JP6426469B2 - Photosensitive resin composition for black matrix and method for producing the same - Google Patents

Description

  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 of high light-shielding and high-resistance fine line patterns and which is excellent in storage stability, and a method for producing the same.

  In recent years, color liquid crystal display devices have come to be 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 that affect the visibility of the color liquid crystal display device, and in order to improve the visibility, that is, to obtain a clearer image, the black matrix of the color filter is further enhanced in light shielding In the photosensitive resin composition, it has become necessary to add a light shielding material such as a pigment in a larger amount than ever before.

  However, when the content of a light shielding material such as a pigment increases, it becomes difficult for the light in the ultraviolet region to reach the deep part of the coating film in the black resist film when forming a color filter, and adhesion of the pattern due to curing failure in the photocurable composition. Problems occur such as defects, pattern peeling during development, and sharpening of the edge shape.

  Therefore, high-sensitivity photopolymerization initiators and acrylic monomers with a high degree of polymerization have come to be used so that curing defects do not occur even when light-shielding materials such as high concentrations of pigments are included. In the present situation, the increase in sensitivity for photopolymerization initiators and acrylic monomers has reached the limit at present, and sufficient sensitivity for forming a good pattern in a high concentration region of a light-shielding material such as a pigment or the like and a glass substrate There is a problem that adhesion and storage stability of the photosensitive resin composition can not be obtained.

  Therefore, the present inventors previously used a pigment dispersion in which specific epoxy (meth) acrylate acid adducts were used as an alkali-soluble resin used in pigment dispersion, and these were co-dispersed with a dispersant. The photosensitive resin composition for color filters was proposed (refer patent document 1). According to the photosensitive resin composition, the photosensitive resin composition has a high sensitivity and high adhesion to a glass substrate in a region including a light shielding material such as a pigment having a high concentration to achieve high light shielding with a black matrix. Excellent storage stability of the object can be achieved.

  However, in addition to the increasingly sophisticated required characteristics such as thinning the black matrix and increasing the degree of shading to achieve brighter and brighter color filters, depending on the display mode of the liquid crystal, black is more than ever before It has become necessary to make the matrix highly resistive. If it is intended to add an amount of light shielding material such as pigment for achieving such high level of high light shielding and high resistance, the development adhesion of a fine line pattern of 10 μm or less can not be sufficiently secured, and the color filter There has also been a problem that it becomes difficult to maintain high adhesion to the glass substrate by the sealing agent when assembled into a panel.

JP, 2008-9401, A

  As described above, it is difficult to obtain a photosensitive resin composition for a black matrix to form a high light-shielding and high-resistance fine line pattern, and for example, 10 μm when a large amount of carbon black is added for light shielding The adhesion of the thin line pattern below and the adhesion to the glass substrate can not be obtained sufficiently and it is difficult to achieve high resistance. Conversely, if the adhesion and resistance of the thin line pattern are to be required levels, the thickness of the coating film It has been strongly demanded to solve the problem that sufficient light blocking property can not be obtained unless the size is increased, and the design becomes inapplicable for the color filter.

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

〔一般式（Ｉ）は、ビスフェノール類から誘導される２個のグリシジルエーテル基を有するエポキシ化合物と（メタ）アクリル酸との反応物に、（ａ）ジカルボン酸若しくはトリカルボン酸又はいずれかの酸一無水物と（ｂ）テトラカルボン酸又はその酸二無水物とを、（ａ）と（ｂ）のモル比が１：１０〜１０：１となるよう反応させて得られるエポキシ（メタ）アクリレート酸付加物である。ここで、式中、Ｒ₁、Ｒ₂、Ｒ₃及びＲ₄は、それぞれ独立して水素原子、炭素数１〜５のアルキル基、ハロゲン原子又はフェニル基を表し、Ｒ₅は、水素原子又はメチル基を表し、Ａは、−ＣＯ−、−ＳＯ₂−、−Ｃ（ＣＦ₃）₂−、−Ｓｉ（ＣＨ₃）₂−、−ＣＨ₂−、−Ｃ（ＣＨ₃）₂−、−Ｏ−、９，９−フルオレニル基又は直結合を表し、Ｘは４価のカルボン酸残基を表し、Ｙ₁及びＹ₂は、それぞれ独立して水素原子又は−ＯＣ−Ｚ−（ＣＯＯＨ）_ｍ（但し、Ｚは２価又は３価カルボン酸残基を表し、ｍは１〜２の数を表す）を表し、ｎは１〜２０の整数を表す。〕The above object of the present invention is achieved by the following means.
(1) The present invention provides the following components (A1) to (A4),
(A1) Dye-coated carbon black, the surface of which is coated with a dye,
(A2) Dispersant,
(A3) unsaturated group-containing alkali-soluble resin having a structure of the following general formula (I),
(A4) After preparing a pigment dispersion having a solvent (A) in advance, the following (B) to (E) components as essential components,
(B) Alkali-soluble resin containing unsaturated group,
(C) a photopolymerizable monomer having an ethylenically unsaturated bond,
(D) Photopolymerization initiator,
(E) A method of producing a photosensitive resin composition for a color filter black matrix, which comprises mixing a blending component containing a solvent and the pigment dispersion (A).

[The general formula (I) is a product of (a) dicarboxylic acid or tricarboxylic acid or any acid of the reaction product of (meth) acrylic acid and an epoxy compound having two glycidyl ether groups derived from bisphenols. Epoxy (meth) acrylate acid obtained by reacting an anhydride and (b) tetracarboxylic acid or its acid dianhydride so that the molar ratio of (a) to (b) is 1:10 to 10: 1 It is an additive. Here, 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 represents 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, 9-fluorenyl group or a direct bond, X represents a tetravalent carboxylic acid residue, and Y ₁ and Y ₂ are each independently 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. ]

〔一般式（Ｉ）は、ビスフェノール類から誘導される２個のグリシジルエーテル基を有するエポキシ化合物と（メタ）アクリル酸との反応物に、（ａ）ジカルボン酸若しくはトリカルボン酸又はいずれかの酸一無水物と（ｂ）テトラカルボン酸又はその酸二無水物とを、（ａ）と（ｂ）のモル比が１：１０〜１０：１となるよう反応させて得られるエポキシ（メタ）アクリレート酸付加物である。ここで、式中、Ｒ₁、Ｒ₂、Ｒ₃及びＲ₄は、それぞれ独立して水素原子、炭素数１〜５のアルキル基、ハロゲン原子又はフェニル基を表し、Ｒ₅は、水素原子又はメチル基を表し、Ａは、−ＣＯ−、−ＳＯ₂−、−Ｃ（ＣＦ₃）₂−、−Ｓｉ（ＣＨ₃）₂−、−ＣＨ₂−、−Ｃ（ＣＨ₃）₂−、−Ｏ−、９，９−フルオレニル基又は直結合を表し、Ｘは４価のカルボン酸残基を表し、Ｙ₁及びＹ₂は、それぞれ独立して水素原子又は−ＯＣ−Ｚ−（ＣＯＯＨ）_ｍ（但し、Ｚは２価又は３価カルボン酸残基を表し、ｍは１〜２の数を表す）を表し、ｎは１〜２０の整数を表す。〕(2) The present invention also provides the following components (A1) to (A4):
(A1) Dye-coated carbon black, the surface of which is coated with a dye,
(A2) Dispersant,
(A3) unsaturated group-containing alkali-soluble resin having a structure of the following general formula (I),
(A4) A pigment dispersion prepared in advance with a solvent, and the following components (B) to (E) as essential components,
(B) Alkali-soluble resin containing unsaturated group,
(C) a photopolymerizable monomer having an ethylenically unsaturated bond,
(D) Photopolymerization initiator,
(E) A photosensitive resin composition for a color filter black matrix, which is obtained by mixing a blending component containing a solvent.

