse. If the pH exceeds the upper limit, the film is easily peeled off.

The raw material carbon black preferably has an ash content of 1.0% or less and a specific surface area of 20 to 300 m 2 / g. If the ash content exceeds the upper limit, the resistance value is lowered. If the specific surface area is below the lower limit, defective shape of the black matrix tends to easily occur. If the content exceeds the upper limit, a large amount of dispersant, resin, It is not preferable either.

The raw material carbon black preferably has at least one acidic functional group on its surface after oxidation treatment in advance, and more preferably has two or more kinds of acidic functional groups on its surface by carrying out oxidation treatment of plural kinds. In the case where the oxidation treatment is not carried out in advance, since the acidic functional group is not present on the surface or the number of the acidic functional groups is insufficient, the dispersibility of the carbon black for black matrix obtained can not be sufficiently secured and the resistance value is lowered, So that the transparent electrode on the color filter and the black matrix yarn or the counter electrode are electrically connected to each other to easily cause image defects. As the oxidation treatment, a method using ozone gas, nitric acid, sodium hypochlorite, hydrogen peroxide, nitrogen monoxide gas, nitrogen dioxide gas, anhydrous sulfuric acid, fluorine gas, concentrated sulfuric acid, nitric acid and various peroxides can be used. As the acidic functional group, A nitro group, a nitro group, an amide group, an imide group, a sulfonic acid group, a sulfinic acid group, a sulfinic acid group, a thiocarboxylic acid group, a chlorosilane group, a thiocarboxylic acid group, , Chloryl group, perchloryl group, iodo group, iodo group and the like.

The dye used in the dye-coated carbon black of the present invention is not particularly limited as long as it can be adsorbed on the surface of carbon black, and alkaline dyes, acid dyes, direct dyes, reactive dyes and the like can be used, The anionic or nonionic dyes can be more preferably used because they interact with functional groups on the giga-carbon black, react with amino groups and alkali-soluble resins, and can be insolubilized with sulfuric acid bands and the like. In order to further enhance the light shielding property of the black matrix to be obtained, it is preferable to use a dye of a dark color series close to black which has high light absorptivity. Specific examples of such dyes include food coloring dyes such as Food Black No. 1, Food Black No. 2, Food Red No. 40, Food Blue No. 1 and Food Yellow No. 7, Bernacid Red 2 BMN, Basacid Black X34 BASF X-34 (BASF X-34) (produced by Nippon Kayaku Company), Dermacarbon 2GT (manufactured by Sandoz), Telon Fast Yellow 4GL-175, BASF Basacid Black SE 0228, Acid dyes of various colors such as Basacid Blue 750 (BASF), Bernacid Red (Bemcolors, Poughkeepsie, NY) and BASF Basacid Black SE 0228 (BASF), Pontamine Brilliant Bond Blue A and other Pontamine Brilliant Bond Blue A and other Pontamine TM dyes (Bayer Chemicals Corporation, Pittsburgh, Pa.), Cartasol Yellow GTF Presscake (Sandoz, Inc); Cartasol Yellow GTF Liquid Special 110 (manufactured by Sandoz, Inc.); (Manufactured by Sandoz, Inc.), Sirius Supra Yellow GD 167, Cartasol Brilliant Yellow 4GF (manufactured by Sandoz), Pergasol Yellow CGP (Manufactured by Ciba-Geigy), Pyrazol Black BG (manufactured by JCI), Diazole Black RN Quad (manufactured by JCJ), Pontamine Brilliant Bond Blue; Cibacron Brilliant Red 3B-A (Reactive Red 4) (Aldrich Chemical, Milwaukee, WI), Drimarene Brilliant Red X-2B (Reactive Red 56) (Pylam Products, Inc. Tempe, (Trade name) manufactured by JCI America Inc.), Levafix Brilliant Red E-4B, Levafix Brilliant Red F-6BA and similar dyes of Levafix (registered trademark) dyes Dystar LP (Charlotte, NC), Procion Red H8B ), Neozapon Red 492 (BASF), Orasol Red G (Ciba-Geigy), Aizen Spilon RedC-BH (Hodogaya Chemical Company), Spirit Fast Yellow 3G, Aizen Spilon Yellow C-GNH (Manufactured by Hodogaya Chemical Company), Orasol Black RL (by Ciba-Geigy), Orasol Black RLP (by Ciba-Geigy), Savinyl Black RLS (by Sandoz), Orasol Blue GN (by Ciba-Geigy), Luxol Blue MBSN Thiokol), Morfast Black Concentrate A (manufactured by Morton-Thiokol), and the like. These may be used alone or in combination of two or more.

