TWI585527B - A photosensitive composition for black matrix and a method for producing the same - Google Patents

Description

Photosensitive resin composition for black matrix and method of producing the same

The present invention relates to a photosensitive resin composition for a black matrix of a color filter which is suitable for forming a black matrix having a high light-shielding and high-resistance thin-line pattern and which is excellent in stability, and a method for producing the same.

In recent years, color liquid crystal display devices have been used in all fields such as liquid crystal televisions, liquid crystal monitors, and color liquid crystal mobile phones. The color filter is one of the important components for the visibility of the left and right color liquid crystal display devices. In order to improve the visibility, that is, a sharp image, the black matrix of the color filter must be further highly shielded and become It is necessary to add a light-shielding material such as a pigment which is larger than the conventional one to the photosensitive resin composition.

However, when the content of the light-shielding material such as a pigment is increased, when the color filter is formed, in the black resist film, the light in the ultraviolet region hardly reaches the deep portion of the coating film, and the hardening property in the photocurable composition is poor. There is a problem that the pattern is poorly attached or the pattern is peeled off during development, and the sharpness of the edge shape is lowered.

Therefore, in order to prevent hardening defects even when a light-shielding material such as a pigment having a high concentration is contained, a high-sensitivity photopolymerization initiator or a high degree of polymerization is used. In the present technology, the photopolymerization initiator or the acrylic monomer has reached a limit in high sensitivity, and it is not available in the high concentration range of the light-shielding material such as a pigment. The pattern is formed with sufficient sensitivity or adhesion to the glass substrate and storage stability of the photosensitive resin composition.

Therefore, the present inventors previously proposed as an alkali-soluble resin used for pigment dispersion, using a specific epoxy (meth) acrylate acid adduct, and using a color filter of a pigment dispersion which is co-dispersed with a dispersant. A photosensitive resin composition for a light sheet (refer patent document 1). In the range of a light-shielding material containing a high-concentration pigment such as a black matrix which is highly shielded by a black matrix, the photosensitive resin composition has high sensitivity and high adhesion to a glass substrate, and a photosensitive resin composition can be obtained. Excellent preservation stability.

However, in order to become a brighter and brighter color filter, the black matrix is further thinned, and the required characteristic of the increase in the degree of opacity is becoming more and more advanced, and the black matrix must be made larger than the conventional one due to the display mode of the liquid crystal. Higher resistance. In order to achieve such a high level of high light-shielding and high electric resistance, when the amount of the light-shielding material such as a desired pigment is added, the image-forming adhesion of a fine line pattern of 10 μm or less cannot be sufficiently ensured, and color filter is assembled on the liquid crystal panel. At the time of the sheet, there is also a problem that it is difficult to maintain high adhesion to the glass substrate by the sealant.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] JP-A-2008-9401

As described above, it is difficult to obtain a photosensitive resin composition for a black matrix of a fine line pattern for forming a high light-shielding and high-resistance type. For example, when a large amount of carbon black is added for light-shielding, a fine line pattern of 10 μm or less is not sufficiently obtained. The adhesion to the glass substrate is also difficult to achieve high resistance. Conversely, if the adhesion or resistance of the thin line pattern is required to be the required level, sufficient shading cannot be obtained without increasing the thickness of the coating film. Sex, but not applicable to the design of color filters, it is strongly required to solve these problems.

The present invention has been made in view of the above problems, and an object of the invention is to provide a photosensitive resin composition for a black matrix and a method for producing the same, which are formed in the photosensitive resin composition while maintaining high light shielding and high electrical resistance. In the case of the thin line pattern, the image-adhesiveness is sufficiently ensured, and the adhesion to the glass substrate is also excellent, and the storage stability is also excellent.

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

(1) The present invention relates to a method for producing a photosensitive resin composition for a color filter black matrix, which is characterized in that (A) a pigment dispersion having the following components (A1) to (A4) is prepared in advance ( A1) A dye-coated dye coated with carbon black, (A2) dispersant, (A3) an alkali-soluble resin having an unsaturated group having a structure of the following formula (I), (A4) a solvent, which will contain The component (B) to (E) as a component of the essential component is mixed with the pigment dispersion (A), (B) an alkali-soluble resin containing an unsaturated group, and (C) light having an ethylenically unsaturated bond. Polymerizable monomer, (D) photopolymerization initiator, (E) solvent, [Formula (I) is a reaction of an epoxy compound having 2 epoxidopropyl ether groups derived from bisphenols with (meth)acrylic acid to give (a) a dicarboxylic acid or a tricarboxylic acid or Ethylene (A) and (b) a tetracarboxylic acid or an acid dianhydride thereof obtained by reacting a molar ratio of (a) to (b) of 1:10 to 10:1. An acrylate acid adduct; wherein, in the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ₅ Represents a hydrogen atom or a methyl group, and A represents -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, 9,9-fluorenyl or a straight bond, X represents a tetravalent carboxylic acid residue, and Y ₁ and Y ₂ each independently represent a hydrogen atom or -OC-Z-(COOH) _m (only, Z represents 2 A valence or a trivalent carboxylic acid residue, m represents a number from 1 to 2, and n represents an integer from 1 to 20].

(2) Further, the present invention relates to a photosensitive resin composition for a color filter black matrix, characterized in that a (A) pigment dispersion having a composition (A1) to (A4) described below is prepared in advance The component (B) to (E) is mixed as a component, and (A1) the dye coated with the dye is coated with carbon black, and the (A2) dispersant (A3) has the following An alkali-soluble resin containing an unsaturated group in the structure of the formula (I), (A4) a solvent, (B) an alkali-soluble resin containing an unsaturated group, and (C) a photopolymerizable monomer having an ethylenically unsaturated bond, ( D) photopolymerization initiator, (E) solvent, [Formula (I) is a reaction of an epoxy compound having 2 epoxidopropyl ether groups derived from bisphenols with (meth)acrylic acid to give (a) a dicarboxylic acid or a tricarboxylic acid or Ethylene (A) and (b) a tetracarboxylic acid or an acid dianhydride thereof obtained by reacting a molar ratio of (a) to (b) of 1:10 to 10:1. An acrylate acid adduct; wherein, in the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ₅ Represents a hydrogen atom or a methyl group, and A represents -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, 9,9-fluorenyl or a straight bond, X represents a tetravalent carboxylic acid residue, and Y ₁ and Y ₂ each independently represent a hydrogen atom or -OC-Z-(COOH) _m (only, Z represents 2 A valence or a trivalent carboxylic acid residue, m represents a number from 1 to 2, and n represents an integer from 1 to 20].

(3) The photosensitive resin composition for a color filter black matrix according to (2), wherein the content of the dye-coated carbon black-based dye (A1) is 0.5 to 10% by mass.

(4) The photosensitive resin composition for a color filter black matrix according to (2) or (3), wherein the dye-coated carbon black dye is an anionic or nonionic dye.

(5) The photosensitive resin composition for a color filter black matrix according to any one of (2) to (4), wherein the dye-coated carbon black dye is a dye of a rich color system.

(6) The photosensitive resin composition for a color filter black matrix according to any one of (2) to (5) wherein the dye-coated carbon black dye is colored by a metal or a metal salt. Deposition.

(7) The photosensitive resin composition for a color filter black matrix according to (6), wherein the metal or metal salt is aluminum or magnesium. Calcium, barium, strontium or manganese or a salt of these.

(8) The photosensitive resin composition for a color filter black matrix according to any one of (2) to (7), wherein the dye-coated carbon black type has at least one type on the surface. The carbon black of the acidic functional group is obtained.

(9) The photosensitive resin composition for a color filter black matrix according to any one of (2) to (8) wherein the acidic functional group is a hydroxyl group, a pendant oxy group, or a hydroperoxy group. Base, carbonyl, carboxyl, peroxycarboxylic acid, aldehyde, keto, nitro, nitroso, decyl, quinone, sulfonate, sulfinate, sulfenate, thio A carboxylic acid group, a chlorooxy group, a dichlorooxy group, a perchlorooxy group, an iodooxy group or an iodonium group.

(10) The photosensitive resin composition for a color filter black matrix according to any one of (2) to (9), wherein (A3) an alkali-soluble resin containing an unsaturated group is blended The amount is 2 to 20% by mass.