[The general formula (I) is a product of (a) dicarboxylic acid or tricarboxylic acid or any acid of the reaction product of (meth) acrylic acid and an epoxy compound having two glycidyl ether groups derived from bisphenols. Epoxy (meth) acrylate acid obtained by reacting an anhydride and (b) tetracarboxylic acid or its acid dianhydride so that the molar ratio of (a) to (b) is 1:10 to 10: 1 It is an additive. Here, 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 represents 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, 9-fluorenyl group or a direct bond, X represents a tetravalent carboxylic acid residue, and Y ₁ and Y ₂ are each independently 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. ]

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

  (4) In the photosensitive resin composition for color filter black matrix according to (2) to (3), the dye-coated carbon black according to the present invention is a dye in which the dye is an anionic or non-ionic dye. is there.

  (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 according to the present invention is a dye having a dark color. It is.

  (6) In the present invention, the dye-coated carbon black according to any one of (2) to (5), wherein the dye is laked with a metal or a metal salt. It is a resin composition.

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

  (8) In the invention, any one of (2) to (7), wherein the dye-coated carbon black is obtained using carbon black having at least one kind of acidic functional group on the surface thereof. It is a photosensitive resin composition for color filter black matrices as described in 4.

  (9) In the present invention, the acidic functional group is a hydroxyl group, oxo group, hydroperoxy group, carbonyl group, carboxyl group, peroxycarboxylic acid group, aldehyde group, ketone group, nitro group, nitroso group, amido group, imide Group, a sulfonic acid group, a sulfinic acid group, a sulfenic acid group, a thiocarboxylic acid group, a chlorosyl group, a chloryl group, a perchloryl group, an iodosyl group or an iodyl group according to any one of (2) to (8) It is a photosensitive resin composition for color filter black matrix.

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

  (11) The present invention also relates to any one of (2) to (10), wherein the blending amount of (A1) dye-coated carbon black in the solid content of the photosensitive resin composition is 45 to 60% by mass. It is a photosensitive resin composition for color filter black matrices as described in 4.

  (12) The present invention is also any one of (2) to (11), wherein the (B) component is an unsaturated group-containing alkali-soluble resin represented by the general formula (I) in (1). It is a photosensitive resin composition for color filters as described in these.

  (13) The present invention is also a coating film formed by curing the photosensitive resin composition for a color filter black matrix according to (2) to (12).

  (14) The present invention is also obtained by coating the photosensitive resin composition for black matrix as described in (2) to (12), forming a film, photocuring at a selective position, and developing with an alkaline developer. Black matrix.

  (15) The present invention is also a color filter on which the black matrix described in (14) is formed.

  The photosensitive resin composition for black matrix of the present invention is produced using a pigment dispersion comprising dye-coated carbon black whose surface is coated with a dye, and a specific epoxy (meth) acrylate acid adduct. A photosensitive resin composition for a black matrix characterized in that the storage stability is excellent and the coating property and the developability are excellent, so a fine line pattern having high light shielding and high resistance and excellent adhesion to a glass substrate. It is possible to form it, and applying it to a color filter makes it possible to create a highly opaque, highly resistant, highly reliable black matrix.

Hereinafter, embodiments of the present invention will be described in detail.
The photosensitive resin composition for a black matrix of the present invention first prepares (A) a pigment dispersion, and its constituent components are (A1) dye-coated carbon black, (A2) dispersant, (A3) general formula (A) It is the unsaturated group containing alkali-soluble resin which has a structure of I), and (A4) solvent.

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

  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 size means an arithmetic mean value of primary particle sizes obtained by observing 1,500 carbon black primary particles with an electron microscope. When the average primary particle size of the raw material carbon black is less than the above lower limit, aggregation is likely to occur, the stability of the mill base is deteriorated, and the dispersion at high concentration becomes difficult. As the surface roughness also deteriorates, both are not preferable.

  The raw material carbon black preferably has a DBP absorption of 100 ml / 100 g or less. Here, the DBP absorption refers to the capacity of dibutyl phthalate (DBP) absorbed by 100 g of carbon black, and is measured according to the method described in JIS K6217-4. When the DBP absorption amount of the raw material carbon black exceeds the above upper limit, the resistance value is lowered and the viscosity is increased, the coating property is deteriorated, and the blackness is lowered, which is not preferable.

  Further, 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, pH value means the value which measured the liquid mixture of carbon black and distilled water with a glass electrode pH meter, and measures it according to the method of JISK6221-1982. If the pH of the raw material carbon black is less than the above lower limit, the entire balance is broken and the dispersion stability is deteriorated, and if it exceeds the above upper limit, film peeling is likely to occur.

Furthermore, as the raw material carbon black, one having an ash content of 1.0% or less and a specific surface area of 20 to 300 m ² / g is suitably used. The ash content is measured according to the method described in JIS K 6218-2, and the specific surface area is measured according to the method C described in JIS K 6217-2. If the ash content exceeds the above upper limit, the resistance value decreases, which is not preferable. If the specific surface area falls below the above lower limit, the shape defect of the black matrix tends to occur, and if the above upper limit is exceeded, the dispersant, resin, dye and the like Both are undesirable because they are required in large quantities.

  In addition, it is preferable that the raw material carbon black be subjected to an oxidation treatment in advance and have at least one kind of acidic functional group on the surface, and a plurality of kinds of oxidation treatments be given to give two or more kinds of acidic functions on the surface It is more preferable to have a group. It is sufficient to uniformly micro-disperse carbon black in the photosensitive resin composition, since those which have not been subjected to oxidation treatment in advance do not have acidic functional groups on the surface or the number of acidic functional groups is insufficient. The resistance value of the black matrix to be obtained is lowered. For this reason, it is not preferable because it becomes easy to cause an image defect by conducting between the transparent electrode on the color filter and the black matrix or between the counter electrode.

  As such oxidation treatment, oxidizing agents such as ozone gas, nitric acid, sodium hypochlorite, hydrogen peroxide, nitrogen monoxide gas, nitrogen dioxide gas, nitrogen dioxide gas, sulfuric anhydride, fluorine gas, concentrated sulfuric acid, nitric acid, various peroxides and the like are used. The method is mentioned. Moreover, as said acidic functional group, a hydroxyl group, an oxo group, a hydroperoxy group, a carbonyl group, a carboxyl group, a peroxycarboxylic acid group, an aldehyde group, a ketone group, a nitro group, a nitro group, an amide group, an imide group, a sulfonic acid group And sulfinic acid group, sulfenic acid group, thiocarboxylic acid group, chlorosyl group, chloryl group, perchloryl group, iodosyl group, iodosyl group and the like.