The content of the dye in the dye-coated carbon black used in the present invention is preferably 0.5 to 10% by mass, more preferably 1 to 7% by mass, and particularly preferably 1 to 5% by mass. If the content of the dye is less than the above lower limit, the coating becomes insufficient and a high resistance value can not be obtained. If the content exceeds the upper limit, the uncoated excess dye inhibits the dispersibility and tends to cause thickening and aggregation.

In the dye-coated carbon black used in the present invention, it is preferable that the dye is lacquered by a metal or a metal salt. By such laying, the dye is fixed to the surface of the carbon black or the acidic functional group with the metal or metal salt interposed therebetween, so that the dye is not easily separated from the surface of the carbon black, so that the dye is hardly eluted and high shielding property can be maintained . Examples of the metal or metal salt used for railing include aluminum, magnesium, calcium, strontium, barium or manganese or a hydrochloride or sulfate thereof, and these may be used alone or in combination of two or more. The amount of the metal or metal salt to be used for racing is preferably 0.3-fold or more, more preferably 0.5-fold or more, and particularly preferably 0.8-fold or more, based on the dye. If the addition amount of the metal or the metal salt is less than the above range, the fixation of the dye becomes insufficient and it tends to separate from the surface of the carbon black and the stability of the mill base deteriorates and the resistance value also deteriorates.

In addition, the carbon black dispersion for black matrix of the present invention may contain carbon black in addition to the above-mentioned dye-coated carbon black.

Next, the method for producing the dye-coated carbon black used in the present invention will be explained. First, the raw material carbon black is mixed with water (prepared by appropriately mixing ion-exchanged water in the tap water so that the electric conductivity is constantly adjusted, the same applies hereinafter) to obtain a slurry, which is heated and stirred for a predetermined time to clean the carbon black, Wash with water again. Next, water is added to the obtained carbon black to obtain a slurry again, the above-described oxidizing agent is added, and the mixture is stirred at a predetermined temperature for a predetermined time to oxidize and wash the surface of the carbon black. The oxidation treatment is carried out by changing the type of the oxidizing agent several times as necessary. The oxidation-treated carbon black thus obtained is mixed with water to obtain a slurry. The desired dye-coating carbon black is added to the above-mentioned predetermined amount of the dye, and the mixture is stirred at 40 to 90 DEG C for 1 to 5 hours to obtain a carbon black The dye is adsorbed on the surface. The same metal or metal salt as the added dye is added and stirred at 30 to 70 DEG C for 1 to 5 hours to dye the dye into a metal or metal salt to fix the dye on the surface of the carbon black. After cooling, it is washed with water, followed by filtration and drying to obtain a desired carbon black for dye coating.

The photocurable resin or thermosetting resin used in the carbon black dispersion for black matrix of the present invention is represented by the following general formula (I)

(2)

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ⁵ is a hydrogen atom or a methyl group, , -SO ₂ -, -C (CF ₃ ) ₂ -, -Si (CH ₃ ) ₂ -, -CH ₂ -, -C (CH ₃ ) ₂ -, -O-, 9,9- It denotes a straight bond, X is a tetravalent carboxylic acid moiety, Y ¹ and Y ² is a hydrogen atom or a -OC-Z- (COOH) _m (end, Z is a divalent or trivalent residue of carbon acid, each independently And m represents a number of 1 to 2), and n represents an integer of 1 to 20), wherein the epoxy (meth) acrylate acid part comprises water.

The epoxy (meth) acrylate acid addition product (I) used in the present invention is a product obtained by reacting a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols with (meth) acrylic acid with dicarboxylic acid or tricarboxylic acid or Can be obtained by reacting an aniline anhydride with a tetracarboxylic acid or an acid thereof.

Bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxyphenyl) (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis Dichlorophenyl) sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl ) Bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane, bis Bis (4-hydroxy-3,5-dibromophenyl) methane, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, Propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, Bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (9-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy- (4-hydroxy-3,5-dibromophenyl) fluorene, 9,9-bis (4-hydroxy- 4,4'-biphenol, 3,3'-biphenol, and derivatives thereof. Of these, those having a 9,9-fluorenyl group in the above general formula (I) are particularly preferably used.