(11) The photosensitive resin composition for a color filter black matrix according to any one of (2) to (10), wherein the (A1) dye in the solid content of the photosensitive resin composition The blending amount of the coated carbon black is 45 to 60% by mass.

(12) The photosensitive resin composition for a color filter black matrix according to any one of (2) to (11), wherein at least a part of the component (B) is the above formula (I) The basic resin containing an unsaturated group is shown.

(13) Further, in the present invention, the color filter black matrix of (2) to (12) is cured by a photosensitive resin composition.

(14) Further, the present invention is a black matrix which will be as (2)~(12) The black matrix described above is coated with a photosensitive resin composition, and after film formation, the selected position is photocured and developed by an alkali developing solution.

(15) Further, the present invention is a color filter formed by forming a black matrix as described in (14).

The photosensitive resin composition for a black matrix of the present invention is obtained by coating a carbon black containing a dye coated with a dye on a surface with a specific epoxy (meth) acrylate acid adduct. The photosensitive resin composition for a black matrix which is characteristic of the manufacturer is excellent in storage stability and excellent in coating film coating property and developing property, so that it has high light-shielding and high electrical resistance, and is formed into a fine line pattern excellent in adhesion to a glass substrate. This is possible, and if it is used in a color filter, it can be made into a black matrix with high light-shielding property and high resistance and high reliability.

[Formation of the Invention]

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

In the photosensitive resin composition for a black matrix of the present invention, (A) a pigment dispersion is first prepared, and the constituent components thereof are (A1) dye-coated carbon black, (A2) dispersant, and (A3) having the formula (I). The structure contains an alkali-soluble resin containing an unsaturated group and (A4) a solvent.

The type of the raw material carbon black used for the dye-coated carbon black of the present invention is not particularly limited, and lamp black, acetylene black, hot carbon black, channel black, furnace can be used. Known carbon black such as black.

Further, the average primary particle diameter of the raw material carbon black is preferably from 5 to 60 nm, more preferably from 10 to 50 nm, particularly preferably from 20 to 45 nm. Here, the average primary particle diameter refers to an average of the primary particle diameters obtained by observing 1500 primary carbon black particles by an electron microscope. When the average primary particle diameter of the raw material carbon black does not reach the above lower limit, aggregation tends to occur, and the stability of the polishing base material is deteriorated, and dispersion at a high concentration becomes difficult. On the other hand, when the upper limit is exceeded, the black matrix is likely to be in a shape defect. Because the surface roughness is also poor, it is not suitable.

Further, the raw material carbon black-based DBP absorption amount is preferably 100 ml/100 g or less. Here, the amount of DBP absorption refers to the capacity of dibutyl phthalate (DBP) absorbed by 100 g of carbon black, and is measured in accordance with the method described in JIS K6217-4. When the DBP absorption amount of the raw material carbon black exceeds the above upper limit, the electric resistance value decreases, and the viscosity is high, the coatability is deteriorated, and the blackness is lowered.

Further, the raw material carbon black has a pH of preferably 2 to 10, more preferably 5 to 9, and particularly preferably 4 to 8. Here, the pH value is a value of a mixture of carbon black and distilled water measured by a glass electrode pH meter, and is measured in accordance with the method of JIS K6221-1982. When the pH of the raw material carbon black does not reach the above lower limit, the entire balance collapses, and the dispersion stability deteriorates. If the upper limit is exceeded, the film peeling is likely to occur, which is not preferable.

Further, the raw material carbon black is preferably one having a ash content of 1.0% or less and a specific surface area of 20 to 300 m ² /g. The ash system was measured in accordance with the method described in JIS K6218-2, and the specific surface area was measured in accordance with the C method described in JIS K6217-2. When the ash content exceeds the above upper limit, the resistance value is lowered, and if the specific surface area is less than the lower limit, the shape of the black matrix is likely to be poor. When the ash content exceeds the upper limit, a large amount of dispersant, resin, dye, or the like is required. Not suitable.

Further, the raw material carbon black is preferably subjected to an oxidation treatment in advance to have at least one type of acidic functional group on the surface, and more preferably a plurality of kinds of acidic functional groups are provided on the surface by applying a plurality of types of oxidation treatment. When the oxidation treatment is not carried out in advance, since the number of the acidic functional groups or the acidic functional groups is not large on the surface, the carbon black is not sufficiently uniformly dispersed in the photosensitive resin composition, and the resistance value of the obtained black matrix is insufficient. reduce. Therefore, it is not preferable to cause conduction between the transparent electrode on the color filter and the black matrix or between the opposing electrodes to cause image failure.

The oxidation treatment includes ozone gas, nitric acid, sodium hypochlorite, hydrogen peroxide, nitrogen monoxide gas, nitrogen dioxide gas, anhydrous sulfuric acid, fluorine gas, concentrated sulfuric acid, nitric acid, various peroxides. Etc. Further, examples of the acidic functional group include a hydroxyl group, a pendant oxy group, a hydroperoxy group, a carbonyl group, a carboxyl group, a peroxycarboxylic acid group, an aldehyde group, a ketone group, a nitro group, a nitroso group, a decylamino group, and an anthracene group. An imido group, a sulfonic acid group, a sulfinic acid group, a sulfenic acid group, a thiocarboxylic acid group, a chlorooxy group, a dichlorooxy group, a perchlorooxy group, an iodooxy group, an iodonium group or 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 known basic dyes, acid dyes, direct dyes, reactive dyes, and the like can be used. But the sulfo or carboxyl group interacts with a functional group on the carbon black, and the amine group and the alkali are soluble. The resin reaction is more preferably an anionic or nonionic dye in view of insolubilization in aluminum sulfate or the like. Further, in order to further improve the light-shielding property of the obtained black matrix, it is preferred to use a dye of a rich color system having a high light absorptivity and a black color. Specific examples of such a dye include food color dyes such as Food Black No. 1, Food Black No. 2, Food Red No. 40, Food Blue No. 1, Food Yellow No. 7, and Bernacid Red 2BMN. Basacid Black X34 (BASFX-34) (manufactured by BASF Corporation), Kayanol Red 3BL (manufactured by Nippon Kayaku Company), Dermacarbon 2GT (manufactured by Sandoz Co., Ltd.), Telon Fast Yellow 4GL-175, BASF Basacid Black SE 0228, Basacid Black X34 ( Acid dyes of various colors such as BASF X-34) (manufactured by BASF Corporation), Basacid Blue 750 (manufactured by BASF Corporation), Bernacid Red (Bemcolors, Poughkeepsie, NY), BASF Basacid Black SE 0228 (manufactured by BASF Corporation), Pontamine Brilliant Bond Blue A and other Pontamine Brilliant Bond Blue A and other Pontamine (registered trademark) dyes (Bayer Chemicals Corporation, Pittsburgh, PA), Cartasol Yellow GTF Presscake (manufactured by Sandoz, Inc.); Cartasol Yellow GTF Liquid Special 110 (manufactured by Sandoz, Inc.); Yellow Shade 16948 (manufactured by Tricon), Direct Brilliant Pink B (manufactured by Crompton & Knowles), Carta Black 2GT (manufactured by Sandoz, Inc.), Sirius Supr a Yellow GD 167, Cartasol Brilliant Yellow 4GF (manufactured by Sandoz Co., Ltd.); Pergaso I Yellow CGP (manufactured by Ciba-Geigy Co., Ltd.), Pyrazol Black BG (manufactured by JCI), DiazoI Black RN Quad (manufactured by JCJ), Pontamine Brilliant Bond Blue; direct dyes of various colors such as Berncolor AY34, Cibacron Brilliant Red 3B-A (Reactive Red 4) (Aldrich Chemical, Milwaukee, WI), Drimarene Brilliant Red X-2B (Reactive Red 56) (Pyram Products, Inc. Tempe, manufactured by AZ), Levafix Brilliant Red E-4B, Levafix Brilliant Red F-6BA, and similar Levafix (registered trademark) dyes Dystar LP (manufactured by Charlotte, NC), Procion Red H8B (Reactive Red 31) (manufactured by JCI America Co., Ltd.) reactive dyes of various colors, Neozapon Red 492 (manufactured by BASF Corporation), Orasol Red G (manufactured by Ciba-Geigy Co., Ltd.), Aizen Spilon Red C-BH (Hodogaya Chemical Company) ), Spirit Fast Yellow 3G, Aizen Spilon Yellow C-GNH (manufactured by Hodogaya Chemical Company), Orasol Black RL (manufactured by Ciba-Geigy Co., Ltd.), Orasol Black RLP (manufactured by Ciba-Geigy Co., Ltd.), Savinyl Black RLS (Sandoz Co., Ltd.) An oil-soluble dye such as Orasol Blue GN (manufactured by Ciba-Geigy Co., Ltd.), Luxol Blue MBSN (manufactured by Morton-Thiokol Co., Ltd.), or Morfast Black Concentrate A (manufactured by Morton-Thiokol Co., Ltd.). These may be used singly or in combination of two or more.