  The dye used for 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 Etc., but since the sulfone group and the carboxyl group interact with the functional group on the carbon black, the amino group and the alkali-soluble resin react, and they can be insolubilized with the sulfuric acid band etc. An ionic or non-ionic dye can be used more suitably. Moreover, in order to make the light-shielding property of the black matrix obtained higher, it is preferable to use a dye of a dark color close to black, which has high light absorption. 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, Food Yellow No. 7, Bernacid Red 2 BMN, Basacid Black X34 (BASF X-34) (manufactured by BASF), Kayanol Red 3BL (manufactured by Nippon Kayaku Company), Dermacarbon 2 GT (manufactured by Sandoz), Telon Fast Yellow 4GL-175, BASF Basacid Black SE 0228, Basacid Black X34 ( Acid dyes of each color such as BASF X-34) (BASF), Basacid Blue 750 (BASF), Bernacid Red (Bemcolors, Poughkeepsie, NY), BASF Basacid Black SE 0228 (BASF), Pontamine Brilliant Bond Blue A and other Pontamine Brilliant Bond Blue A and other Pontamine® dyes (Bayer Chemicals Corporation, Pittsburgh, PA), Cartasol Yellow GTF Presscake (Sandoz, Inc.); Cartasol Yellow GTF Liquid Special Special 110 (Sandoz, Inc.); Yellow Shade 16948 (Tricon), Direct Brilliant Pink B (Crompton & Knowles), Carta Black 2 GT (Sandoz, Inc.) Made, Sirius Supra Yellow GD 167, Cartasol Brilliant Yellow 4 GF (Sandoz); Pergasol Yellow CGP (Ciba-Geigy), Pyrazol Black BG (JCI), Diazol Black RN Quad (JCJ), Direct dyes of each color such as Pontamine Brilliant Bond Blue; Berncolor AY 34, Cibacron Brilliant Red 3B-A (Reactive Red 4) (Aldrich Chemical, Milwaukee, WI), Drimarene Brilliant Red X-2B (Reactive Red 56) (Pylam Products, Inc. Tempe, AZ), Levafix Brilliant Red E-4B, Levafix Brilliant Red F-6BA, and similar Levafix® dyes Dystar Dy (manufactured by Charlotte, NC) dyes, Procion Red H8B (Reactive Red 31) (manufactured by JCI America), reactive dyes of respective colors such as Neozapon Red 492 (manufactured by BASF), Orasol Red G (manufactured by Ciba-Geigy), Aizen Spilon Red C-BH (manufactured by Hodogaya Chemical Company) ), Spirit Fast Yellow 3G, Aizen Spilon Yellow C-GNH (Hodogaya Chemical Company), Orasol Black RL (Ciba-Geigy), Orasol Black RLP (Ciba-Geigy), Savinyl Black RLS (Sandoz) Made), Oras Examples thereof include oil-soluble dyes such as ol Blue GN (manufactured by Ciba-Geigy), Luxol Blue MBSN (manufactured by Morton-Thiokol), Morfast Black Concentrate A (manufactured by Morton-Thiokol), and the like. These may be used alone or in combination of two or more.

  Moreover, 0.5-10 mass% is preferable, as for content of the dye in dye-coated carbon black utilized by this invention, 1-7 mass% is more preferable, and 1-5 mass% is especially preferable. If the content of the dye is less than the above lower limit, the coating is insufficient and a high resistance value can not be obtained, and if the content exceeds the above upper limit, the excess dye not coated is likely to inhibit the dispersion and to cause thickening and aggregation. Both are not preferable.

  Furthermore, in the dye-coated carbon black used in the present invention, the dye is preferably laked with a metal or a metal salt. Since the dye is fixed to the surface of the carbon black or the acidic functional group via metal or metal salt by this lake formation, the dye is less likely to be separated from the surface of the carbon black, so the dye is difficult to elute and high shielding properties are achieved. Can be maintained. Examples of metals or metal salts used for such lake formation include single substances of aluminum, magnesium, calcium, strontium, barium or manganese, or their hydrochlorides, sulfates and the like, and these may be used alone or in combination of two or more. Can be used. The amount of the metal or metal salt used for lake formation is preferably 0.3 times by mole or more, more preferably 0.5 times by mole or more, and particularly preferably 0.8 times by mole or more, relative to the dye. If the amount of metal or metal salt added is less than the above, the fixation of the dye is insufficient and the carbon black surface is easily detached, and the stability of the mill base is poor, and the resistance value is also reduced.

  Next, the method for producing the dye-coated carbon black used in the present invention will be described. First, carbon black as a raw material is mixed with water (which is prepared by appropriately mixing ion-exchanged water with tap water so that the electric conductivity is constant, and the same applies hereinafter) to form a slurry, which is heated and stirred for a predetermined time. Is washed, cooled and washed again with water. Next, water is added to the obtained carbon black to form a slurry again, the above-mentioned oxidizing agent is added, and the mixture is stirred at a predetermined temperature for a predetermined time to oxidize the surface of the carbon black and wash it. The oxidation treatment is performed by changing the type of oxidizing agent a plurality of times as necessary. Next, the obtained oxidized carbon black is mixed with water to form a slurry again, and a dye is added to the target dye-coated carbon black to have the above-mentioned predetermined content, and the mixture is added at 40 to 90 ° C. Stir for a time to adsorb and coat the dye on the surface of the carbon black. Furthermore, an equimolar amount of the above-described metal or metal salt is added to the added dye, and the mixture is stirred at 30 to 70 ° C. for 1 to 5 hours to lake the dye with the metal or metal salt to fix the dye on the surface of carbon black. Let Then, this is cooled, washed with water, and filtered and dried to obtain the intended dye-coated carbon black.

  The compounding amount of the dye-coated carbon black in the (A) pigment dispersion of the present invention is 15 to 35% by mass, preferably 20 to 30% by mass. If the compounding amount of the dye-coated carbon black is less than the above lower limit, the light shielding property is not sufficient, the film thickness must be thickened in order to obtain the desired contrast, and it is difficult to obtain the surface smoothness of the black matrix. In addition, when the compounding amount of the dye-coated carbon black exceeds the above upper limit, the dispersion stability of the pigment dispersion is reduced, and the content of the photosensitive resin to be the original binder is also reduced. Both are not preferable because they can not be obtained.

  The pigment dispersion (A) of the present invention may contain, in addition to the dye-coated carbon black, carbon black which has been subjected to a normal or predetermined treatment. In addition, other pigments, light shielding materials, etc. may be included. Other pigments include, for example, black organic pigments such as perylene black and cyanine black, and mixed colors of pseudo blackened by mixing at least two or more pigments selected from red, blue, green, purple, yellow, cyan, magenta, etc. Organic pigments can be used. Moreover, chromium oxide, iron oxide, titanium black, aniline black, cyanine black can be mentioned as another light shielding material. The pigment and the light shielding material other than the dye-coated carbon black can be appropriately selected and used as two or more kinds respectively, and may be used in combination with each other.

  The dispersant of the component (A2) of the present invention may be any one having a function of stably dispersing the dye-coated carbon black of the component (A1) and other pigments optionally contained as a pigment dispersion, Known dispersants such as various polymer dispersants can be used. Specific examples of the polymer dispersant include polymer dispersants having basic functional groups such as primary, secondary or tertiary amino groups, and nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine. About the compounding quantity of this (A2) component, it is 1-30 mass% with respect to dye processing CB, Preferably it is 2-25 mass%.

〔式中、Ｒ₁、Ｒ₂、Ｒ₃及びＲ₄は、それぞれ独立して水素原子、炭素数１〜５のアルキル基、ハロゲン原子又はフェニル基を表し、Ｒ₅は、水素原子又はメチル基を表し、Ａは、−ＣＯ−、−ＳＯ₂−、−Ｃ（ＣＦ₃）₂−、−Ｓｉ（ＣＨ₃）₂−、−ＣＨ₂−、−Ｃ（ＣＨ₃）₂−、−Ｏ−、９，９−フルオレニル基又は直結合を表し、Ｘは４価のカルボン酸残基を表し、Ｙ₁及びＹ₂は、それぞれ独立して水素原子又は−ＯＣ−Ｚ−（ＣＯＯＨ）_ｍ（但し、Ｚは２価又は３価カルボン酸残基を表し、ｍは１〜２の数を表す）を表し、ｎは１〜２０の整数を表す〕で示されるエポキシ（メタ）アクリレート酸付加物である。The unsaturated group-containing alkali-soluble resin of the component (A3) of the present invention has the following general 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, and R ₅ represents a hydrogen atom or a methyl group the stands, a _{is, -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, and 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, m represents a number of 1 to 2), n represents an integer of 1 to 20, and the epoxy (meth) acrylate acid adduct represented by is there.

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

  Among these, as bisphenols giving the epoxy (meth) acrylate acid adduct of the general formula (I) of the present invention, bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone Bis (4-hydroxy-3,5-dichlorophenyl) ketone, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) ) Sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4 -Hydroxyphenyl) dimethylsilane, bis (4-hydride) X-3,5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) 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) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4- (4) Hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-) Hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, 4, 4'-biphenol, 3,3'-biphenol etc. and derivatives thereof are mentioned. Among these, those having a 9,9-fluorenyl group are particularly preferably used.