The next step of obtaining water (I) of the epoxy (meth) acrylate acid part of the present invention is to react the above bisphenols with epichlorohydrin to obtain an epoxy compound having two glycidyl ether groups. In this reaction, oligomerization of the diglycidyl ether compound is generally accompanied by the following general formula (II)

(3)

≪ / RTI > Here, R ¹ , R ² , R ³ , R ⁴ and A in the general formula (II) have the same meanings as in the general formula (I) and l is an integer of 0 to 10. Preferred R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms, and preferred A is a 9,9-fluorenyl group. The average value of 1 is 0 to 3 (preferably, 0 to 3), although the average value of 1 is usually 0 to 10 (not limited to an integer) because a plurality of values are mixed. When the value of I exceeds the upper limit value, the viscosity of the composition becomes excessively large when the resin composition is used as the compound of the general formula (I), so that the application is not performed well or the alkali solubility can not be sufficiently provided.

(Meth) acrylic acid (acrylic acid or methacrylic acid or both) is reacted with a compound represented by the general formula (II), and the reaction product having a hydroxy group obtained is reacted with at least one of a dicarboxylic acid or a tricarboxylic acid and a tetracarboxylic acid The epoxy (meth) acrylate acid part is reacted to obtain water. Since the epoxy (meth) acrylate acid addition product (I) combines an ethylenically unsaturated double bond and a carboxyl group, it is possible to obtain a good black matrix by imparting excellent photo-curability, good developing property and patterning property to the alkali developing type photosensitive resin composition You can.

Examples of the dicarboxylic acids used in the epoxy (meth) acrylate acid part (I) of the present invention include chain (chain) hydrocarbon dicarboxylic acids, acid anhydrides thereof, alicyclic dicarboxylic acids or acid anhydrides thereof, aromatic dicarboxylic acids and their acids Anhydrides are used. Examples of the chain hydrocarbon dicarboxylic acid or its acid anhydride include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramelic acid, malonic acid, glutaric acid, citric acid, , Pimelic acid, sebacic acid, suberic acid, diglycolic acid, and the like, and further may be a dicarboxylic acid or an acid anhydride to which an arbitrary substituent has been introduced. Examples of the alicyclic dicarboxylic acid or its acid anhydride include compounds such as hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid and norbornanedicarboxylic acid, and further, Or an acid anhydride. Examples of the aromatic dicarboxylic acid or its acid anhydride include compounds such as phthalic acid and isophthalic acid, and further dicarboxylic acids or an acid anhydrides to which an arbitrary substituent has been introduced. In place of the dicarboxylic acids, tricarboxylic acids or their anhydrides may be used, and specific examples thereof include trimellitic acid or its acid anhydride.

The tetracarboxylic acids used in the epoxy (meth) acrylate acid part of the present invention as the water (I) include chain hydrocarbon tetracarboxylic acids, acid anhydrides thereof, alicyclic tetracarboxylic acids or acid anhydrides thereof, aromatic polycarboxylic acids or Acid dianhydrides are used. Examples of the chain type tetracarboxylic acid or its acid anhydride include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid and the like, and further tetracarboxylic acids into which a substituent is introduced or its acid anhydride may be used. Examples of the alicyclic tetracarboxylic acid or its acid anhydride include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid and cycloheptanetetracarboxylic acidboronanetetracarboxylic acid. Further, the substituent The introduced tetracarboxylic acids or their anhydrides may be used. Examples of the aromatic tetracarboxylic acid and its acid dianhydride include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, biphenyl ether tetracarboxylic acid or its acid dianhydride, and furthermore, Tetracarboxylic acids or their anhydrides.

The ratio of the (a) dicarboxylic acids and (b) tetracarboxylic acids used in the water (I) of the epoxy (meth) acrylate acid part of the present invention is preferably from 1:10 to 10 : 1, preferably 1: 5 to 1: 1. If the ratio of the use of the dicarboxylic acids and the tetracarboxylic acids in the epoxy (meth) acrylate acid part (I) is out of the above-mentioned range, the optimum molecular weight can not be obtained and the alkali developability, light transmittance, heat resistance, Shape or the like is deteriorated. In addition, the larger the ratio of the tetracarboxylic acids used, the greater the alkali solubility and the higher the molecular weight.