Further, the content of the dye in the dye-coated carbon black used in the present invention is preferably from 0.5 to 10% by mass, more preferably from 1 to 7% by mass, particularly preferably from 1 to 5% by mass. When the content of the dye does not reach the above lower limit, the coating becomes insufficient, and a high electric resistance value is not obtained. When the content exceeds the above upper limit, the remaining dye is not inhibited from dispersing, and it is not preferable because it is likely to cause sticking and aggregation.

Furthermore, the dyes used in the present invention are coated with carbon black, preferably via gold. The genus or metal salt is used to lake the aforementioned dye. By the lamination, the dye is fixed to the surface of the carbon black or the acidic functional group by a metal or a metal salt, and since the dye becomes difficult to be detached from the surface of the carbon black, the dye is hardly eluted and the high hiding property can be maintained. Examples of the metal or metal salt used for the lake formation include a monomer of aluminum, magnesium, calcium, strontium, barium or manganese, or a hydrochloride or a sulfate thereof. These may be used alone or in combination of two or more. Use this to use. The amount of the metal or metal salt to be used for the lake is preferably 0.3 times or more, more preferably 0.5 times or more, and particularly preferably 0.8 times or more based on the dye. When the amount of the metal or metal salt added is less than the above, the fixing of the dye is insufficient, and the surface of the carbon black is easily removed. The stability of the polishing base is poor, and the electric resistance value is also lowered.

Next, a method for producing the dye-coated carbon black used in the present invention will be described. First, the carbon black of the raw material is mixed with water (the conductivity is adjusted to a certain extent, and the ion-exchanged water is appropriately mixed in tap water, and the same applies hereinafter) to form a slurry, and the mixture is heated and stirred for a predetermined time to wash the carbon black. After cooling, wash again. Next, water is added to the obtained carbon black to be a slurry again, and the above oxidizing agent is added thereto, and the mixture is stirred at a predetermined temperature for a predetermined time to oxidize the surface of the carbon black, followed by washing with water. The oxidation treatment is carried out as many times as necessary to change the type of the oxidizing agent. Subsequently, the obtained oxidized carbon black is mixed with water to be a slurry again, and the dye for the purpose is coated with carbon black, and the dye is added so as to have the specified content, and stirred at 40 to 90 ° C for 1 to 5 hours. Adsorbs and coats the dye on the surface of the carbon black. Further, adding the above-mentioned metal or metal salt such as the added dye, and stirring at 30 to 70 ° C for 1 to 5 hours, dyeing with metal or metal salt The material is desublimated and the dye is fixed to the surface of the carbon black. Then, this was cooled, washed with water, and dried by filtration to obtain a desired dye-coated carbon black.

The blending amount of the dye-coated carbon black in the (A) pigment dispersion of the present invention may be 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 is insufficient, and in order to obtain a desired contrast, it is necessary to increase the film thickness, and it is difficult to obtain the surface smoothness of the black matrix. In addition, when the blending amount of the dye-coated carbon black exceeds the above upper limit, the dispersion stability of the pigment dispersion is lowered, and the content of the photosensitive resin of the original binder is also reduced, and good development characteristics are not obtained. Not suitable.

Further, the (A) pigment dispersion of the present invention may contain, in addition to the dye-coated carbon black, carbon black which is usually or subjected to a specified treatment. Further, other pigments or light-shielding materials may be contained. As another pigment, for example, at least two kinds of pigments selected from black organic pigments such as sapphire or cyanine black, red, blue, green, purple, yellow, cyan, magenta, and the like can be used to simulate blackening. Mixed color organic pigments. Further, examples of the other light shielding material include chromium oxide, iron oxide, titanium black, aniline black, and cyanine black. The pigment or the light-shielding material other than the dye-coated carbon black may be used in combination of two or more kinds, or may be used in combination with each other.

The dispersing agent of the component (A2) of the present invention may have a function of allowing the dye-coated carbon black of the component (A1) or, if necessary, other pigments to be contained as a pigment dispersion and stably dispersing, for example, it can be used. A well-known dispersant such as various polymer dispersants. Specific examples of the polymer dispersant include, for example, a primary, secondary or tertiary amine group, a pyridine, a pyrimidine, and a pyridyl group. A polymer dispersant having a basic functional group such as a nitrogen-containing heterocyclic ring. The amount of the component (A2) is from 1 to 30% by mass, preferably from 2 to 25% by mass, based on the dye-treated CB.

The alkali-soluble resin containing an unsaturated group of the component (A3) of the present invention is of the following formula (I) Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ₅ represents a hydrogen atom or a methyl group, and A represents -CO. -, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, 9,9-fluorenyl or Direct bond, X represents a tetravalent carboxylic acid residue, and Y ₁ and Y ₂ each independently represent a hydrogen atom or -OC-Z-(COOH) _m (only, Z represents a divalent or trivalent carboxylic acid residue, m represents an epoxy (meth) acrylate acid adduct represented by the number of 1 to 2), and n represents an integer of 1 to 20.

The epoxy (meth) acrylate acid adduct of the formula (I) used in the present invention is an epoxy compound having two epoxypropyl ether groups derived from bisphenols and (methyl) The reaction of acrylic acid is obtained by reacting a dicarboxylic acid or a tricarboxylic acid or an acid monoanhydride of any of them with a tetracarboxylic acid or an acid dianhydride thereof.

Among them, examples of the bisphenol to which the epoxy (meth) acrylate acid addition product of the formula (I) of the present invention is administered include bis(4-hydroxyphenyl) ketone and bis(4-hydroxy-3). ,5-dimethylphenyl)one, bis(4-hydroxy-3,5-dichlorophenyl) ketone, bis(4-hydroxyphenyl)anthracene, bis(4-hydroxy-3,5-dimethyl Phenyl, bis(4-hydroxy-3,5-dichlorophenyl)fluorene, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl) Hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethyloxane, bis(4-hydroxy-3,5-dimethyl Phenyl) dimethyl decane, bis(4-hydroxy-3,5-dichlorophenyl)dimethyl decane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichloro Phenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5- Dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2, 2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl)ether, bis(4-hydroxy-3,5-dimethylphenyl)ether, bis(4-hydroxy-) 3,5-dichlorophenyl)ether, 9,9-bis(4-hydroxyphenyl) 9,9-bis(4-hydroxy-3-methylphenyl)indole, 9,9-bis(4-hydroxy-3-chlorophenyl)indole, 9,9-bis(4-hydroxy-3- Bromophenyl)anthracene, 9,9-bis(4-hydroxy-3-fluorophenyl)anthracene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene, 9,9- Bis(4-hydroxy-3,5-dichlorophenyl)anthracene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)anthracene, 4,4'-bisphenol, 3,3' - bisphenols and the like and derivatives thereof. Among these, it is particularly suitable to use a person having a 9,9-fluorene group.

Further, an epoxy compound having two epoxypropyl ether groups was obtained by using the above bisphenols and epichlorohydrin. In the case of this reaction, a compound of the following formula (II) is generally obtained by oligomerization of a diglycidyl ether compound. In the formula of the formula (II), R ₁ , R ₂ , R ₃ , R ₄ and A are as defined in the formula (I). 1 is an integer from 0 to 10. Desirable R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, and a preferred A is a 9,9-fluorenyl group. Further, since 1 is usually a mixture of plural values, the average value is 0 to 10 (not limited to an integer), and the average value of 1 is preferably 0 to 3. If the value of 1 exceeds the upper limit, When the compound of the compound I) forms a resin composition, the viscosity of the composition becomes too large, the coating cannot be smoothly performed, or the alkali solubility is not sufficiently provided, and the alkali developability is extremely poor.