Then, the bisphenol and epichlorohydrin are reacted to obtain an epoxy compound having two glycidyl ether groups. Since this reaction generally involves the oligomerization of the diglycidyl ether compound, a compound of the following general formula (II) is obtained. In the formula of general formula (II), R ₁ , R ₂ , R ₃ , R ₄ and A have the same meaning as in general formula (I). 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. Moreover, since several values are mixed normally, 1 becomes average value 0-10 (it is not necessarily an integer), but the average value of preferable l is 0-3. When the value of l exceeds the upper limit value, when the resin composition is made as a compound of the general formula (I), the viscosity of the composition becomes too high and coating may not be performed well, or alkali solubility can not be sufficiently imparted and alkali The developability becomes very bad.

  Next, the compound of the general formula (II) is reacted with acrylic acid or methacrylic acid or both of them, and the resultant reaction product having a hydroxy group is a polybasic acid dicarboxylic acid (or tricarboxylic acid) and tetracarboxylic acid. At least one of each of the acids is reacted to obtain an epoxy (meth) acrylate acid adduct (I). The epoxy (meth) acrylate acid adduct (I) has both an ethylenically unsaturated double bond and a carboxyl group, so that it has excellent photocurability, good developability, and patterning characteristics for an alkali-developable photosensitive resin composition. To give a good black matrix.

  As the dicarboxylic acids used for the epoxy (meth) acrylate acid adduct of the general formula (I) of the present invention, a chain hydrocarbon dicarboxylic acid or an acid anhydride thereof, an alicyclic dicarboxylic acid or an acid anhydride thereof, an aroma Family dicarboxylic acids and their acid anhydrides are used. Here, as the chain hydrocarbon dicarboxylic acid or acid anhydride thereof, for example, succinic acid, acetyl succinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citra malic acid, malonic acid, glutaric acid, citric acid, There are compounds such as tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid and the like, and further, dicarboxylic acids having an optional substituent introduced therein or an acid anhydride thereof may be used. Moreover, as an alicyclic dicarboxylic acid or its acid anhydride, for example, there are compounds such as hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, norbornane dicarboxylic acid, etc., and further introduction of an optional substituent It may be dicarboxylic acids or their acid anhydrides. Further, examples of the aromatic dicarboxylic acid and the acid anhydride thereof include compounds such as phthalic acid and isophthalic acid, and further, dicarboxylic acids into which any substituent is introduced or an acid anhydride thereof may be used. Moreover, although tricarboxylic acids may be used instead of dicarboxylic acids, for example, trimellitic acid or its acid anhydride can be mentioned.

  Moreover, as tetracarboxylic acids utilized for the epoxy (meth) acrylate acid adduct of general formula (I) of this invention, chain hydrocarbon tetracarboxylic acid or its acid dianhydride, alicyclic tetracarboxylic acid or The acid dianhydride or an aromatic polyvalent carboxylic acid or its acid dianhydride is used. Here, as the chain hydrocarbon tetracarboxylic acid or its acid dianhydride, there are, for example, butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid and the like, and further tetracarboxylic acids having a substituent introduced therein. Or the acid dianhydride may be sufficient. Further, examples of the alicyclic tetracarboxylic acid or acid dianhydride thereof include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptan tetracarboxylic acid norbornane tetracarboxylic acid, etc. May be substituted tetracarboxylic acids or their acid dianhydrides. Furthermore, as the aromatic tetracarboxylic acid and the acid dianhydride thereof, for example, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid or the acid dianhydride thereof may be mentioned, and further, substitution may be carried out It may be a tetracarboxylic acid introduced with a group or its acid dianhydride.

  The molar ratio of (a) to (b) is the ratio of (a) dicarboxylic acids to (b) tetracarboxylic acids used in the epoxy (meth) acrylate adduct of the general formula (I) of the present invention. The range is 1:10 to 10: 1, preferably 1: 5 to 1: 1. When the use ratio of the dicarboxylic acid and the tetracarboxylic acid in the epoxy (meth) acrylate acid adduct of the general formula (I) deviates from the above range, the optimum molecular weight can not be obtained, and the alkali developability, light transmittance, heat resistance, and resistance It is not preferable because the solvent property, pattern shape and the like deteriorate. The larger the proportion of tetracarboxylic acids used, the higher the alkali solubility and the higher the molecular weight.

  The epoxy (meth) acrylate acid adduct of the general formula (I) used in the present invention preferably has a weight average molecular weight (Mw) of between 2000 and 10000, and between 3000 and 7000. Is particularly preferred. If the weight average molecular weight (Mw) is less than 2000, the adhesion of the pattern during development can not be maintained, pattern peeling occurs, and if the weight average molecular weight (Mw) exceeds 10000, the adhesion to the glass substrate is high. The residual film and the residual film of the pattern portion are easily left. Furthermore, as for the epoxy (meth) acrylate acid adduct of general formula (I), it is desirable for the acid value to be in the range of 30-200 KOHmg / g. If this value is less than 30 KOHmg / g, alkaline development may not be successful, or special developing conditions such as strong alkali are required, and if it exceeds 200 KOHmg / g, the alkali developer will accelerate penetration and peeling development will occur. Is not preferable.

  The epoxy (meth) acrylate acid adduct of the general formula (I) used in the present invention can be produced by the above-mentioned steps according to a known method, for example, the method described in Patent Document 1. First, as a method of reacting an unsaturated group-containing monocarboxylic acid with an epoxy compound of the general formula (II), for example, an epoxy group of the epoxy compound and an equimolar amount of unsaturated group-containing monocarboxylic acid are added to a solvent In the presence of a catalyst (triethylbenzylammonium chloride, 2,6-diisobutylphenol or the like), there is a method of heating and stirring at 90 to 120 ° C. with air blowing to cause a reaction. Next, as a method of reacting an acid anhydride with a hydroxyl group of an epoxy acrylate compound which is a reaction product, predetermined amounts of an epoxy acrylate compound, an acid dianhydride and an acid monoanhydride are added to a solvent to The reaction is carried out by heating and stirring at 90 to 130 ° C. in the presence of tetraethylammonium chloride, triphenylphosphine and the like).

  Moreover, the compounding quantity of the said epoxy (meth) acrylate acid adduct [component (A3)] in the (A) pigment dispersion of this invention is 2-20 mass%, Preferably it is 5-15 mass%. If the compounding amount of the epoxy (meth) acrylate acid adduct is less than the above lower limit, the stability of the mill base is deteriorated and the resistance value is lowered, which is not preferable. If the above upper limit is exceeded, the viscosity of the mill base is increased and the coatability is poor and smooth It is not preferable because the nature is reduced.

  The solvent (A4) of the present invention includes alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol and propylene glycol, terpenes such as α- or β-terpineol, etc., acetone, methyl ethyl ketone, cyclohexanone, N- Ketones such as methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether , Glycol ethers such as 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 A single or mixed solvent such as acetic acid esters such as glycol monoethyl ether acetate may be mentioned.

  The pigment dispersion (A) of the present invention is a dye after the epoxy (meth) acrylate acid adduct of the general formula (I) and other components added as needed are added and mixed and dissolved in an optimum amount of solvent. Add coated carbon black and add media such as glass beads and zirconia beads, then disperse with paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, ultrasonic wave etc. singly or in combination. Obtained by By this dispersion treatment, the dye-coated carbon black is micronized and the dispersion is stabilized, so that the coating characteristics of the photosensitive resin composition using the pigment dispersion can be improved, and the light shielding ability of the black matrix can be improved and the carbon black It is advantageous to increase resistance when using a light shielding material having such conductivity.