The epoxy (meth) acrylate acid addition product (I) used in the present invention preferably has a weight average molecular weight (Mw) of 2000 to 10,000, particularly preferably 3000 to 7000. If the weight average molecular weight (Mw) is less than 2000, the pattern adhesion can not be maintained at the time of development and pattern peeling occurs. If the weight average molecular weight (Mw) exceeds 10,000, adhesion to the glass substrate becomes excessively high, The residual film of the pattern portion is likely to remain. It is also preferable that the acid value of the epoxy (meth) acrylate acid part (I) is in the range of 30 to 200 KOHmg / g. If this value is less than 30 KOHmg / g, alkali development can not be performed properly or special development conditions such as strong alkali are required. If it exceeds 200 KOHmg / g, penetration of the alkaline developer is accelerated and peeling phenomenon occurs.

The epoxy (meth) acrylate acid addition product (I) used in the present invention can be produced by the above-described process by a known method, for example, the method described in Patent Document 1. [ As a method for reacting the epoxy compound of the general formula (II) with an unsaturated group-containing monocarboxylic acid, for example, an epoxy compound and an unsaturated group-containing monocarboxylic acid containing the corresponding moles are added in a solvent and a catalyst (triethylbenzylammonium chloride , 2,6-diisobutylphenol, etc.), and heating and stirring the mixture at 0 to 120 캜 while blowing air therein. Next, as a method of reacting the acid anhydride with the hydroxyl group of the epoxy acrylate compound as the reaction product, a predetermined amount of the epoxy acrylate compound, the acid dianhydride and the acid anhydride is added to the solvent and the catalyst (tetraethylammonium bromide, triphenylphosphine ) At 90 to 130 占 폚.

The content of the dye-coated carbon black in the carbon black dispersion for a black matrix of the present invention is 15 to 35% by mass, preferably 20 to 30% by mass. When the blending amount of the dye-coated carbon black is less than the above lower limit, the light shielding property becomes insufficient, and in order to obtain a preferable contrast, it is difficult to obtain the surface smoothness of the black matrix. When the blending amount of the dye-coated carbon black exceeds the upper limit, the dispersion stability of the carbon black dispersion is lowered, and the content of the photosensitive resin as the original binder is also decreased, so that good developing characteristics can not be obtained. I do not.

The amount of the epoxy (meth) acrylate acid addition product in the black matrix carbon black dispersion of the present invention is 2 to 20% by mass, preferably 5 to 15% by mass. If the blending amount of the epoxy (meth) acrylate acid part is less than the lower limit described above, the stability of the mill base deteriorates and the resistance value is lowered. If the upper limit is exceeded, the viscosity of the mill base becomes high and the applicability is poor and the smoothness is lowered I do not.

The carbon black dispersion for black matrix of the present invention may further contain, if necessary, carbon black other than the dye-coated carbon black, a light shielding material such as chromium oxide, iron oxide, titanium black, aniline black and cyanine black, (Meth) acrylate acid part other than the water (I) or a thermosetting resin other than the water (I), a coloring material such as a coloring material such as a black organic pigment or a mixture of two or more kinds of pigments to make a pseudo- A secondary or tertiary amino group, or a polymeric dispersant having an alkaline functional group such as a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine may be added.

Examples of the solvent used in the carbon black dispersion for black matrix of the present invention include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol and propylene glycol, terpenes such as alpha or beta terpineol, Ketones such as acetone, methyl ethyl ketone, cyclohexanone and N-methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, cellosolve, methylcellosolve, ethylcellosolve, Propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monomethyl ether, triethylene glycol monomethyl ether, triethylene glycol monomethyl ether, Glycol ethers such as monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve There may be mentioned the three Tate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol, alone or mixed solvents, such as monoethyl ethers, esters such as ethyl acetate.

The carbon black dispersion for a black matrix of the present invention is prepared by adding water (I) and other components to be added to an epoxy (meth) acrylate acid part in an optimal amount of a solvent, mixing and dissolving them, adding a dye- A ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, an ultrasonic wave, or the like, and dispersing the mixture in a single or a plurality of combinations after adding media such as beads and zirconia beads. Since the pigment component is microparticulated and stabilized by the dispersion treatment, the coating property of the resist composition is improved, which is advantageous for improving the light shielding ability of the black matrix and increasing the resistance when using a light-shielding material having conductivity such as carbon black .