Next, a compound of the formula (II) is reacted with acrylic acid or methacrylic acid or both, and a dicarboxylic acid (or tricarboxylic acid) and a tetracarboxylic acid of a polybasic acid are reacted with the obtained reactant having a hydroxyl group. At least one type of each reaction is reacted to obtain an epoxy (meth) acrylate acid adduct (I). The epoxy (meth) acrylate acid addition product (I) imparts excellent photocurability and good developability to an alkali-developing photosensitive resin composition by having an ethylenically unsaturated double bond and a carboxyl group. The patterning characteristics give a good black matrix.

As the dicarboxylic acid used in the epoxy (meth) acrylate acid addition product of the general formula (I) of the present invention, a chain hydrocarbon dicarboxylic acid or an anhydride thereof or an alicyclic dicarboxylic acid or an anhydride thereof is used. An aromatic dicarboxylic acid or an anhydride thereof. Here, as a chain a hydrocarbon dicarboxylic acid or an anhydride thereof, for example, succinic acid, acetyl succinic acid, maleic acid, adipic acid, itaconic acid, sebacic acid, citramalic acid, malonic acid, glutaric acid, citric acid A compound such as tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid or diglycolic acid, or a dicarboxylic acid or an anhydride thereof to which an arbitrary substituent is introduced. Further, examples of the alicyclic dicarboxylic acid or an acid anhydride thereof include compounds such as hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, and norbornanedicarboxylic acid, and the like. A dicarboxylic acid or an anhydride thereof having an arbitrary substituent is introduced. In addition, as the aromatic dicarboxylic acid or an acid anhydride thereof, for example, a compound such as phthalic acid or isophthalic acid may be used as a dicarboxylic acid or an anhydride thereof to which an arbitrary substituent is introduced. Further, a tricarboxylic acid may be used instead of the dicarboxylic acid, and examples thereof include trimellitic acid or an acid anhydride thereof.

Further, as the tetracarboxylic acid used in the epoxy (meth) acrylate acid addition product of the general formula (I) of the present invention, a chain hydrocarbon tetracarboxylic acid or an acid dianhydride or an alicyclic tetracarboxylic acid is used. Or an acid dianhydride thereof, or an aromatic polycarboxylic acid or an anhydride thereof. Here, the chain hydrocarbon tetracarboxylic acid or an acid anhydride thereof may, for example, be butane tetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid or the like, or may be a tetracarboxylic acid to which a substituent is introduced or Anhydride. Further, examples of the alicyclic tetracarboxylic acid or an acid anhydride thereof include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid norbornanetetracarboxylic acid, and the like. Further, it may be a tetracarboxylic acid or an anhydride thereof to which a substituent is introduced. Further, examples of the aromatic tetracarboxylic acid or an anhydride thereof include pyromellitic acid, diphenylketonetetracarboxylic acid, biphenyltetracarboxylic acid, biphenylethertetracarboxylic acid or an anhydride thereof. It may also be a tetracarboxylic acid or an anhydride thereof to which a substituent is introduced.

The ratio of use of (a) dicarboxylic acid to (b) tetracarboxylic acid used in the epoxy (meth) acrylate acid addition product of the formula (I) of the present invention is (a) and (b) The molar ratio is in the range of 1:10 to 10:1, preferably in the range of 1:5 to 1:1. When the ratio of use of the dicarboxylic acid and the tetracarboxylic acid in the epoxy (meth) acrylate acid addition product of the formula (I) is out of the above range, the most suitable molecular weight is not obtained, and alkali developability and light are exhibited. It is not preferable to deteriorate by permeability, heat resistance, solvent resistance, pattern shape, and the like. Further, the larger the use ratio of the tetracarboxylic acid, the larger the alkali solubility and the higher the molecular weight.

Further, the epoxy (meth) acrylate acid adduct of the formula (I) used in the present invention preferably has a weight average molecular weight (Mw) of from 2,000 to 10,000, particularly preferably from 3,000 to 7,000. . When the weight average molecular weight (Mw) is less than 2,000, the adhesion of the pattern at the time of development cannot be maintained, and pattern peeling occurs. When the weight average molecular weight (Mw) exceeds 10,000, the adhesion to the glass substrate is too high. The residual film in the residue or the pattern portion tends to remain. Further, the epoxy (meth) acrylate acid addition product of the formula (I) preferably has an acid value in the range of 30 to 200 KOH mg/g. If the value is 30 KOHmg/g, the alkali imaging cannot be performed smoothly, or a special development condition such as a strong alkali is required. If it exceeds 200 KOHmg/g, the penetration of the alkali developing solution becomes faster, and the image peeling occurs. Not suitable.

The epoxy (meth) acrylate acid addition product of the formula (I) used in the present invention is produced by a known method, for example, the method described in Patent Document 1, by the above procedure. First, as a method of reacting the epoxy compound of the formula (II) with an unsaturated group-containing monocarboxylic acid, for example, a solvent such as an epoxy group or an epoxy group such as an epoxy group may be added to the solvent. Carboxylate The acid is heated in the presence of a catalyst (triethylbenzylammonium chloride, 2,6-diisobutylphenol, etc.) while being heated to 90 to 120 ° C while stirring, and the reaction is carried out. Next, as a method of reacting a hydroxyl group of an epoxy acrylate compound of a reaction product with an acid anhydride, a specified amount of an epoxy acrylate compound, an acid anhydride, and an acid anhydride is added to a solvent, and the catalyst (tetraethyl bromide) A method in which the reaction is carried out by heating and stirring at 90 to 130 ° C in the presence of ammonium or triphenylphosphine.

Further, the amount of the epoxy (meth) acrylate acid adduct [(A3) component] in the (A) pigment dispersion of the present invention is 2 to 20% by mass, preferably 5 to 15% by mass. . When the amount of the epoxy (meth) acrylate acid adduct is less than the above lower limit, the stability of the polishing base is deteriorated, and the resistance value is lowered. If the above upper limit is exceeded, the viscosity of the polishing base is changed. It is high, the coating property is poor, and the smoothness is lowered.

Examples of the solvent (A4) of the present invention include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol, and terpenes such as α- or β-terpineol. Ketones such as alcohol, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, etc., cellosolve, methyl solution Fiber, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, Glycol ethers such as dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve Acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl A single or mixed solvent such as an acetate such as an ether acetate.

The (A) pigment dispersion system of the present invention is obtained by adding an epoxy (meth) acrylate acid addition product of the formula (I) and other components added as needed to an optimum amount of a solvent, mixing and dissolving, Adding dye-coated carbon black, adding a medium such as glass beads or zirconia beads, and then making a varnisher, a sand mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, an ultrasonic wave, etc. in separate or plural Combine and obtain a dispersion treatment. By the dispersion treatment, the dye-coated carbon black is micronized and dispersed, and the coating property of the photosensitive resin composition using the pigment dispersion can be improved, which contributes to an increase in the light-shielding ability of the black matrix and the use thereof. When the carbon black has a conductive light-shielding material, the resistance is increased.

(A) The average secondary particle diameter of the dye-coated carbon black after the dispersion treatment of the pigment dispersion is preferably 50 to 200 nm, more preferably 80 to 150 nm. The average secondary particle diameter as referred to herein is, for example, a value of an average particle diameter obtained by a well-known laser Doppler type particle size analyzer. Further, (A) the viscosity of the pigment dispersion is preferably adjusted to 3.0 to 100.0 mPa at a liquid temperature of 25 ° C when obtained by a well-known cone-and-plate type viscometer. s, better adjusted to 3.0~20.0mPa. s.