  The average secondary particle diameter of the dye-coated carbon black after dispersion treatment of the (A) pigment dispersion is preferably 50 to 200 nm, preferably 80 to 150 nm. The average secondary particle size here is, for example, a value of the average particle size obtained by a known laser Doppler type particle size measurement device. The viscosity of the (A) pigment dispersion is 3.0 to 100.0 mPa · s, preferably 3.0 at a liquid temperature of 25 ° C. of the (A) pigment dispersion, as determined from a known cone-plate viscometer. It is preferable to adjust to -20.0 mPa · s.

  Next, as the unsaturated group-containing alkali-soluble resin (B), it is more preferable to use the epoxy (meth) acrylate acid adduct of the general formula (I) which is the component (A3). In addition to this, for example, it is a photosensitive group using a compound having two or more glycidyl ether groups such as a phenol novolac epoxy compound and a cresol novolac epoxy compound instead of an epoxy compound derived from bisphenols. An unsaturated group-containing alkali-soluble resin derivatized into a compound having an unsaturated double bond and an acidic functional group such as a carboxyl group which brings about alkali solubility can be used. The unsaturated group-containing alkali-soluble resin (B) may be used alone or in combination of two or more. For the high light-shielding and high-resistance photosensitive resin composition, it is preferable to use the same component as the co-dispersed resin (A3) of the (A) pigment dispersion.

  Examples of the photopolymerizable monomer having an ethylenically unsaturated bond of component (C) include hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 2-ethylhexyl (meth) acrylate. (Meth) acrylic esters, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) Acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol (Tetra) (meth) acrylate, dipentaerythritol tetra (meth) acrylate, glycerol (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, or dipentaerythritol hexa (meth) acrylate, sorbitol hexa ( (Meth) acrylates, alkylene oxide-modified hexa (meth) acrylates of phosphazenes, caprolactone-modified dipentaerythritol hexa (meth) acrylates and the like (meth) acrylates can be mentioned, and one or more of these may be used can do. Moreover, it is preferable that the photopolymerizable monomer which has the said ethylenically unsaturated bond has 3 or more of photopolymerizable groups, and can use what can bridge | crosslink molecules of unsaturated group containing alkali-soluble resin. In addition, the photopolymerizable monomer which has an ethylenically unsaturated bond of (C) component does not have a free carboxy group.

  In the photosensitive resin composition of the present invention, the blending ratio of the unsaturated group-containing resin ((A3) + (B)) component to the component (C) (each component is the amount of solid content excluding the solvent) ((A3) + (B)): (C) is preferably 20:80 to 90:10, preferably 40:60 to 80:20. If the blending ratio of the ((A3) + (B)) component is low, the cured product after photocuring becomes brittle, and the acid value of the coating film is low in the unexposed area, so the solubility in an alkaline developer decreases. As a result, there is a problem that the pattern edge is not rattled and sharpened. On the other hand, if the amount is too large, the proportion of the photoreactive functional group in the resin is small and the formation of a crosslinked structure is not sufficient. Furthermore, the acid value of the resin component is too high, and the solubility in an alkaline developer in the exposed area is high. As a result, there may be a problem that the formed pattern may be thinner than the target line width, or the pattern may be easily lost.

  As a photoinitiator of (D) component, one or more types of initiators can be used. In addition, the photoinitiator as used in the field of this invention is used in the meaning containing a sensitizer.

  Examples of usable photopolymerization initiators include acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone and p-tert-butylacetophenone , Benzophenones such as benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, etc. Benzoin ethers such as benzyl, 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-diphenylbiimidazole, 2 -(o-methoxyphenyl)- Biimidazole compounds such as 4,5-diphenylbiimidazole and 2,4,5-triarylbiimidazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl- Halomethylthiazole compounds such as 5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole, etc. 2,4,6-Tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6- Bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl) -4 , 6-Bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloroR methyl) -1,3,5-triazine, 2- (4- (4-methoxynaphthyl) -1,5-triazine Methoxystyryl) -4,6-bi (Trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4 Halomethyl-S-triazine compounds such as -methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 1,2-octanedione, 1- [4- (phenylthio) phenyl] -, 2- (o-benzoyloxime), 1- (4-phenylsulfanylphenyl) butane-1,2-dione-2-oxime-o-benzoate, 1- (4-methylsulfanylphenyl) butane-1, O-Acyloxime compounds such as 2-dione-2-oxime-o-acetate, 1- (4-methylsulfanylphenyl) butan-1-one oxime-o-acetate, etc., benzyl dimethyl ketal, thioxanthone, 2-chlorothio Xanson, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxa Sulfur compounds such as nsonson, anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, etc., organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, etc. And thiol compounds such as 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole, and tertiary amines such as triethanolamine and triethylamine.

  The amount of the photopolymerization initiator of component (D) used is 2 to 2 parts by mass based on the total of 100 parts by mass of each of the unsaturated group-containing alkali-soluble resin of (A3) and (B) and each component of (C) photopolymerizable monomer. It may be 60 parts by mass, preferably 10 to 50 parts by mass. When the proportion of the component (D) is small, the photopolymerization speed is low and the sensitivity is lowered. On the other hand, when the proportion is too large, the sensitivity is too high and the pattern line width becomes thicker than the pattern mask. On the other hand, there may be a problem that a faithful line width can not be reproduced, or the pattern edge is not rattling and sharp.

  As the solvent of the component (E), any solvent exemplified as the component (A4) can be suitably used, and it is preferable to include the same solvent as at least the component (A4). In addition, two or more types of solvents can also be used.

  The photosensitive resin composition for black matrix of the present invention comprises the above-mentioned (A) pigment dispersion, (B) unsaturated group-containing alkali-soluble resin, (C) photopolymerizable monomer having an ethylenically unsaturated bond, (D) ) A photopolymerization initiator and (E) a solvent are included as essential components, but if necessary, it is separately used for a curing accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a leveling agent, an antifoaming agent, and a dispersing agent. And additives such as surfactants can be blended. As a thermal polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butyl catechol, phenothiazine etc. can be mentioned, As a plasticizer, dibutyl phthalate, dioctyl phthalate, tricresyl phosphate etc. can be mentioned, and filling Examples of the material include glass fiber, silica, mica, and alumina. Examples of the antifoaming agent and the leveling agent include silicon-based, fluorine-based, and acrylic-based compounds.

  The photosensitive resin composition of the present invention contains the above components (A) to (E) as main components, but the solid components including monomers etc. which become solid components after curing except for the solvent It is desirable that the total amount of components excluding the solvent of each component of (D) is 70% by mass or more, preferably 80% by mass, more preferably 90% by mass or more. The amount of solvent varies depending on the target viscosity, but a range of 20 to 90% by mass is desirable. The solid content can be measured by heating the solution of the photosensitive resin composition at 160 ° C. for 2 hours to remove the solvent.

  The content of the dye-coated carbon black of the component (A1) is preferably 40% by mass or more in the solid content of the photosensitive resin composition. Preferably, it is in the range of 45 to 60% by mass, more preferably 50 to 55% by mass. If the content of the component (A1) is low, the light shielding property will not be sufficient, the film thickness must be increased to obtain a desired contrast, and it is difficult to obtain the surface smoothness of the black matrix. Conversely, if 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 reduced, and the content of the photosensitive resin to be a binder is also reduced. There is a possibility that the problem of reduction in the development adhesion and the adhesion with the glass substrate can not be sufficiently imparted, or there is an undesirable problem that the alkali solubility is insufficient and good development characteristics can not be obtained.

  The coating film of the present invention can be obtained, for example, by applying a solution of the photosensitive resin composition for the black resist to a substrate or the like, drying it, and irradiating it with light (including ultraviolet light and radiation) to cure it. can get. By providing a portion to be exposed to light and a portion not to be exposed, only the portion to be exposed to light is cured, and the other portion is dissolved with an alkaline solution to obtain a coating having a desired pattern.