The secondary particle diameter after dispersion is preferably adjusted so that the dispersed particle size of the carbon black is 50 to 200 nm, preferably 80 to 150 nm. Here, the dispersed particle size is, for example, an average particle diameter obtained by a known particle size measuring device of laser Doppler type. The viscosity of the dispersion is preferably adjusted to 3.0 to 100.0 mPa 占 퐏, preferably 3.0 to 20.0 mPa 占 퐏 at a liquid temperature of 25 占 폚 of the dispersion liquid as obtained by a known cone plate type clay system.

The carbon black dispersion for a black matrix of the present invention may contain a known photo-curing resin, a thermosetting resin, a photopolymerizable monomer, a photopolymerization initiator and a solvent, and optionally a curing accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, An additive such as a surfactant different from that used for the dispersing agent may be mixed and used as a resist composition for a black matrix of a color filter or the like.

Next, the carbon black dispersion for black matrix of the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[Referential Example 1]

Preparation of dye-coated carbon black (1)

1000 g of carbon black (TPX-1099, manufactured by Cabot) was mixed with water to prepare 10 L of a slurry. The mixture was stirred at 95 캜 for 1 hour for cooling, and then washed with water. This was mixed with water again to prepare 10 L of a slurry, 42.9 g of 70% nitric acid was added, and the mixture was stirred at 40 캜 for 4 hours. This was washed with water and then washed again with water to prepare 10 L of a slurry. 769.2 g of a 13% sodium hypochlorite aqueous solution was added and stirred at 40 ° C for 6 hours. This was washed with water, washed with water and then mixed with water to prepare 10 L of a slurry. 38.1 g of dyestuff (Direct Deep BLACK) having a purity of 38.4% was added and stirred at 40 캜 for 1 hour. C < / RTI > for 1 hour. This was allowed to cool, washed with water, and then filtered and dried to obtain carbon black for dye coating.

The amount of carboxyl groups (amount)  Measure

The amount of the acidic functional group (carboxyl group amount) of the obtained dye-coated carbon black was measured according to the method described in Japanese Patent Application Laid-Open No. 2000-248197 as follows.

10 g of dye-coated carbon black was weighed and reacted by shaking in 50 ml of 0.1 N sodium bicarbonate aqueous solution for 1 hour, filtered, and 20 ml of the supernatant of the filtrate was collected and titrated with 0.01 N aqueous hydrochloric acid solution. The amount of the carboxyl group was determined according to the following equation with the millimolar amount (mmol / g) in 1 g of carbon black.

  Amount of carboxyl group = (50/20 x 0.01 x (volume-empty volume)) / carbon black Sample mass

The amount of the carboxyl group of the obtained dye-coated carbon black was 53.9 mmol / g.

[Reference Example 2]

dyes Uncoated  Preparation of carbon black

Dye-coated carbon black was obtained in substantially the same manner as in Reference Example 1, except that the dye coating and the rake treatment with aluminum sulfate were not carried out.

[Referential Example 3]

Preparation of resin-coated carbon black

Cyclohexanone was added to polyvinyl chloride (NISSAN Vinyl E-430 manufactured by Nissan Chemical Industries, Ltd.) and dissolved by heating at about 90 ° C to prepare a cyclohexanone solution containing 10 wt% of polyvinyl chloride. On the other hand, water and carbon black (manufactured by Mitsubishi Chemical Corporation, manufactured by Mitsubishi Chemical Corporation) were mixed and vigorously stirred to prepare a uniform suspension containing 6% by weight of carbon black. Next, the suspension was added to the cyclohexanone solution with stirring to allow the carbon black in the water phase to pass through the solvent phase. Subsequently, the water separated from the carbon black was removed by decantation, and the mixture was kneaded for about 5 minutes with a roll mill having two rolls heated to 80 to 120 캜 to obtain a resin composition. Next, the resin composition was cut into a sheet form by a heating roll, passed through a roll mill having two rolls at room temperature and crushed to a size of about 30 mm or less, transferred into water and stirred for about 3 minutes at a speed of about 3000 rpm, (Granular) having a particle diameter of 0.1 to 3 mm. The sized product was dried at 80 to 150 캜 to obtain a resin-coated carbon black.