Next, as the (B) alkali-soluble resin containing an unsaturated group, an epoxy (meth) acrylate acid addition product of the formula (I) of the component (A3) can be suitably used. In addition, for example, instead of the epoxy compound derived from a bisphenol, a phenol novolak type epoxy compound or a cresol novolak type epoxy compound or the like may be used, and two or more epoxypropyl ether groups may be used. a compound that uses a derivative to form an unsaturated double bond having a photosensitive group and brings about alkali solubility An alkali-soluble resin containing an unsaturated group of a compound having an acidic functional group such as a carboxyl group. (B) The alkali-soluble resin containing an unsaturated group may be used singly or in combination of two or more kinds. For the photosensitive resin composition having high light-shielding and high electrical resistance, it is preferred to use the same components as the co-dispersion resin (A3) of the (A) pigment dispersion.

Examples of the photopolymerizable monomer having an ethylenically unsaturated bond as the component (C) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid. a (meth) acrylate having a hydroxyl group such as 2-ethylhexyl ester, or ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, or triethylene glycol di(a) Acrylate, tetraethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tris(A) Acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol (meth)acrylate, Modification of sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, or dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene (meth) acrylates such as hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate, etc., can be used One or two or more. Further, the photopolymerizable monomer having an ethylenically unsaturated bond is preferably one obtained by crosslinking molecules of an alkali-soluble resin containing an unsaturated group having three or more photopolymerizable groups. Further, the photopolymerizable single system having an ethylenically unsaturated bond of the component (C) does not have a free carboxyl group.

In the photosensitive resin composition of the present invention, the ratio of the unsaturated group-containing resin ((A3) + (B)) component to the component (C) (the amount of each component is a solid component other than the solvent) is The mass ratio ((A3) + (B)): (C) may be 20: 80 to 90: 10, preferably 40: 60 to 80: 20. When the blending ratio of the (A3)+(B) component is small, the cured product after photocuring becomes brittle, and the solubility in the alkali developing solution is lowered due to the low acid value of the coating film in the unexposed portion. There is a problem that the edges of the pattern are not aligned and become sharp. On the other hand, if the amount is large, the proportion of the photoreactive functional group in the resin is small, the formation of the crosslinked structure is insufficient, and the acid value of the resin component is too high, and the solubility of the exposed portion in the alkali developing solution is high. When it becomes higher, it may occur that the pattern formed is smaller than the line width of the target, or the pattern defect is likely to occur.

As the photopolymerization initiator of the component (D), one type or more of initiators can be used. Further, the photopolymerization initiator described in the present invention is used in the sense of containing a sensitizer.

Examples of the photopolymerization initiator which can be used include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, and dichloro Acetophenones such as acetophenone, trichloroacetophenone, p-t-butylacetophenone, diphenyl ketone, 2-chlorodiphenyl ketone, p,p'-bisdimethylamino group Diphenyl ketones such as diphenyl ketone, benzoin ethers such as benzoin, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2- (o-fluorophenyl)-4,5-diphenyldiimidazole, 2-(o-methoxyphenyl)-4,5-diphenyldiimidazole, 2,4,5-triaryl Bi-diimidazole compounds such as diimidazole, 2-trichloromethyl-5-styryl-1,3,4- Diazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4- Diazole, 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4- a halomethylthiazole compound such as oxadiazole, 2,4,6-tris(trichloromethyl)-1,3,5-three 2-methyl-4,6-bis(trichloromethyl)-1,3,5-three 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-three 2-(4-Methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-three Halomethyl-S-three Compounds, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(o-benzhydrylhydrazine), 1-(4-phenylmercaptophenyl) Butane-1,2-dione-2-indole-o-benzoate, 1-(4-methylnonylphenyl)butane-1,2-dione-2-indole-o-acetic acid O-mercapto oxime compounds such as esters, 1-(4-methylmercaptophenyl)butan-1-one oxime-o-acetate, benzyldimethylketal, thioxanthone, 2 a sulfur compound such as chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone or 2-isopropylthioxanthone, 2-ethylhydrazine, octamethylguanidine An organic peroxide such as 1,2-benzopyrene or 2,3-diphenylanthracene, azobisisobutyronitrile, benzammonium peroxide, cumene peroxide, etc. 2-mercaptobenzimidazole, 2-mercaptobenzoene a thiol compound such as azole or 2-mercaptobenzothiazole, a tertiary amine such as triethanolamine or triethylamine, or the like.

The amount of the photopolymerization initiator of the component (D) is based on 100 parts by mass of the total of the components of the (A3) and (B) unsaturated group-containing alkali-soluble resin and (C) photopolymerizable monomer. It can be 2 to 60 parts by mass, preferably It is 10 to 50 parts by mass. When the mixing ratio of the component (D) is small, the speed of photopolymerization is slow and the sensitivity is lowered. On the other hand, if the amount is too large, the sensitivity is too strong, and the pattern line width is thick to the pattern mask, which may not be correct. The mask reproduces the faithful line width, or the pattern edges are not aligned and become unsharp.

The solvent of the component (E) is applicable as long as it is a solvent exemplified as the component (A4), and may contain at least the same solvent as the component (A4). Further, two or more types of solvents may be used.

The essential component of the photosensitive resin composition for a black matrix of the present invention is the above (A) pigment dispersion, (B) an alkali-soluble resin containing an unsaturated group, and (C) a photopolymerizable single sheet having an ethylenically unsaturated bond. (D) photopolymerization initiator and (E) solvent, but may be blended with a hardening accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a leveling agent, an antifoaming agent, or a dispersing agent, as needed Additives such as surfactants. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butyl catechol, and thiophene Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of the filler include glass fiber, vermiculite, mica, alumina, and the like. Examples of the antifoaming agent or the leveling agent include a lanthanoid, fluorine-based, and acrylic-based compound.

The photosensitive resin composition of the present invention contains the components (A) to (E) as a main component, and the solid component contained in the monomer which is a solid component after being removed by curing, (A) to (D) The amount of the components other than the solvent of each component is 70% by mass or more, preferably 80% by mass, and more preferably 90% by mass or more. Although the amount of the solvent varies depending on the viscosity of the target, it is preferably in the range of 20 to 90% by mass. Solid component can be The solution of the photosensitive resin composition was heated at 160 ° C for 2 hr, and the solvent was removed and measured.

The content of the dye-coated carbon black of the component (A1) may be 40% by mass or more, preferably 45 to 60% by mass, more preferably 50%, based on the solid content of the photosensitive resin composition. ~55 mass% range. When the content of the component (A1) is low, the light-shielding property is insufficient, and in order to obtain a desired contrast, it is necessary to increase the film thickness, and it is difficult to obtain the smoothness of the surface of the black matrix. On the other hand, when the content of the component (A1) is high, not only the pigment dispersion of the component (A) but also the dispersion stability of the photosensitive resin composition is lowered, and the content of the photosensitive resin of the binder is also reduced. Adhesive adhesion or adhesion to a glass substrate is sufficiently imparted, or alkali solubility is insufficient, and good development characteristics are not obtained, which may cause such a problem.

The coating film of the present invention is obtained by applying a solution of the photosensitive resin composition for black photoresist to a substrate or the like, drying it, and irradiating light (including ultraviolet rays, radiation, or the like) to cure the film. When the light-irradiated portion and the unirradiated portion are provided, only the light-irradiated portion is hardened, and the other portion is dissolved in the alkali solution to obtain a coating film of a desired pattern.

Next, a method of producing a color filter using the photosensitive resin composition for black photoresist of the present invention will be described. First, a photosensitive resin composition for black photoresist is applied onto a substrate on the surface of the substrate to form a light shielding layer (black matrix) so as to partially separate the pixels. Next, on the substrate, for example, a liquid photosensitive resin composition (ink) in which a red pigment is dispersed is applied, and then pre-baked to evaporate the solvent to form a coating film. Subsequently, after the film is exposed through a photomask, an alkaline developing solution is used for image formation and dissolution. The unexposed portions of the coating film are removed, and then, by post-baking, a red pixel pattern is formed to arrange the array of pixels in a specified arrangement. Thereafter, using the ink in which the green or blue pigment is dispersed, the liquid composition is applied, prebaked, exposed, developed, and post-baked on the same substrate as the red pixel array. A green pixel array and a blue pixel array are sequentially formed, whereby the pixel arrays of the three primary colors of red, green, and blue are disposed on the substrate, and further, as a protective film thereon, the colorant is not contained. The liquid composition of the photosensitive resin is applied, prebaked, exposed, developed, and post-baked in the same manner as described above to obtain a color filter in which a protective film is formed.