  Next, the manufacturing method of the color filter using the photosensitive resin composition for black resists of this invention is demonstrated. First, on the surface of a substrate, a photosensitive resin composition for a black resist is applied to the substrate, and a light shielding layer (black matrix) is formed so as to partition a portion to form a pixel. Next, a liquid photosensitive resin composition (ink) in which, for example, a red pigment is dispersed is applied onto the substrate, and then prebaked to evaporate the solvent to form a coating film. Then, the coating film is exposed to light through a photomask, and then developed using an alkaline developer to dissolve and remove unexposed portions of the coating film, and then post-baked to obtain a predetermined red pixel pattern. Form a pixel array arranged in an array. Thereafter, using the ink in which the green or blue pigment is dispersed and applying, pre-baking, exposing, developing and post-baking each liquid composition in the same manner as the red pixel array, the green pixel array and blue By sequentially forming the pixel array on the same substrate, the pixel arrays of three primary colors of red, green and blue are disposed on the substrate, and further, a liquid composition of a photosensitive resin containing no coloring agent as a protective film thereon. The product is coated, prebaked, exposed, developed and post-baked in the same manner as described above to obtain a color filter having a protective film formed thereon.

  When the liquid composition of the photosensitive resin composition for black resist of the present invention is applied to a substrate, a roller coater, a land coater, a slit coater, a spin coater, a screen printing method, in addition to a known solution dipping method and spraying method. Alternatively, any method such as inkjet printing can be adopted. By applying these methods to a desired thickness, a film is formed by removing the solvent (pre-baking). Prebaking is performed by heating with an oven, a hot plate or the like, vacuum drying, or a combination thereof. The heating temperature and heating time in prebaking are suitably selected according to the solvent to be used, for example, are performed at the temperature of 80-120 degreeC for 1 to 10 minutes.

  As radiation used for exposing and curing the photosensitive resin composition when producing a color filter, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like can be used. Radiation having a wavelength in the range of 250 to 450 nm is preferred. Next, although alkali development is performed, examples of a developer suitable for alkali development include aqueous solutions of carbonates of alkali metals and alkaline earth metals, and aqueous solutions of hydroxides of alkali metals, and the like. It is preferable to develop at a temperature of 20 to 30 ° C. using a weak alkaline aqueous solution containing 0.05 to 10% by mass of carbonates such as sodium carbonate, potassium carbonate and lithium carbonate, and commercially available developing machines and ultrasonic cleaners Fine images can be precisely formed using After alkali development, washing is usually carried out. As the development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid buildup) development method or the like can be applied. The development conditions are preferably 10 to 120 seconds at normal temperature.

  After development in this manner, heat treatment (post-baking) is performed at a temperature of 180 to 250 ° C. and a condition of 20 to 100 minutes. This post-baking is performed for the purpose of enhancing the adhesion between the patterned coating film and the substrate. This is performed by heating with an oven, a hot plate or the like as in the pre-baking. The patterned coating film of this invention is formed through each process by the above photolithographic method.

  As a substrate used when forming a color filter provided with pixels and a black matrix, for example, a transparent electrode such as ITO or gold on glass, a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether sulfone etc.) What is vapor-deposited or patterned is used. In addition, these substrates can be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

  Next, the method for producing a 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 way of examples, but the present invention is limited to these examples. It is not a thing.

Preparation Example 1
Preparation of Dye-Coated Carbon Black (1)
A slurry 10 L was prepared by mixing 1000 g of carbon black (TPX-1099: manufactured by Cabot) with water to prepare a slurry, stirred at 95 ° C. for 1 hour, allowed to cool, and washed with water. The mixture was again mixed with water to prepare 10 liters of slurry, 42.9 g of 70% nitric acid was added, and the mixture was stirred at 40 ° C. for 4 hours. The mixture was allowed to cool, washed with water, and mixed with water again to prepare 10 L of slurry. 769.2 g of a 13% aqueous solution of sodium hypochlorite was added and stirred at 40 ° C. for 6 hours. The mixture is allowed to cool, washed with water and mixed with water again to prepare 10 L of slurry, 38.1 g of 38.4% pure dye (Direct Deep BLACK) is added and the mixture is stirred at 40 ° C. for 1 hour, and then added. 10.1 g of aluminum sulfate was added and stirred at 40 ° C. for 1 hour. The mixture was allowed to cool, then washed with water and filtered and dried to obtain dye-coated carbon black.

Measurement of Carboxyl Group Amount The acidic functional group weight (carboxyl group weight) of the obtained dye-coated carbon black was measured as follows according to the method described in JP-A-2000-248197.

10 g of dye-coated carbon black is weighed and reacted by shaking in 50 ml of 0.1 N aqueous sodium hydrogen carbonate solution for 1 hour and then filtered, and 20 ml of supernatant liquid of filtrate is collected and treated with 0.01 N aqueous hydrochloric acid solution Titrated. The amount of carboxyl groups was determined according to the following formula as the amount of mmol (mmol / g) in 1 g of carbon black.
Carboxyl group content = (50/20 × 0.01 × (titrate−empty titer)) / carbon black sample mass The obtained carboxyl group content of the dye-coated carbon black was 53.9 mmol / g.

Preparation Example 2
<Preparation of dye-free carbon black>
A dye-uncoated carbon black was obtained in the same manner as in Preparation Example 1 except that the dye coating and the lake treatment with aluminum sulfate were not performed.

Preparation Example 3
Preparation of Resin-Coated Carbon Black
Cyclohexanone was added to polyvinyl chloride (Nissan Chemical Co., Ltd. Nissan Vinyl E-430) and heated to about 90 ° C. to dissolve it, thereby preparing a cyclohexanone solution containing 10% by mass of polyvinyl chloride. On the other hand, carbon black (furness black, manufactured by Mitsubishi Chemical Corporation # 3050) and water were mixed and vigorously stirred to prepare a uniform suspension containing 6% by mass of carbon black. Next, the suspension was added to the cyclohexanone solution with stirring to transfer the carbon black of the aqueous phase to the solvent phase. Subsequently, water separated from carbon black was removed by decantation, and then kneaded for about 5 minutes with a roll mill having two rolls heated to 80 to 120 ° C. to obtain a resin composition. Next, the resin composition is cut into a sheet by a heating roll, passed through a roll mill having two rolls at normal temperature, pulverized to a size of about 30 mm or less, and then transferred into water, at a speed of about 3000 rpm. The mixture was stirred for about 3 minutes and crushed and sized so as to be particles having an average secondary particle size of 0.1 to 3 mm, to obtain a sized product. The sized product was dried at 80 to 150 ° C. to obtain resin-coated carbon black.

Preparation Example 4
<(A) -1 Preparation of pigment dispersion of the present invention>
An epoxy acrylate having 600 g of the dye-coated carbon black (component A1) obtained in Preparation Example 1, 93.2 g of BYK-167 (manufactured by Bick Chemie Japan) as a component A2 and a fluorene skeleton as a component A3. A bead mill disperses 378 g of a propylene glycol monomethyl ether acetate solution of an acid adduct (resin solid concentration = 56.5% by mass, "V 259 ME" manufactured by Nippon Steel Sumikin Chemical Co., Ltd.) and 1328.8 g of solvent propylene glycol monomethyl ether acetate as A4 component. Thus, a pigment dispersion (A) -1 of the present invention was obtained. The average secondary particle diameter of the dye-coated carbon black of the obtained pigment dispersion (A) -1 was 110 nm.

Preparation Example 5
<Preparation of (A) -2 Comparative pigment dispersion (using dye-uncoated carbon black)>
A pigment dispersion for comparison (A) -2 was obtained by treating in substantially the same manner as in Preparation Example 4 except that dye-coated carbon black obtained in Preparation Example 2 was used instead of dye-coated carbon black.

Preparation Example 6
<Preparation of (A) -3 Comparative Pigment Dispersion (Use of Resin-Coated Carbon Black)>
A pigment dispersion for comparison (A) -3 was obtained in substantially the same manner as in Preparation Example 4 except that the resin-coated carbon black obtained in Preparation Example 3 was used instead of dye-coated carbon black.