≪ Example 1 >

The carbon black of the present invention Dispersion  pharmacy

600 g of the dye-coated carbon black obtained in Referential Example 1, 93.2 g of a urethane-based dispersant BYK-167 (manufactured by Big-Chem Japan Co., Ltd.) and a propylene glycol monomethyl ether acetate solution of an epoxy acrylate acid having a fluorene skeleton = 56.5 mass%, "V259ME" manufactured by Shin-Etsu Chemical Co., Ltd.) and 1328.8 g of a solvent propylene glycol monomethyl ether acetate were dispersed with a bead mill to obtain a carbon black dispersion of the present invention.

[Comparative Example 1]

Comparative carbon black Dispersant  1 (Dye Uncoated  Carbon black) was prepared

Comparative carbon black dispersion 1 was obtained in substantially the same manner as in Example 1 except that the dye-uncoated carbon black obtained in Reference Example 2 was used in place of the dye-coated carbon black.

[Comparative Example 2]

Comparative carbon black Dispersant  2 (using resin-coated carbon black)

Comparative carbon black dispersion 2 was obtained in substantially the same manner as in Example 1 except that the resin-coated carbon black obtained in Reference Example 3 was used in place of the dye-coated carbon black.

[Comparative Example 3]

Comparative carbon black Dispersant  3 (without dispersion resin)

Fluorene skeleton was changed to 1706.8 g of solvent propylene glycol monomethyl ether acetate without adding a propylene glycol monomethyl ether acetate solution of water to obtain a comparative carbon black dispersion 3.

[evaluation]

For Black Matrix Resist  Preparation of composition

The carbon black dispersions of the present invention obtained in Example 1 and the comparative carbon black dispersions 1 to 3 obtained in Comparative Examples 1 to 3 were uniformly mixed with the respective mixing ingredients shown in Table 1 to prepare resist compositions 1 to 4 . The following ingredients were used in the formulation.

(Resin solid content concentration = 56.5 mass%, "V259ME" manufactured by Shin-Etsu Chemical Co., Ltd.) solution of epoxy acrylate acid part having water: fluorene skeleton of epoxy (meth) acrylate acid part was dissolved in propylene glycol monomethyl ether acetate solution

Monomer: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (" KAYARAD-DPHA "

Photopolymerization initiator 1: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime) ("Irgacure OXE02" )

Silane coupling agent: 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.)

Surfactant: Megafac F475 (manufactured by DIC)

Solvent 1: Propylene glycol monomethyl ether acetate

Solvent 2: Cyclohexanone

[Table 1]

Development Characteristic (Pattern Line width ·pattern Linearity · Resolution)

Each resist composition obtained above was coated on a glass substrate (Corning 1737) of 125 mm x 125 mm using a spin coater so as to have a film thickness of 1.0 mu m after post-baking and prebaked at 90 DEG C for 1 minute. Then, the exposure gap was adjusted to 100 탆, and line / space = 2 탆 / 2 탆, 4 탆 / 4 탆, 5 탆 / 5 탆, 6 탆 / 6 탆, 8 탆 / 8 탆, 10 탆 / A negative type photomask of 10 mu m and 20 mu m / 20 mu m was coated and irradiated with ultraviolet light of 80 mJ / cm < 2 > with an ultrahigh pressure mercury lamp of 30 mW / cm < 2 > Next, the exposed board is exposed to a pressure of 5 kgf / cm 2 after development of +10 seconds from +20 seconds of development time (break time = BT) at which a pattern starts to appear in a 0.08% potassium hydroxide aqueous solution at 25 ° C with a shower developing pressure of 1 kgf / To remove the unexposed portion of the coating film to form a pixel pattern on the glass substrate. Thereafter, the resist film was baked at 230 占 폚 for 30 minutes using a hot-air drier to form a line width , Pattern linearity and resolution were evaluated. The results are shown in Table 2. In addition, each evaluation method is as follows.

Pattern line width: A pattern line width of a mask width of 10 mu m was measured using a length measuring microscope ("XD-20" manufactured by Nikon Corporation).

Pattern Linearity: A 10 占 퐉 mask pattern after post-baking was observed under a microscope to find that notches on the substrate or notches of the pattern edge portion were not recognized.

Resolution: The minimum pattern size remaining on the substrate in the mask patterns of 2 탆, 4 탆, 5 탆, 6 탆, 8 탆, 10 탆 and 20 탆 was set as the resolution.