When the liquid composition of the photosensitive resin composition for black photoresist of the present invention is applied to a substrate, a roll coater, a flash coater, or a slit coat may be used in addition to a well-known solution dipping method or a spray method. Any method such as a machine or a spin coater, a screen printing method or an inkjet printing method. After the desired thickness is applied by this method, the solvent is removed (prebaking) to form a film. The prebaking is carried out by heating by an oven, a hot plate or the like, vacuum drying or a combination thereof. The heating temperature and heating time of the prebaking are suitably selected according to the solvent to be used, for example, at a temperature of 80 to 120 ° C for 1 to 10 minutes.

In the case of producing a color filter, as the radiation used for exposing and curing the photosensitive resin composition, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and the wavelength is preferably 250~. Radiation in the range of 450 nm. Next, alkali imaging is carried out, and a developing solution suitable for alkali imaging is, for example, a water-soluble solution of an alkali metal or an alkaline earth metal carbonate. An aqueous solution of a liquid or an alkali metal hydroxide is particularly used at a temperature of 20 to 30 ° C using a weakly alkaline aqueous solution containing 0.05 to 10% by mass of a carbonate such as sodium carbonate, potassium carbonate or lithium carbonate. As a result, a fine image can be precisely formed using a commercially available developing machine or an ultrasonic cleaner. Further, after alkali development, water washing is usually carried out. As the development processing method, a shower development method, a spray development method, a dip development method, an immersion (full liquid) development method, or the like can be used. The development condition is preferably 10 to 120 seconds at normal temperature.

After such development, heat treatment (post-baking) is carried out at a temperature of 180 to 250 ° C and a temperature of 20 to 100 minutes. Thereafter, the baking is performed for the purpose of improving the adhesion between the patterned coating film and the substrate. This is carried out by heating in an oven, a hot plate or the like as in the case of prebaking. The patterned coating film of the present invention is formed by the respective steps of the above lithography method.

As a substrate used for forming a color filter having a pixel and a black matrix, for example, it is used for vapor deposition on glass, a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether oxime, etc.) or A transparent electrode such as ITO or gold is patterned. Further, for these substrates, an appropriate pretreatment such as a drug treatment such as a decane coupling agent, a plasma treatment, an ion plating, a sputtering, a gas phase reaction method, or a vacuum vapor deposition may be applied in advance.

[Examples]

Next, the method for producing the photosensitive resin composition for a black matrix of the present invention and the characteristics of the photosensitive resin composition will be described in more detail by showing examples, but the present invention is not limited by the examples.

[Modulation Example 1] <Modulation of Dye-Coated Carbon Black (1)>

1000 g of carbon black (TPX-1099: manufactured by Cabot Co., Ltd.) was mixed with water to prepare a slurry 10 L, and the mixture was stirred at 95 ° C for 1 hour, left to cool, and then washed with water. This was again mixed with water to prepare a slurry 10 L, and 42.9 g of 70% nitric acid was added thereto, and the mixture was stirred at 40 ° C for 4 hours. The mixture was cooled, washed with water, and mixed with water to prepare a slurry of 10 L, and a 76% sodium hypochlorite aqueous solution of 769.2 g was added thereto, followed by stirring at 40 ° C for 6 hours. The mixture was cooled, washed with water, and mixed with water to prepare a slurry of 10 L. 38.1 g of a dye (Direct Deep BLACK) having a purity of 38.4% was added, and the mixture was stirred at 40 ° C for 1 hour, and then 10.1 g of aluminum sulfate was further added thereto. Stir at °C for 1 hour. After this was allowed to stand for cooling, it was washed with water, and dried by filtration to obtain a dye-coated carbon black.

Determination of the amount of carboxyl groups

The amount of the acidic functional group (amount of carboxyl group) of the obtained dye-coated carbon black was measured by the method described in JP-A-2000-248197.

10 g of carbon black was weighed and the mixture was shaken in 50 ml of a 0.1 N aqueous sodium hydrogencarbonate solution for 1 hour to filter the mixture, and 20 ml of the supernatant of the filtrate was collected and titrated with 0.01 equivalent of an aqueous hydrochloric acid solution. The amount of carboxyl groups was determined as the millimolar amount (mmol/g) in 1 g of carbon black, and was determined according to the following formula.

Carboxyl group = (50/20 × 0.01 × (titration - empty titration)) / carbon black sample quality

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

[Modulation Example 2] <Dyeing of uncoated carbon black>

The dye was not coated with carbon black except that the lake treatment by the dye coating and the aluminum sulfate was not applied, and the treatment was carried out in substantially the same manner as in Preparation Example 1.

[Modulation Example 3] <Resin coated carbon black modulation>

To a polyvinyl chloride (Nissan Vinyl E-430 manufactured by Nissan Chemical Co., Ltd.), cyclohexanone was added and heated to about 90 ° C to dissolve, and a cyclohexanone solution containing 10% by mass of polyvinyl chloride was prepared. On the other hand, carbon black (furnace black, manufactured by Mitsubishi Chemical Corporation, #3050) was mixed with water and vigorously stirred to prepare a uniform suspension containing 6% by mass of carbon black. Next, while stirring the suspension in the above cyclohexanone solution, the carbon black of the aqueous phase was moved to the solvent phase. Next, the water separated from the carbon black was removed by decantation, and then kneaded for about 5 minutes using a roll mill heated to 80 to 120 ° C with two rolls to obtain a resin composition. Subsequently, the resin composition was cut into a sheet shape by a heating roll, and this was pulverized to a size of about 30 mm or less by a roll mill having two rolls at normal temperature, and then transferred to water to be stirred at about 3000 rpm. The granules were pulverized and granulated in such a manner that the average secondary particle diameter was 0.1 to 3 mm in about 3 minutes to obtain a granule. Dry at 80~150°C The whole granule was dried to obtain a resin-coated carbon black.

[Modulation Example 4] <(A)-1 Modulation of Pigment Dispersion of the Present Invention>

In the bead mill, 600 g of the dye-coated carbon black (component A1) obtained in the preparation example 1 and the urethane-based dispersing agent of the A2 component were used, and 93.2 g of the A3 component was obtained by the BYK-167 (manufactured by BYK Chemical Co., Ltd.). A propylene glycol monomethyl ether acetate solution of an epoxy acrylate acid addition product of an anthracene skeleton (resin solid content concentration = 56.5 mass%, "V259ME" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) 378 g, solvent propylene glycol of A4 component The pigment dispersion (A)-1 of the present invention was obtained by 1328.8 g of methyl ether acetate. The average secondary particle diameter of the dye-coated carbon black of the obtained pigment dispersion (A)-1 was 110 nm.

[Modulation Example 5] <(A)-2 Preparation of Comparative Pigment Dispersion (Use of Dye Uncoated Carbon Black)>

The pigment dispersion (A)-2 for comparison was obtained in the same manner as in Preparation Example 4 except that the dye obtained by the preparation example 2 was not coated with carbon black instead of the dye-coated carbon black.

[Modulation Example 6] <(A)-3 Preparation of Comparative Pigment Dispersion (Used for Resin-Coated Carbon Black)>

In addition to coating the carbon black in place of the dye, the resin obtained in Preparation Example 3 was coated with carbon black, and treated in the same manner as in Preparation Example 4 to obtain a comparative color. Dispersion (A)-3.

[Reference Example 7] <(A)-4 Preparation of Comparative Pigment Dispersion (No Dispersion Resin)>

The treatment was carried out in substantially the same manner as in Preparation Example 4, except that the propylene glycol monomethyl ether acetate solution of the acid addition product of the epoxy acrylate having an anthracene skeleton was not added, and the solvent propylene glycol monomethyl ether acetate was 1706.8 g. A pigment dispersion (A)-4 for comparison was obtained.

[Use of (B)~(E) ingredients and additives (F)~(G) ingredients] <(B)-1 alkali-soluble resin having an unsaturated group having a structure of the general formula (I)>

A propylene glycol monomethyl ether acetate solution of an acid addition product of an epoxy acrylate having an anthracene skeleton (resin solid content concentration = 56.5 mass%, "V259ME" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.)