[Reference Example 7]
<(A) -4 Preparation of Comparative Pigment Dispersion (Without Dispersion Resin)>
The pigment dispersion for comparison was prepared in the same manner as in Preparation Example 4 except that a propylene glycol monomethyl ether acetate solution of an acid adduct of an epoxy acrylate having a fluorene skeleton was not added, and 1706.8 g of a solvent propylene glycol monomethyl ether acetate was used. Body (A) -4 was obtained.

[(B)-(E) component to be used and additive (F)-(G) component]
<(B) -1 unsaturated group-containing alkali-soluble resin having a general formula (I) structure>
Propylene glycol monomethyl ether acetate solution of acid adduct of epoxy acrylate having fluorene skeleton (resin solid concentration = 56.5% by mass, "V 259 ME" manufactured by Nippon Steel Sumikin Chemical Co., Ltd.)
<(B) -2 unsaturated group-containing alkali-soluble resin other than the general formula (I) structure>
Propylene glycol monomethyl ether acetate solution of N-phenyl maleimide / acrylic acid / styrene copolymer (resin solid concentration = 35.5 mass%, N-phenyl maleimide: acrylic acid: styrene = 19: 22: 59 mol%, weight Average molecular weight 9000, acid number 80)
<(C) Photopolymerizable Monomer Having Ethylenically Unsaturated Bond>
Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd. "KAYARAD-DPHA")
<(D) Photopolymerization initiator>
Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime) ("IRGACURE OXE02" manufactured by BASF Corporation)
<(E) -1 Solvent 1>
Propylene glycol monomethyl ether acetate <(E) -2 solvent 2>
Cyclohexanone <(F) Silane Coupling Agent>
3-Methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical "KBM-503")
<(G) surfactant>
Megafuck F475 (made by DIC Corporation)

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

Comparative Example 1
A photosensitive resin composition for comparison with a black matrix was prepared in substantially the same manner as in Example 1 except that (A) -2 was used instead of the pigment dispersion (A) -1.

Comparative Example 2
The procedure of Example 1 was repeated except that pigment dispersion (A) -1 was replaced by (A) -3, except that the compounding ingredients were as shown in Table 1, to which the sensitivity for comparison with a black matrix was applied. Resin composition was prepared.

Comparative Example 3
The procedure is substantially the same as Example 1 except that (B) -2 is used instead of the unsaturated group-containing alkali-soluble resin (B) -1, except that the compounding ingredients are as shown in Table 1, for comparison A photosensitive resin composition for black matrix was prepared.

Comparative Example 4
The procedure of Example 1 was repeated except that (A) -4 was used instead of the pigment dispersion (A) -1, except that the formulation components were as shown in Table 1. Resin composition was prepared.

[Evaluation]
Evaluation described below was performed using the photosensitive resin composition of Example 1 and Comparative Examples 1-4. The evaluation results are shown in Table 2.

<Evaluation of development characteristics (pattern line width, pattern linearity, resolution)>
Each photosensitive resin composition obtained above is coated on a 125 mm × 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking becomes 1.0 μm, and it is at 90 ° C. Prebaked for 1 minute. Thereafter, the exposure gap is adjusted to 100 μm, and the line / space = 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 on the dried coating A photo mask was placed, and an ultraviolet ray of 80 mJ / cm ² was irradiated by an ultra-high pressure mercury lamp with an i-line illuminance of 30 mW / cm ² to carry out a photocuring reaction of the photosensitive portion.

Next, the exposed coated plate was subjected to a developing time (break time = BT) at which a pattern starts to appear at a shower developing pressure of 1 kgf / cm ^{2 in} a 0.08% aqueous solution of potassium hydroxide at 25 ° C., +10 seconds, +20. After developing for 2 seconds, spray washing with 5 kgf / cm ² pressure is performed to remove the unexposed area of the coating to form a pixel pattern on the glass substrate, and then using a hot air drier at 230 ° C. for 30 minutes The line width, pattern linearity and resolution with respect to the mask width of 10 μm lines after post-baking were evaluated. In addition, each evaluation method is as follows.
Pattern line width: A pattern line width of 10 μm in mask width was measured using a length measurement microscope (“XD-20” manufactured by Nikon Corporation).
Pattern linearity: A 10 μm mask pattern after post-baking is observed microscopically, and those with no peeling on the substrate and no jaggedness at the pattern edge are recognized as ○, those with some recognition are Δ, those with throughout It evaluated as x.
Resolution: Among the mask patterns of 2 μm, 4 μm, 5 μm, 6 μm, 8 μm, 10 μm and 20 μm, the minimum pattern size remaining on the substrate was taken as the resolution.

<Evaluation of OD>
Each photosensitive resin composition obtained above is coated on a 125 mm × 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking becomes 1.0 μm, and it is at 90 ° C. Prebaked for 1 minute. After that, the exposure gap is adjusted to 100 μm, a 15 mm × 15 mm aperture is covered with a negative photomask, and 80 mJ / cm ² of ultraviolet light is applied with an i-line illuminance of 30 mW / cm ^2. Irradiation was performed to carry out a photocuring reaction of the photosensitive part.

Next, this exposed coated plate was developed at a shower development pressure of 1 kgf / cm ^{2 in} a 0.08% aqueous potassium hydroxide solution at 25 ° C., for a development time of +20 seconds from the development time (break time = BT) at which a pattern starts to appear After that, spray water washing at 5 kgf / cm ² pressure is performed to remove the unexposed area of the coating film to form a pixel pattern on the glass substrate, and then heat post-baked for 30 minutes at 230 ° C. using a hot air dryer. The OD of the pixel formed in the 15 mm × 15 mm opening was evaluated using a Macbeth transmission densitometer.

<Evaluation of surface resistance>
Each photosensitive resin composition obtained above is coated on a 125 mm × 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking becomes 1.0 μm, and it is at 90 ° C. Prebaked for 1 minute. Thereafter, ultraviolet light of 80 mJ / cm ² was irradiated without using a photo mask with an ultra-high pressure mercury lamp with an i-line illuminance of 30 mW / cm ² to carry out a photocuring reaction. Next, a development time at which a pattern starts to appear when the exposed coated plate is covered with a photomask at a shower development pressure of 1 kgf / cm ^{2 in} a 0.08% aqueous solution of potassium hydroxide at 25 ° C. (break time = BT) Then, after development for +20 seconds, spray water washing at 5 kgf / cm ² pressure was performed, and after heat post baking at 230 ° C. for 30 minutes and 180 minutes using a hot air drier, the surface resistance was measured.

<Evaluation of adhesion to glass substrate>
Each photosensitive resin composition obtained above is coated on a 125 mm × 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking becomes 1.0 μm, and it is at 90 ° C. Prebaked for 1 minute. Thereafter, solid exposure was performed at 80 mJ / cm ² with an i-line illuminance of 30 mW / cm ^{2 with} an ultra-high pressure mercury lamp without using a negative photomask, and heat post-baked for 30 minutes at 230 ° C. using a hot air dryer. And about the post-baking board | substrate obtained above, the adhesion strength with a glass substrate was evaluated as follows by the evaluation method according to the three-point bending adhesion test method of JISK6856-1994.

  Each of the post-baked substrate and the glass substrate (Corning 1737) not coated with the resin composition was cut into a strip of 20 mm × 63 mm to prepare a test piece. The overlapping width of the post-baked coated film plate and the glass substrate not coated with the photosensitive resin composition via a certain amount of a sealing agent epoxy-based adhesive (Structbond XN-21s (made by Mitsui Chemicals)) The two substrates (specimen) were pasted together so that the length of the sample was 8 mm. The shape of the sealant epoxy-based adhesive when it was superposed was circular and the diameter was about 5 mm. Thereafter, the stacked test pieces were subjected to prebaking at 90 ° C. for 20 minutes, followed by post-baking at 150 ° C. for 2 hours to prepare three-point bending test pieces. Furthermore, 20 mm × 63 mm uncoated glass pieces were also bonded in the same manner as described above to prepare a sample for comparison test.