[Table 2]

OD Evaluation of

Each resist composition obtained above was coated on a glass substrate (Corning 1737) of 125 mm x 125 mm using a spin coater so as to have a film thickness of 1.0 mu m after post-baking and prebaked at 90 DEG C for 1 minute. Thereafter, a negative-type photomask having an opening of 15 mm x 15 mm was placed on the dried coating film adjusted to an exposure gap of 100 mu m, and ultraviolet rays of 80 mJ / cm < 2 > A photo-curing reaction was carried out. Next, the exposed plate was subjected to spraying at a pressure of 5 kgf / cm 2 after development of + 20 seconds from the development time (break time = BT) at which the pattern starts to appear at 25 ° C. in a 0.08% potassium hydroxide aqueous solution at a shower developing pressure of 1 kgf / And the pixel pattern was formed on the glass substrate. Thereafter, the substrate was subjected to thermal post-baking at 230 DEG C for 30 minutes using a hot-air drier. Then, the OD of the pixel formed in the opening of 15 mm x 15 mm was passed through Markbeth Using a densitometer. The results are shown in Table 3.

Surface resistance evaluation

Each resist composition obtained above was coated on a glass substrate (Corning 1737) of 125 mm x 125 mm using a spin coater so as to have a film thickness of 1.0 mu m after post-baking and prebaked at 90 DEG C for 1 minute. Thereafter, an ultraviolet ray of 80 mJ / cm 2 was irradiated by an ultrahigh-pressure mercury lamp of 30 mW / cm 2 for i-line illumination without a mask to perform photo-curing reaction. Next, the exposed plate was subjected to a shower developing pressure of 1 kgf / cm 2 in a 0.08% potassium hydroxide aqueous solution at 25 ° C, and after a development time (break time = BT) at which a pattern starts to appear when the photomask was put on, / Cm < 2 > pressure was subjected to thermal post-baking at 230 DEG C for 30 minutes and 180 minutes using a hot air drier, and the surface resistance was measured. The results are shown in Table 3.

Evaluation of adhesion to glass substrate

Each resist composition obtained above was coated on a glass substrate (Corning 1737) of 125 mm x 125 mm using a spin coater so as to have a film thickness of 1.0 mu m after post-baking and prebaked at 90 DEG C for 1 minute. Thereafter, the i-line illumination was subjected to beta exposure with an ultrahigh pressure mercury lamp of 30 mW / cm < 2 > at 80 mJ / cm < 2 > without using a negative type photomask and thermal postbaking was performed using a hot air drier at 230 DEG C for 30 minutes. The post-baked substrate obtained above was evaluated for adhesion strength to a glass substrate by the following evaluation method in accordance with the three-point bending adhesion test method of JIS K6856-1994. Each of the post-baked substrate and the glass substrate (Corning 1737) not coated with the resist composition was cut into a rectangular shape of 20 mm x 63 mm to prepare a test piece. The post-baked coating plate and the glass substrate to which the resin composition was not applied were fed through a certain amount of a sealant epoxy adhesive (" Stick Bond XN-21s ", Mitsui Chemicals) The substrate (test piece) was fused. When this polymerization was carried out, the shape of the sealing agent epoxy adhesive was circular and had a diameter of about 5 mm. Thereafter, the polymerized test pieces were subjected to prebaking at 90 DEG C for 20 minutes and postbaking at 150 DEG C for 2 hours, respectively, to prepare three-point bending test pieces. Further, a sample for comparison test in which uncoated glass pieces of 20 mm x 63 mm were adhered in the same manner as described above was also prepared. The coated plate and the counter substrate (uncoated substrate) or the uncoated glass substrate for comparative test were supported with two points of support (the length of the two points of the support was 3 cm) so that the polymerization site was the center in the test piece obtained above, The weight was added at a rate of 1 mm / min using UCT-100 manufactured by Orientec Co., Ltd., and the observation of the release surface and the weight at that time were read out and divided by the application area of the sealing agent epoxy adhesive The weight per unit area was taken as the adhesion strength. Further, PCT (pressure cooker test) was performed under the conditions of 121 캜, 100% RH, 2 atm and 5 hours, and then the same adhesion strength test was carried out to evaluate the adhesion strength before and after PCT. The adhesion strength of each composition when the adhesion strength of the glass before and after the PCT was 100 was taken as a relative value. Before and after the PCT, a value of 70 or more was evaluated as?, And a value of less than 70 was evaluated as?. The results are shown in Table 3.