<(B)-2 an alkali-soluble resin containing an unsaturated group other than the structure of the general formula (I)>

Propylene glycol monomethyl ether acetate solution of N-phenylmaleimide/acrylic acid/styrene copolymer (resin solid content concentration = 35.5 mass%, N-phenylmaleimide: acrylic acid: styrene =19:22:59% by mole, weight average molecular weight 9000, acid price 80)

<(C) Photopolymerizable monomer having an ethylenically unsaturated bond>

Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate ("KAYARAD-DPHA" manufactured by Nippon Kayaku Co., Ltd.)

<(D) Photopolymerization Initiator>

Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(0-ethylindenyl) (Irgacure, manufactured by BASF Corporation) OXE02")

<(E)-1 Solvent 1>

Propylene glycol monomethyl ether acetate

<(E)-2 Solvent 2>

Cyclohexanone

<(F)decane coupling agent>

3-Methyl propylene methoxy propyl trimethoxy decane ("KBM-503" manufactured by Shin-Etsu Chemical Co., Ltd.)

<(G) surfactant]

Megafac F475 (made by DIC)

[Example 1] <Preparation of photosensitive resin composition for black matrix>

The pigment dispersion (A)-1 565g, (B)-1 43.7g, (C) 25g, (D) obtained in Preparation Example 4 were uniformly mixed in the solvent (E)-1 537.9 g and (E)-2 752.0 g. 15 g and 2.5 g of a decane coupling agent (F) and 2.0 g of a surfactant (G) were used to prepare a photosensitive resin composition for a black matrix. Table 1 shows this compounding ingredient And the components of the following comparative examples.

[Comparative Example 1]

A photosensitive resin composition for a comparative black matrix was prepared in the same manner as in Example 1 except that the pigment dispersion (A)-1 was used instead of the pigment dispersion (A)-1.

[Comparative Example 2]

A photosensitive resin composition for a black matrix for comparison was prepared in the same manner as in Example 1 except that the pigment dispersion (A)-1 was used instead of the pigment dispersion (A)-1 (except that the components are as shown in Table 1). .

[Comparative Example 3]

The same applies to Example 1 except that (B)-2 is used instead of the alkali-soluble resin (B)-1 containing an unsaturated group (except that the compounding component is as shown in Table 1). A photosensitive resin composition.

[Comparative Example 4]

A photosensitive resin composition for a black matrix for comparison was prepared in the same manner as in Example 1 except that the pigment dispersion (A)-1 was used instead of the pigment dispersion (A)-1 (except that the compounding component is as shown in Table 1). .

[Evaluation]

Using the photosensitive resin compositions of Example 1 and Comparative Examples 1 to 4, the evaluations described below were carried out. The evaluation results of these are shown in Table 2.

<Evaluation of imaging characteristics (pattern line width ‧ pattern linearity ‧ resolution) >

Each of the photosensitive resin compositions obtained above was applied onto a 125 mm × 125 mm glass substrate (Corning 1737) by a spin coater, and the film thickness after post-baking was 1.0 μm, and pre-baked at 90 ° C. minute. Then, the exposure gap was adjusted to 100 μm, over the dried coating film, covering line/gap = 2 μm / 2 μm, 4 μm / 4 μm, 5 μm / 5 μm, 6 μm / 6 μm, 8 μm / 8 μm, 10 μm / 10 μm and 20 μm / 20 μm negative In the reticle, ultraviolet rays of 80 mJ/cm ² were irradiated with an ultrahigh pressure mercury lamp having an i-line illuminance of 30 mW/cm ² to carry out a photohardening reaction of the photosensitive portion.

Next, the exposed coated plate was sprayed at a spray pressure of 1 kgf/cm ² at 25 ° C, 0.08% potassium hydroxide aqueous solution, from the start of the development time of the pattern (break time = BT). After +10 seconds and +20 seconds of development, a spray washing with a pressure of 5 kgf/cm ^{2 was} performed to remove the unexposed portion of the coating film to form a pixel pattern on the glass substrate, and then a hot air dryer was used at 230. After hot baking at ° C for 30 minutes, the line width, pattern linearity, and resolution of the mask width with respect to the 10 μm line were evaluated. Furthermore, each evaluation method is as follows.

Pattern line width: A line length of a pattern having a mask width of 10 μm was measured using a length measuring microscope ("XD-20" manufactured by NIKON Co., Ltd.).

Linearity of the pattern: The 10 μm mask pattern after post-baking was observed with a microscope, and the sawtooth which showed no peeling of the substrate or the edge portion of the pattern was evaluated as ○, and was evaluated as Δ in some of the viewers. It is evaluated as × in all the viewers.

Resolution: In the 2 μm, 4 μm, 5 μm, 6 μm, 8 μm, 10 μm, and 20 μm mask patterns, the minimum pattern size remaining on the substrate was taken as the resolution.

<Evaluation of OD>

Each of the photosensitive resin compositions obtained above was applied onto a 125 mm × 125 mm glass substrate (Corning 1737) by a spin coater, and the film thickness after post-baking was 1.0 μm, and pre-baked at 90 ° C. 1 minute. Then, the exposure gap was adjusted to 100 μm, and a negative mask having an opening of 15 mm × 15 mm was overlaid on the dried coating film, and an ultraviolet ray of 80 mJ/cm ² was irradiated with an ultrahigh pressure mercury lamp having an i illuminance of 30 mW/cm ² . Photohardening reaction of the photosensitive portion.

Next, the exposed coated plate was sprayed at a spray pressure of 1 kgf/cm ² at 25 ° C, 0.08% potassium hydroxide aqueous solution, from the start of the development time of the pattern (break time = BT). After +20 seconds of development, a spray washing with a pressure of 5 kgf/cm ^{2 was} performed to remove the unexposed portion of the coating film to form a pixel pattern on the glass substrate, and then a hot air dryer was used at 230 ° C for 30 minutes. After hot post-baking, the OD of the pixel formed at the opening of 15 mm × 15 mm was evaluated by a Macbeth through a densitometer.

<Evaluation of surface resistance>

Each of the photosensitive resin compositions obtained above was applied onto a 125 mm × 125 mm glass substrate (Corning 1737) by a spin coater, and the film thickness after post-baking was 1.0 μm, and pre-baked at 90 ° C. minute. Then, an ultrahigh pressure mercury lamp having an i-line illuminance of 30 mW/cm ² was used, and a light-hardening reaction was carried out by irradiating ultraviolet rays of 80 mJ/cm ² without a photomask. Next, the exposed coated plate was sprayed at a pressure of 1 kgf/cm ² at 25 ° C, 0.08% potassium hydroxide aqueous solution, and the development time of the pattern began to appear when the reticle was covered (disconnection time) From BT), after +20 seconds of development, a spray washing with a pressure of 5 kgf/cm ^{2 was} performed, and after baking at 230 ° C, 30 minutes, and 180 minutes using a hot air dryer, the surface resistance was measured.

<Evaluation of adhesion to glass substrate>

Each of the photosensitive resin compositions obtained above was applied onto a 125 mm × 125 mm glass substrate (Corning 1737) by a spin coater, and the film thickness after post-baking was 1.0 μm, and pre-baked at 90 ° C. minute. Then, without using a negative mask, an ultrahigh pressure mercury lamp having an i-line illumination of 30 mW/cm ² was used, and the whole was exposed at 80 mJ/cm ² , and baked at 230 ° C for 30 minutes using a hot air dryer. Then, the adhesion of the glass substrate was evaluated by the evaluation method of the 3-point bending adhesion test method according to JIS K6856-1994.

The above-mentioned post-baked substrate and the glass substrate (Corning 1737) to which the resin composition was not applied were each cut into a rectangular shape of 20 mm × 63 mm to prepare a test piece. Superimposed and baked film by a certain amount of sealant epoxy adhesive (Strucbond XN-21s (manufactured by Mitsui Chemicals)) The glass substrate on which the photosensitive resin composition was not applied was bonded to the substrate (test piece) having a width of 8 mm. The sealant epoxy-based adhesive at the time of lamination is circular in shape and has a diameter of about 5 mm. Then, the laminated test pieces were prebaked at 90 ° C for 20 minutes, respectively, and then baked at 150 ° C for 2 hours to prepare a three-point bending test piece. Further, 20 mm × 63 mm uncoated glass sheets were also subjected to a comparative comparative test sample by the same method as described above.