  In the test piece obtained above, the coated plate and the opposite substrate (substrate without coating) or the glass substrate for comparison test not coated are supported by two supports so that the overlapping portion is centered (2 The length of the support of the point is 3 cm), and weight is applied at a speed of 1 mm / min from “Octech Tech's“ UCT-100 ”from directly above to directly below the overlapping portion, and observation of the peeled surface And the load at that time was read, it was divided by the application area of the sealant epoxy adhesive, and the load per unit area was taken as the adhesive strength. Moreover, after performing PCT (pressure cooker test) under the conditions of 121 ° C., 100% RH, 2 atm, and 5 hours, the same adhesion strength test was performed to evaluate the adhesion strength before and after PCT. The adhesion strength of each composition was shown as a relative value when the adhesion strength of the glass which has not apply | coated the resist in before and behind PCT is set to 100, respectively. 70 or more was taken as ○ and less than 70 as x before and after PCT.

  As is clear from Table 2, the photosensitive resin composition for the black matrix of Example 1 of the present invention has development characteristics of pattern line width, pattern linearity and resolution as compared with the photosensitive resin composition of each comparative example. In addition to exhibiting excellent performance in any of the above, the surface resistance and the adhesion strength with the glass substrate were also excellent. Specifically, when dye-uncoated carbon black is used as in Comparative Example 1, development characteristics such as pattern linearity and resolution are not problematic, but necessary characteristics in surface resistance and adhesion to the glass substrate were not obtained. . When resin-coated carbon black was used as in Comparative Example 2, when the light shielding degree and the surface resistance conditions were satisfied, the development characteristics and the adhesion strength with the glass substrate were not sufficient. When a resin having a structure other than the general formula (I) is used as the unsaturated group-containing alkali-soluble resin blended with the pigment dispersion as in Comparative Example 3, the development characteristics are not sufficient, and the surface resistance decreases after heat treatment. It was seen. When the photosensitive resin composition using the pigment dispersion which does not co-disperse resin (A3) of General formula (I) at the time of preparation like Comparative Example 4 was used, the fall of the surface resistance after heat processing was seen.

  As described above, when the carbon black dispersion for black matrix of the present invention is used for the photosensitive resin composition for black matrix, it is possible to form a fine line pattern having high resistance and excellent developing characteristics and adhesion to a glass substrate. When this is applied to a color filter, it becomes possible to create a highly light-shielding, high-resistance, highly reliable black matrix. Therefore, the ink is used for various multicolor displays such as color liquid crystal display devices, color facsimiles, image sensors, and optical devices, and used for color filters having a black matrix, television, video monitor, computer display, etc. It is extremely useful when In particular, it is useful for small and medium size high definition displays for smartphones.

Claims (13)

The following (A1) to (A4) components,
(A1) Dye-coated carbon black obtained by coating the surface of carbon black having at least one type of acidic functional group with a dye on the surface that has been subjected to oxidation treatment with an oxidizing agent in advance, and then laked with metal or metal salt ,
(A2) Dispersant,
(A3) unsaturated group-containing alkali-soluble resin having a structure of the following general formula (I),
(A4) A pigment dispersion having an organic solvent is prepared in advance so that the compounding amount of (A1) dye-coated carbon black in the (A) pigment dispersion is 15 to 35% by mass, and then it is used as an essential component The following (B) to (E) components,
(B) Alkali-soluble resin containing unsaturated group,
(C) a photopolymerizable monomer having an ethylenically unsaturated bond,
(D) Photopolymerization initiator,
(E) A method for producing a photosensitive resin composition for a color filter black matrix, which comprises mixing a blending component containing an organic solvent and the pigment dispersion (A).

[The general formula (I) is a product of (a) dicarboxylic acid or tricarboxylic acid or any acid of the reaction product of (meth) acrylic acid and an epoxy compound having two glycidyl ether groups derived from bisphenols. Epoxy (meth) acrylate acid obtained by reacting an anhydride and (b) tetracarboxylic acid or its acid dianhydride so that the molar ratio of (a) to (b) is 1:10 to 10: 1 It is an additive. Here, 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 represents 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, 9-fluorenyl group or a direct bond, X represents a tetravalent carboxylic acid residue, and Y ₁ and Y ₂ are each independently 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. ] The following (A1) to (A4) components,
(A1) Dye-coated carbon in which the surface of carbon black having at least one kind of acidic functional group is coated with a dye after being subjected to oxidation treatment with an oxidizing agent in advance, and then laked with a metal or metal salt black,
(A2) Dispersant,
(A3) unsaturated group-containing alkali-soluble resin having a structure of the following general formula (I),
( A) a pigment dispersion prepared in advance such that the compounding amount of (A1) dye-coated carbon black in the (A) pigment dispersion has an organic solvent (A4) of 15 to 35% by mass ; The following components (B) to (E) as components,
(B) Alkali-soluble resin containing unsaturated group,
(C) a photopolymerizable monomer having an ethylenically unsaturated bond,
(D) Photopolymerization initiator,
(E) A photosensitive resin composition for a color filter black matrix, which is mixed with a compounding component containing an organic solvent.

[The general formula (I) is a product of (a) dicarboxylic acid or tricarboxylic acid or any acid of the reaction product of (meth) acrylic acid and an epoxy compound having two glycidyl ether groups derived from bisphenols. Epoxy (meth) acrylate acid obtained by reacting an anhydride and (b) tetracarboxylic acid or its acid dianhydride so that the molar ratio of (a) to (b) is 1:10 to 10: 1 It is an additive. Here, 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 represents 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, 9-fluorenyl group or a direct bond, X represents a tetravalent carboxylic acid residue, and Y ₁ and Y ₂ are each independently 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. ] The photosensitive resin composition for color filter black matrices of Claim 2 whose content rate of the dye in (A1) dye-coated carbon black is 0.5-10 mass%.   The photosensitive resin composition for a color filter black matrix according to claim 2 or 3, wherein the dye-coated carbon black is a dye in which the dye is an anionic or non-ionic dye. The photosensitive resin composition for a color filter black matrix according to claim 2 or 3 , wherein the dye-coated carbon black is a dye of a dark color type. The photosensitive resin composition for a color filter black matrix according to claim 2 , wherein the metal or metal salt is aluminum, magnesium, calcium, strontium, barium or manganese or a salt thereof. The acidic functional group is a hydroxyl group, oxo group, hydroperoxy group, carbonyl group, carboxyl group, peroxycarboxylic acid group, aldehyde group, ketone group, nitro group, nitroso group, amido group, imide group, sulfonic acid group, sulfinic acid The photosensitive resin composition for a color filter black matrix according to claim 2 , which is a group, a sulfenic group, a thiocarboxylic acid group, a chlorosil group, a chloryl group, a perchloryl group, an iodosyl group or a iodol group. (A3) the amount of the unsaturated group-containing alkali-soluble resin, 2 to 20 wt%, a color filter black matrix photosensitive resin composition according to claim 2. The photosensitive resin composition for color filter black matrices of Claim 2 whose compounding quantity of (A1) dye-coated carbon black in solid content of the photosensitive resin composition is 45-60 mass%. The photosensitive resin composition for color filters according to claim 2 , wherein at least a part of the component (B) is an unsaturated group-containing alkaline resin represented by the general formula (I). It claims 2 to a coating film formed by curing a 10 color filter black matrix for a photosensitive resin composition. A black matrix obtained by coating the photosensitive resin composition for a black matrix according to any one of claims 2 to 10 , forming a film, photocuring it at a selective position, and developing with an alkaline developer. A color filter on which the black matrix according to claim 12 is formed.