[Table 3]

As can be seen from Tables 2 and 3, the resist composition 1 using the carbon black dispersion of the present invention had a pattern line width, a pattern straight line And exhibited an excellent performance in terms of surface resistance and adhesion strength to a glass substrate. In addition, the resist composition 1 using the carbon black dispersion of the present invention is superior in both the pattern line width, the pattern linearity, and the resolution developing property as compared with the resist composition 3 using the comparative carbon black dispersion 2 (using resin-coated carbon black) Exhibited excellent performance and had excellent adhesion strength to a glass substrate. Moreover, it had excellent resolution and excellent surface resistance as compared with the resist composition 4 using the comparative carbon black dispersion 3 (no dispersion resin).

≪ Industrial applicability >

As described above, the carbon black dispersion for a black matrix of the present invention can form a fine line pattern having high resistance and excellent in developing properties and adhesion to a glass substrate when used in a resist composition for a black matrix. When applied to a color filter, And a black matrix with high reliability and high reliability can be produced. Therefore, it is extremely useful when it is used in a color filter having a black matrix, a television monitor, a video monitor, a computer display, or the like, which is used for various multicolor display devices such as a color liquid crystal display device, a color facsimile, It is extremely useful for high-precision displays.

Claims (10)

1. A carbon black dispersion for black matrix obtained by dispersing carbon black, a photo-curable resin or a thermosetting resin in a solvent,
Wherein the carbon black comprises a dye-coated carbon black whose surface is coated with a dye,
The photocurable resin or the thermosetting resin is obtained by reacting a reaction product of an epoxy compound having two glycidyl ether groups derived from a bisphenol and (meth) acrylic acid with (a) a dicarboxylic acid, a tricarboxylic acid or its anhydride and (b) (I), which is obtained by reacting tetracarboxylic acid or its acid dianhydride so that the molar ratio of (a) to (b) is 1: 10 to 10:
[Chemical Formula 1]

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ⁵ is a hydrogen atom or a methyl group, , -SO ₂ -, -C (CF ₃ ) ₂ -, -Si (CH ₃ ) ₂ -, -CH ₂ -, -C (CH ₃ ) ₂ -, -O-, 9,9- It denotes a straight bond, X is a tetravalent carboxylic acid moiety, Y ¹ and Y ² is a hydrogen atom or a -OC-Z- (COOH) _m (end, Z is a divalent or trivalent residue of carbon acid, each independently And m represents a number of from 1 to 2, and n represents an integer of 1 to 20), wherein the epoxy (meth) acrylate acid part is water. The carbon black dispersion for a black matrix according to claim 1, wherein the dye-coated carbon black has a content of the dye of 0.5 to 10 mass%. The carbon black dispersion for a black matrix according to claim 1 or 2, wherein the dye-coated carbon black is an anionic or nonionic dye. 4. The carbon black dispersion for a black matrix according to any one of claims 1 to 3, wherein the dye-coated carbon black is a dye of a dark color series. The carbon black dispersion according to any one of claims 1 to 4, wherein the dye-coated carbon black has been dyeed with a metal or a metal salt. The carbon black dispersion according to claim 5, wherein the metal or metal salt is aluminum, magnesium, calcium, strontium, barium or manganese or a salt thereof. The carbon black dispersion for a black matrix according to any one of claims 1 to 6, wherein the dye-coated carbon black is obtained by using carbon black having at least one acidic functional group on its surface. [Claim 7] The method according to claim 7, wherein the acidic functional group is selected from the group consisting of hydroxyl group, oxo group, hydroperoxy group, carbonyl group, carboxyl group, peroxycarboxylic acid group, aldehyde group, ketone group, nitro group, nitroso group, amide group, A carbon black dispersion for a black matrix, which is a sulfinic acid group, a sulfinic acid group, a thiocarboxylic acid group, a chlorosilyl group, a chloryl group, a perchloryl group, an iodosyl group or a iodoyl group. The carbon black dispersion for a black matrix according to any one of claims 1 to 8, wherein the blending amount of the dye-coated carbon black is 15 to 35 mass%. The carbon black dispersion for a black matrix according to any one of claims 1 to 9, wherein the blending amount of the epoxy (meth) acrylate acid part and water is 2 to 20 mass%.