In the test piece obtained as described above, the coated sheet and the counter substrate (the uncoated substrate) were supported by a two-point support so that the overlapped portion was centered (the length of the support at 2 points was 3 cm). Or the glass substrate for the comparative test, which was not coated, was directly under the superimposed portion, and the UCT-100 made by ORIENTEC Co., Ltd. was used to apply the load at a speed of 1 mm/min. With the load at that time, the load per unit area was taken as the adhesion strength by dividing the coating area of the sealant epoxy-based adhesive. Further, after performing PCT (pressure cooking test) under conditions of 121 ° C, 100% RH, 2 atm, and 5 hours, 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 between the uncoated photoresists before and after the PCT was taken as 100 was expressed as a relative value. Before and after the PCT, 70 or more is ○, and less than 70 series ×.

As is clear from Table 2, the photosensitive resin composition for a black matrix of Example 1 of the present invention is in comparison with the photosensitive resin composition of each comparative example, in the pattern line width, pattern linearity, and resolution. Excellent performance is exhibited in the development characteristics, and the surface resistance and the adhesion strength to the glass substrate are also excellent. Specifically, as in Comparative Example 1, if the dye is not coated with carbon black, However, the development characteristics such as linearity and resolution of the pattern are not problematic, but the necessary properties are not obtained in the surface resistance and the adhesion to the glass substrate. When the carbon black was coated with a resin in Comparative Example 2, the development characteristics and the adhesion strength to the glass substrate were insufficient when the conditions of the light shielding degree and the surface resistance were satisfied. In Comparative Example 3, when an alkali-soluble resin containing an unsaturated group is added to the pigment dispersion, when a resin having a structure other than the formula (I) is used, the development characteristics are insufficient, and the surface resistance after the heat treatment is lowered. . In Comparative Example 4, when a photosensitive resin composition using a pigment dispersion in which the resin (A3) of the general formula (I) was not dispersed was used in the preparation, a decrease in surface resistance after the heat treatment was observed.

[Industry use possibility]

As described above, when the carbon black dispersion for a black matrix of the present invention is used for a photosensitive resin composition for a black matrix, it is possible to form a fine line pattern forming system having high electric resistance and excellent development characteristics and adhesion to a glass substrate. By using this color filter, a black matrix having high light-shielding property and high resistance and high reliability can be obtained. Therefore, it is used for inks used in various multi-color display bodies or optical devices such as color liquid crystal display devices, color facsimile machines, and image sensors, and color filters having black matrices, or televisions and video monitors. It is very useful when it is used for a computer monitor. In particular, it is useful as a small and medium-sized high-definition display oriented to a smart phone.

Claims (13)

A method for producing a photosensitive resin composition for a color filter black matrix, which comprises preliminarily preparing (A1) to (A4) components and (A) dye-coated carbon in (A) pigment dispersion After the amount of black is 15 to 35 mass% of the (A) pigment dispersion, (A1) the surface of the carbon black which has been previously subjected to oxidation treatment and has at least one type of acidic functional group on the surface is coated with a dye, and then passed through the metal. Or a dye-coated metal salt, carbon black, (A2) dispersant, (A3) an alkali-soluble resin having an unsaturated group-containing structure of the following formula (I), (A4) solvent, which will contain The component (B) to (E) as a component of the essential component is mixed with the pigment dispersion (A), (B) an alkali-soluble resin containing an unsaturated group, and (C) light having an ethylenically unsaturated bond. Polymerizable monomer, (D) photopolymerization initiator, (E) solvent, [Formula (I) is a reaction of an epoxy compound having 2 epoxidopropyl ether groups derived from bisphenols with (meth)acrylic acid to give (a) a dicarboxylic acid or a tricarboxylic acid or Ethylene (A) and (b) a tetracarboxylic acid or an acid dianhydride thereof obtained by reacting a molar ratio of (a) to (b) of 1:10 to 10:1. An acrylate acid adduct; wherein, in the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ₅ Represents a hydrogen atom or a methyl group, and A represents -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, 9,9-fluorenyl or a straight bond, X represents a tetravalent carboxylic acid residue, and Y ₁ and Y ₂ each independently represent a hydrogen atom or -OC-Z-(COOH) _m (only, Z represents 2 A valence or a trivalent carboxylic acid residue, m represents a number from 1 to 2, and n represents an integer from 1 to 20]. A photosensitive resin composition for a color filter black matrix, which has the following components (A1) to (A4) and is prepared in advance to make (A1) dye-coated carbon in (A) pigment dispersion The (A) pigment dispersion having a black content of 15 to 35% by mass is mixed with a component containing the following components (B) to (E) as essential components, and (A1) is previously subjected to oxidation treatment. After the surface of the carbon black having at least one kind of acidic functional group on the surface is coated with a dye, the dye which is formed by lake or metal salt is coated with carbon black, (A2) dispersant, and (A3) has the following formula (I) an alkali-soluble resin containing an unsaturated group, (A4) a solvent, (B) an alkali-soluble resin containing an unsaturated group, and (C) a photopolymerizable monomer having an ethylenically unsaturated bond, (D) ) photopolymerization initiator, (E) solvent, [Formula (I) is a reaction of an epoxy compound having 2 epoxidopropyl ether groups derived from bisphenols with (meth)acrylic acid to give (a) a dicarboxylic acid or a tricarboxylic acid or Ethylene (A) and (b) a tetracarboxylic acid or an acid dianhydride thereof obtained by reacting a molar ratio of (a) to (b) of 1:10 to 10:1. An acrylate acid adduct; wherein, in the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ₅ Represents a hydrogen atom or a methyl group, and A represents -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, 9,9-fluorenyl or a straight bond, X represents a tetravalent carboxylic acid residue, and Y ₁ and Y ₂ each independently represent a hydrogen atom or -OC-Z-(COOH) _m (only, Z represents 2 A valence or a trivalent carboxylic acid residue, m represents a number from 1 to 2, and n represents an integer from 1 to 20]. The photosensitive resin composition for a color filter black matrix of claim 2, wherein the content of the dye in the (A1) dye-coated carbon black is 0.5 to 10% by mass. The photosensitive resin composition for a color filter black matrix according to claim 2 or 3, wherein the dye of the (A1) dye-coated carbon black is an anionic or nonionic dye. The photosensitive resin composition for a color filter black matrix according to claim 2 or 3, wherein the dye of the (A1) dye-coated carbon black is a dye of a rich color system. The photosensitive resin composition for a color filter black matrix according to claim 2, wherein the metal or metal salt is aluminum, magnesium, calcium, barium, strontium or manganese or a salt thereof. The photosensitive resin composition for a color filter black matrix according to claim 2, wherein the acidic functional group is a hydroxyl group, a pendant oxy group, a hydroperoxy group, a carbonyl group, a carboxyl group, a peroxycarboxylic acid group, an aldehyde group, or a ketone group. , nitro, nitroso, decylamino, quinone imine, sulfonate, sulfinate, sulfenyl, thiocarboxylic acid, chlorooxy, dichlorooxy, perchloroxy , iodooxy or iodonium. The photosensitive resin composition for a color filter black matrix of claim 2, wherein the amount of the (A3) alkali-soluble resin containing an unsaturated group is 2 to 20% by mass. The photosensitive resin composition for a color filter black matrix of claim 2, wherein the amount of the (A1) dye-coated carbon black in the solid content of the photosensitive resin composition is 45 to 60% by mass. The photosensitive resin composition for a color filter black matrix of claim 2, wherein at least a part of the component (B) is an alkali-soluble resin containing an unsaturated group represented by the above formula (I). A coating film formed by hardening a color filter black matrix of claims 2 to 10 with a photosensitive resin composition. A black matrix in which a color filter black matrix according to claims 2 to 10 is coated with a photosensitive resin composition, and after film formation, a selected position is photocured, and an alkali developing solution is used for image formation. Got it. A color filter formed as a black matrix of claim 12.